Crown ether amines and methods of use
By preparing the crown ether material reacts with the macromolecular support to form C-N or C=N bonds, the problem of low binding efficiency of crown ether material in non-polar solvents in the prior art is solved, and efficient and selective removal of metal ions in the solution is achieved.
Patent Information
- Application Number
- CN202380082738.4
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Priority Date
- 2022-11-04
- Filing Date
- 2023-10-20
- Publication Date
- 2025-07-11
AI Technical Summary
In the prior art, there is a lack of efficient crown ether-based materials and preparation methods and their methods, and it is difficult to effectively bind specific cations and perform selective metal ions removal in non-polar solvents.
The material containing crown ether is prepared, and the selective removal of metal ions is achieved by reacting benzo crown ether or dibenzo crown ether with an aminobenzoic acid compound to form crown ether and reacting with a macromolecular carrier such as a film, fiber medium or polymer coating to form a C-N bond or C=N bond.
It achieves efficient binding of cations in non-polar solvents, selectively removes metal ions in the solution, such as sodium, magnesium, calcium, potassium, etc., and the removal efficiency can reach 50-70%.
Smart Images
Figure CN120303256A_ABST
Abstract
Description
Background Art
[0001] Crown ethers are cyclic organic molecules containing repeating units based on oxygen and carbon. Crown ethers are known to stably bind specific 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. Thus, complexes containing crown ethers and cations can be dissolved in nonpolar solvents. For this reason, crown ethers can be useful in phase transfer catalysis.
[0002] Due to the high utility of crown ether-based compounds, there is still a need to develop materials containing crown ether-based compounds and new and efficient ways to prepare such materials. The present invention provides such materials and methods of preparation. Additional benefits and aspects of the present invention will be apparent from the disclosure provided herein. Summary of the Invention
[0003] The present invention provides a material comprising: (i) a crown ether of formula (I):
[0004]
[0005] (ii) a crown ether of formula (II):
[0006]
[0007] or a salt thereof, wherein each m is independently an integer from 1 to 8, each denotes an optionally present bond and / or structure, each X is independently -N(R1)2, -N*(R1), -N**, -N*(R1)2 + Z - or -N**(R1) + Z - , provided that at least one X is -N*(R1), -N**, -N*(R1)2 + Z - or -N**(R1) + Z - , wherein each R1 is independently hydrogen or C 1-6 alkyl, each Z is optionally present and independently an anti-ion to balance the charge on the nitrogen, and * represents a bond connecting to the remainder of the material.
[0008] The present invention also provides a material of formula (III):
[0009]
[0010] a material of formula (IV):
[0011]
[0012] or a salt thereof, wherein each m is independently an integer from 1 to 8, each R2 is optionally present and independently is hydrogen or C 1-6 alkyl, each designating an optionally present bond and / or structure, each R3 is optionally present and independently is hydrogen, C 1-6 alkyl or MS, each Z is optionally present and independently is a counterion to balance the charge on the nitrogen, each Y is R2 or MS, provided that at least one Y is MS, and each MS is independently a macromolecular support selected from a membrane, a fibrous medium, a polymeric coating or material, a metalorganic framework, a monolith support, a bead, a filter or a resin.
[0013] The invention also provides a method for preparing the materials described herein, the method comprising: (i) reacting a benzo crown ether or a dibenzo crown ether with an aminobenzoic acid compound to form (a) a crown ether of formula (V):
[0014]
[0015] (b) a crown ether of formula (VI):
[0016]
[0017] (ii) reacting the crown ether of formula (V) or the crown ether of formula (VI) with a macromolecular support to form at least one C-N bond or C=N bond.
[0018] The invention also provides a method for removing one or more metal ions from a solution, comprising passing the solution through the materials described herein.
[0019] BRIEF DESCRIPTION OF THE DRAWINGS
[0020] The drawings provide a bar graph showing the percentage of metal removal efficiency (MRE) of sodium, potassium, calcium, magnesium and nickel for three tests (n = 1 - 3) exhibited by the crown ether amine resin as described in Example 5. DETAILED DESCRIPTION
[0021] The invention provides materials comprising: (i) a crown ether of formula (I):
[0022]
[0023] (ii) a crown ether of formula (II):
[0024]
[0025] or a salt thereof, wherein each m is independently an integer from 1 to 8, each Indicating optionally present bonds and / or structures, each X is independently -N(R1)2, -N*(R1), -N**, -N*(R1)2 + Z - or -N**(R1) + Z - , provided that at least one X is -N*(R1), -N**, -N*(R1)2 + Z - or -N**(R1) + Z - , wherein each R1 is independently hydrogen or C 1-6 alkyl, each Z is optionally present and independently is a counterion to balance the charge on the nitrogen, and * represents a bond connecting to the remainder of the material.
[0026] In some embodiments, the material comprises a crown ether of formula (I):
[0027]
[0028] 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), each indicating optionally present bonds and / or structures, and X is -N*(R1), -N**, -N*(R1)2 + Z - or -N**(R1) + Z - , wherein each R1 is independently hydrogen or C 1-6 alkyl, Z is an optionally present counterion to balance the charge on the nitrogen, and * represents a bond connecting to the remainder of the material.
[0029] In some embodiments, the material comprises a crown ether of formula (II):
[0030]
[0031] 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), each X is independently -N(R1)2, -N*(R1), -N**, -N*(R1)2 + Z - or -N**(R1) + Z - , provided that at least one X is -N*(R1), -N**, -N*(R1)2 + Z - or -N**(R1) + Z - , wherein each R1 is independently hydrogen or C 1-6An alkyl group, each Z is optionally present and independently an anti-ion to balance the charge on the nitrogen, and * represents a bond connecting to the remainder of the material.
[0032] In any embodiment of the materials described herein, each m is independently an integer from 1 to 8 (e.g., 1, 2, 3, 4, 5, 6, 7, or 8). Generally, each m is selected from the integers from 1 to 8 to provide a crown ether selected from 12-crown-4, 15-crown-5, 18-crown-6, 21-crown-7, 24-crown-8, 27-crown-9, or 30-crown-10. For example, each m can be 2 to provide 12-crown-4, each m can be 3 to provide 18-crown-6, each m can be 4 to provide 24-crown-8, or each m can be 5 to provide 30-crown-10. Alternatively or additionally, each m can be different to provide 12-crown-4, 15-crown-5, 18-crown-6, 21-crown-7, 24-crown-8, 27-crown-9, or 30-crown-10. In some embodiments, each m is independently an integer from 1 to 4. In certain embodiments, each m is independently an integer selected from 1 or 2. In other embodiments, each m is 2.
[0033] In any embodiment of the materials described herein, each X is independently -N(R1)2, -N*(R1), -N**, -N*(R1)2 + Z - or -N**(R1) + Z - provided that at least one X is -N*(R1), -N**, -N*(R1)2 + Z - or -N**(R1) + Z - wherein each R1 is independently hydrogen or C 1-6 alkyl, Z is an optionally present anti-ion to balance the charge on the nitrogen, and * represents a bond connecting to the remainder of the material. In other words, the crown ether of formula (I) or the crown ether of formula (II) can be bonded to the remainder of the material 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 material 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 material at multiple positions via one or two bonds at each position such that the nitrogen atom has a neutral charge or a cationic charge. Those of ordinary skill in the art will readily understand that a variety of crown ethers of formula (I) or formula (II) can be incorporated into the material.
[0034] In some embodiments, each X is independently -N(R1)2, -N*(R1), or -N**, provided that at least one X is -N*(R1) or -N**, where each R1 is independently hydrogen or C 1-6 alkyl, and * represents a bond connecting to the remainder of the material. For example, each X can be -N(R1)2 or -N*(R1), provided that at least one X is -N*(R1), where each R1 is independently hydrogen or C 1-6 alkyl, and * represents a bond connecting to the remainder of the material. In other embodiments, each X is independently -N(R1)2 or -N**, provided that at least one X is -N**, where each R1 is independently hydrogen or C 1-6 alkyl, and * represents a bond connecting to the remainder of the material. In certain embodiments, each X is independently -N(R1)2 or -N*(R1), provided that at least one X is -N*(R1), such that the crown ether of formula (I) or the crown ether of formula (II) can be bonded to the remainder of the material via a single bond (e.g., to form an amine or an amide).
[0035] In other embodiments, each X is independently -N(R1)2, -N*(R1)2 + Z - or -N**(R1) + Z - provided that at least one X is -N*(R1)2 + Z - or -N**(R1) + Z - where each R1 is independently hydrogen or C 1-6 alkyl, Z is an optionally present counterion to balance the charge on the nitrogen, and * represents a bond connecting to the remainder of the material.
[0036] In any of the embodiments of the materials described herein, each R1 is independently hydrogen or C 1-6 alkyl (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 alkyl.
[0037] In any of the embodiments of the materials described herein, each designates an optionally present bond and / or structure. In other words, depending on whether Y is R2 or MS, the bond connecting to the variable Y can be a single bond or a double bond, and the bond connecting to MS can be a single bond or a double bond, such that one of the optionally present bonds is present, and an optionally present benzene ring is indicated by a dashed line.
[0038] In any embodiment of the materials described herein, each * independently represents a bond connecting to the remainder of the material, provided that at least one * is present. The bond connecting to the remainder of the material can be any suitable bond, provided that at least one bond is a C-N bond or a C=N bond. In some embodiments, a material comprising a crown ether of formula (I) or a crown ether of formula (II) has more than one C-N bond or C=N bond connecting to the remainder of the material. For example, the crown ether can (i) be attached to the remainder of the material via two separate nitrogen atoms as (a) two separate * or (b) two separate **, and / or (ii) be attached to the remainder of the material via a single nitrogen as (a) a single *, (b) two separate *, or (c) a single **. Thus, as used herein, ** refers to two separate single bonds or a single double bond.
[0039] In any embodiment of the materials described herein, each Z is optionally present and independently is a counterion to balance the charge on the nitrogen. Z can be any suitable counterion to balance the cationic charge on the nitrogen atom. For example, Z can be a halogen (such as chlorine, bromine, or iodine), NO3 - or OH - and the like. In some embodiments, Z is a halogen (such as chlorine or bromine).
[0040] The crown ether of formula (I) or the crown ether of formula (II) can be incorporated into any suitable material (such as a chemical compound or a medium), provided that the crown ether of formula (I) or the crown ether of formula (II) is attached to the remainder of the material via at least one bond (which is a C-N bond or a C=N bond denoted by * in formulas (I) and (II)). One of ordinary skill in the art can readily understand that the crown ether of formula (I) or the crown ether of formula (II) can be incorporated into the material any number of times at any number of positions. Thus, the material can be any suitable material (such as a chemical compound or a medium) capable of forming 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 such that a liquid or fluid can flow through the material.
[0041] In some embodiments, the remaining portion of the material (to which the crown ether of formula (I) or the crown ether of formula (II) is bound) is a macromolecular carrier selected from membranes (e.g., porous membranes or permeable membranes), fibrous media, polymer coatings (e.g., sheet products or sealants such as polyurethane coatings, epoxy coatings, acrylic coatings, etc.) or materials (e.g., gelatin, alginate, starch, polyethylene, polypropylene, nylon, polyvinylidene fluoride, polyethylene oxide, polypropylene oxide, polyethylene / polypropylene oxide, polyacrylonitrile, poly(meth)acrylate, poly(meth)acrylamide, polyamide, polyimide, polyester, cellulose, polystyrene, etc.), metal-organic frameworks, monolithic supports (e.g., catalyst supports), beads (e.g., polymer beads), filter media or resins (e.g., chromatographic resins). In some embodiments, the macromolecular carrier comprises gelatin, alginate, starch, polyethylene (e.g., high-density polyethylene), polypropylene, nylon, polyvinylidene fluoride, polyethylene oxide, polypropylene oxide, polyethylene / polypropylene oxide, polyacrylonitrile, poly(meth)acrylate, poly(meth)acrylamide, polyamide (e.g., nylon), polyimide, polyester, cellulose, polystyrene or combinations thereof. In certain embodiments, the macromolecular carrier comprises polyacrylonitrile, poly(meth)acrylate, poly(meth)acrylamide, polyimide, polyester, polystyrene or combinations thereof.
[0042] In certain embodiments, the crown ether compounds described herein are used to functionalize coatings such as those containing benzyl chloride groups. Alternatively or additionally, the crown ether compounds described herein can be directly converted to polyamides or polyimides via polymerization reactions.
[0043] Thus, in some embodiments, the material has the following:
[0044] Formula (III):
[0045]
[0046] Formula (IV):
[0047]
[0048] or their salts, wherein each m is independently an integer from 1 to 8, each R2 is optionally present and independently is hydrogen or C 1-6 alkyl, each designates an optionally present bond and / or structure, each R3 is optionally present and independently is hydrogen, C 1-6Alkyl or MS, each Z is optionally present and independently is a counterion to balance the charge on the nitrogen, each Y is R2 or MS, provided that at least one Y is MS, and each MS is independently a macromolecular carrier selected from membranes, fibrous media, polymer coatings or materials, metal-organic frameworks, monoliths, beads, filter media or resins. All other definitions and embodiments regarding the variables m, R2, R3, Y and Z and the macromolecular carrier are as described herein regarding the materials of the present invention.
[0049] In any embodiment of the materials described herein, each Y is R2 or MS, provided 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 the crown ether of formula (I) or the crown ether of formula (II).
[0050] In any embodiment of the materials described herein, each R2 is optionally present and independently is hydrogen or C 1-6 alkyl (such as methyl, ethyl, propyl, butyl, pentyl or hexyl). In some embodiments, each R2 is hydrogen. In other embodiments, each R2 is C 1-6 alkyl. In certain embodiments, R2 is absent.
[0051] In any embodiment of the materials described herein, each R3 is optionally present and independently is hydrogen, C 1-6 alkyl (such as 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 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 the anionic charge provided by the counterion Z described herein. Without wishing to be bound by any particular theory, it is believed that the charged variant of the crown ether modifies the material to behave like an ion exchange resin, which is desirable for certain applications.
[0052] In some embodiments, the material has formula (III):
[0053]
[0054] 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, each designates an optionally present bond and / or structure, R3 is optionally present and is hydrogen, C 1-6Alkyl or MS, where Z is optionally present and is a counterion to balance the charge on the nitrogen, and each MS is independently a macromolecular carrier selected from membranes, fibrous media, polymer coatings or materials, metal-organic frameworks, monoliths, beads, filter media or resins. All other definitions and embodiments regarding the variables m, R2, R3 and Z and the macromolecular carrier are as described herein for the materials of the present invention.
[0055] In other embodiments, the material has the formula (IV):
[0056]
[0057] or a salt thereof, wherein each m is independently an integer from 1 to 8, each R2 is optionally present and is independently hydrogen or C 1-6 alkyl, each designates an optionally present bond and / or structure, each R3 is optionally present and is independently hydrogen, C 1-6 alkyl or MS, each Z is optionally present and is independently a counterion to balance the charge on the nitrogen, each Y is R2 or MS, provided that at least one Y is MS, and each MS is independently a macromolecular carrier selected from membranes, fibrous media, polymer coatings or materials, metal-organic frameworks, monoliths, beads, filter media or resins. All other definitions and embodiments regarding the variables m, R2, R3, Y and Z and the macromolecular carrier are as described herein for the materials of the present invention.
[0058] The object of the present application is to incorporate a crown ether of formula (I) or a crown ether of formula (II) into the material via a C-N bond or a C=N bond. Accordingly, the present invention also provides a method for preparing the described materials, the method comprising:
[0059] (i) reacting a benzo crown ether or a dibenzo crown ether with an aminobenzoic acid compound to form (a) a crown ether of formula (V):
[0060]
[0061] (b) a crown ether of formula (VI):
[0062]
[0063] (ii) reacting the crown ether of formula (V) or the crown ether of formula (VI) with a macromolecular carrier selected from membranes, fibrous media, polymer coatings or materials, metal-organic frameworks, monoliths, beads, filter media or resins to form at least one C-N bond or C=N bond. All other definitions and embodiments regarding the variables m and R2 and the macromolecular carrier are as described herein for the materials of the present invention.
[0064] A method for reacting a benzo crown ether or a 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.) with the benzo crown ether or the dibenzo crown ether, heated, refluxed, or a combination thereof for any period of time as long as the desired crown ether of formula (V) or the crown ether of formula (VI) is formed.
[0065] The aminobenzoic acid compound can be any suitable benzoic acid as long as the aromatic 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 a particular embodiment, the aminobenzoic acid compound is 4-aminobenzoic acid. In other embodiments, the aminobenzoic acid compound is 4-(methylamino)benzoic acid.
[0066] The aminobenzoic acid compound can be used in any suitable amount. Generally, the aminobenzoic acid compound is added in an amount slightly in excess of the number of ketone moieties required (e.g., about 1 molar equivalent, about 1.05 molar equivalents, about 1.1 molar equivalents, about 1.15 molar equivalents, or about 1.2 molar equivalents). Thus, in some embodiments, the aminobenzoic acid compound is added in an amount of at least 1x, at least 1.05x, at least 1.1x, at least 1.15x, or at least 1.2x molar equivalents relative to the number of ketone moieties required.
[0067] 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 crown ether or the 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., greater than 100 °C) such as toluene, etc. 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., less than 100 °C) such as diethyl ether, tetrahydrofuran, ethanol, methanol, acetonitrile, or dichloromethane, etc.
[0068] 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 heating. 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, or Eaton's reagent. In a particular embodiment, 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 crown ether or a dibenzo crown ether and an aminobenzoic acid compound can be heated to about 25 °C or higher, about 50 °C or higher, about 75 °C or higher. In a particular embodiment, the reaction between a benzo crown ether or a dibenzo crown ether and an aminobenzoic acid compound is heated to a temperature of about 25 °C to about 100 °C.
[0069] The method further includes reacting the crown ether of formula (V) or the crown ether of formula (VI) with a macromolecular support selected from membranes, fibrous media, polymer coatings or materials, metal-organic frameworks, monoliths, beads, filter media, or resins 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) with the macromolecular support, mixed (e.g., shaken, stirred, etc.), heated, refluxed, or a combination thereof for any period of time as 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.
[0070] The materials described herein can be used for any suitable industrial application for any suitable purpose. For example, the materials described herein can be used in water purification applications, wastewater treatment applications, mining applications, electronic (e.g., microelectronic) applications, paper-making applications, pharmaceutical applications, biomedical applications, energy applications (e.g., as a separator in a fuel cell or battery), or metallurgical applications. Generally, the materials described herein are used for the selective removal of one or more metal ions from a fluid (i.e., a solution). The fluid can be any suitable liquid containing a solvent (e.g., water, alcohol, sulfoxide, sulfide, acetate, ether, amide, nitrile, or a combination thereof) and one or more metal ions. In a particular embodiment, the fluid (i.e., the solution) is an aqueous solution.
[0071] In some embodiments, the materials described herein can be used in methods for removing one or more metal ions from a solution, the method comprising flowing the solution over the material. For example, the material can be used as a filter media, porous medium, chromatographic resin, or membrane, etc., and the solution flows through them to remove one or more metal ions. Accordingly, the present invention also provides a method for removing one or more metal ions from a solution, which comprises flowing the solution over a material, the material comprising (i) a crown ether of formula (I):
[0072]
[0073] (ii) a crown ether of formula (II):
[0074]
[0075] or a salt thereof, wherein each m is independently an integer from 1 to 8, each designates an optionally present bond and / or structure, each X is independently -N(R1)2, -N*(R1), -N**, -N*(R1)2 + Z - or -N**(R1) + Z - , provided that at least one X is -N*(R1), -N**, -N*(R1)2 + Z - or -N**(R1) + Z - , wherein each R1 is independently hydrogen or C 1-6 alkyl, Z is an optionally present counterion to balance the charge on the nitrogen, and * represents a bond connecting to the remainder of the material. All other definitions and embodiments regarding the variables m and X are as described herein for the materials of the present invention.
[0076] The method can be used to remove any suitable ions. Alternatively or additionally, the method can be used to allow any suitable ions to flow through the material. For example, the method can be used to selectively remove one or more metal ions selected from sodium, magnesium, aluminum, potassium, calcium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, molybdenum, cadmium, tin, barium, tungsten, lead, or combinations thereof. Alternatively or additionally, the method can be used to selectively allow one or more metal ions selected from sodium, magnesium, aluminum, potassium, calcium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, molybdenum, cadmium, tin, barium, tungsten, lead, or combinations thereof to pass through the material. In certain embodiments, the method selectively allows lithium to flow through the material and removes one or more metal ions selected from sodium, magnesium, aluminum, potassium, calcium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, molybdenum, cadmium, tin, barium, tungsten, lead, or combinations thereof.
[0077] The method can remove any suitable amount of one or more metal ions from a solution. For example, the method can remove at least 40% of one or more metal ions from the solution, at least 50% of one or more metal ions from the solution, at least 60% of one or more metal ions from the solution, at least 70% of one or more metal ions from the solution, at least 80% of one or more metal ions from the solution, or at least 90% of one or more metal ions from the solution. In some embodiments, the method removes at least 50% of one or more metal ions selected from sodium, magnesium, aluminum, potassium, calcium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, molybdenum, cadmium, tin, barium, tungsten, lead, or combinations thereof. In certain embodiments, the method removes at least 60% of one or more metal ions selected from sodium, magnesium, aluminum, potassium, calcium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, molybdenum, cadmium, tin, barium, tungsten, lead, or combinations thereof. In preferred embodiments, the method removes at least 70% of one or more metal ions selected from sodium, magnesium, aluminum, potassium, calcium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, molybdenum, cadmium, tin, barium, tungsten, lead, or combinations thereof.
[0078] In some embodiments, the solution that has flowed through the material is the desired product of the method described herein. Thus, in such embodiments, the method can further include recovering the solution (e.g., an aqueous solution) that has flowed through the material. Without wishing to be bound by any particular theory, it is believed that when smaller metal ions such as lithium and / or sodium are desired, the recovered solution will be the desired product, as smaller metal ions such as lithium and / or sodium are more likely to flow through the material described herein.
[0079] In other embodiments, the one or more metal ions removed from the solution are the desired product of the method described herein. Thus, in these embodiments, the method can further include recovering the one or more metal ions removed from the solution. The one or more metal ions can be recovered by any suitable means. For example, the material containing the one or more metal ions can be washed with the recovered solution. Without wishing to be bound by any particular theory, it is believed that when larger metal ions such as magnesium, aluminum, potassium, calcium, manganese, iron, barium, etc. are desired, these desired metal ions will remain in the material, as larger metal ions are less likely to flow through the material described herein.
[0080] Aspects of the invention described herein, including embodiments, may be advantageous alone or in combination with one or more other aspects or embodiments. Without being limited by the foregoing description, specific non-limiting embodiments numbered 1-26 are provided below. As will be apparent to those skilled in the art when reading this disclosure, each individually numbered embodiment may be used or combined with any preceding or following individually numbered embodiment. This is intended to provide support for all such combinations of embodiments and is not limited to the combinations of embodiments explicitly provided below:
[0081] Embodiment
[0082] (1) In Embodiment (1), there is a material comprising: (i) a crown ether of formula (I):
[0083]
[0084] (ii) a crown ether of formula (II):
[0085]
[0086] or a salt thereof, wherein each m is independently an integer from 1 to 8, each designates an optionally present bond and / or structure, each X is independently -N(R1)2, -N*(R1), -N**, -N*(R1)2 + Z - or -N**(R1) + Z - , provided that at least one X is -N*(R1), -N**, -N*(R1)2 + Z - or -N**(R1) + Z - , wherein each R1 is independently hydrogen or C 1-6 alkyl, each Z is optionally present and independently an anti-ion to balance the charge on the nitrogen, and * represents a bond connecting to the remainder of the material.
[0087] (2) In Embodiment (2), there is the material of Embodiment (1), wherein the material comprises a crown ether of formula (I):
[0088]
[0089] or a salt thereof, wherein each m is independently an integer from 1 to 8, each designates an optionally present bond and / or structure, and X is -N*(R1), -N**, -N*(R1)2 + Z - or -N**(R1) + Z -, where each R1 is independently hydrogen or C 1-6 alkyl, Z is an optionally present counterion to balance the charge on the nitrogen, and * represents a bond to the remainder of the material.
[0090] (3) The material of embodiment (1) is present in embodiment (3), wherein the material comprises a crown ether of formula (II):
[0091]
[0092] or a salt thereof, wherein each m is independently an integer from 1 to 8, each X is independently -N(R1)2, -N*(R1), -N**, -N*(R1)2 + Z - or -N**(R1) + Z - , provided that 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, each Z is optionally present and independently a counterion to balance the charge on the nitrogen, and * represents a bond to the remainder of the material.
[0093] (4) The material of any one of embodiments (1)-(3) is present in embodiment (4), wherein each m is independently an integer from 1 to 4.
[0094] (5) The material of embodiments (1)-(4) is present in embodiment (5), wherein each m is independently an integer selected from 1 or 2.
[0095] (6) The material of any one of embodiments (1)-(5) is present in embodiment (6), wherein each m is 2.
[0096] (7) The material of any one of embodiments (1)-(6) is present in embodiment (7), wherein each X is independently -N(R1)2, -N*(R1) or -N**, provided that at least one X is -N*(R1) or -N**, where each R1 is independently hydrogen or C 1-6 alkyl, and * represents a bond to the remainder of the material.
[0097] (8) The material of embodiment (7) is present in embodiment (8), wherein each R1 is hydrogen.
[0098] (9) The material of embodiment (7) is present in embodiment (9), wherein each R1 is C 1-6 alkyl.
[0099] (10) In embodiment (10), there is the material of embodiment (1), wherein the material has the following:
[0100] Formula (III):
[0101]
[0102] Formula (IV):
[0103]
[0104] or a salt thereof, wherein each m is independently an integer from 1 to 8, each R2 is optionally present and independently is hydrogen or C 1-6 alkyl, each designates an optionally present bond and / or structure, each R3 is optionally present and independently is hydrogen, C 1-6 alkyl or MS, each Z is optionally present and independently is a counterion to balance the charge on the nitrogen, each Y is R2 or MS, provided that at least one Y is MS, and each MS is independently a macromolecular carrier selected from a membrane, a fibrous medium, a polymer coating or material, a metal-organic framework, a monolithic support, beads, a filter medium or a resin.
[0105] (11) In embodiment (11), there is the material of embodiment (10), wherein the material has Formula (III):
[0106]
[0107] 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, each designates an optionally present bond and / or structure, R3 is optionally present and is hydrogen, C 1-6 alkyl or MS, Z is optionally present and is a counterion to balance the charge on the nitrogen, and each MS is independently a macromolecular carrier selected from a membrane, a fibrous medium, a polymer coating or material, a metal-organic framework, a monolithic support, beads, a filter medium or a resin.
[0108] (12) In embodiment (12), there is the material of embodiment (10), wherein the material has Formula (IV):
[0109]
[0110] or a salt thereof, wherein each m is independently an integer from 1 to 8, each R2 is optionally present and independently is hydrogen or C 1-6 alkyl, each designates an optionally present bond and / or structure, each R3 is optionally present and independently is hydrogen, C 1-6An alkyl group or an MS, each Z is optionally present and independently an anti-ion to balance the charge on the nitrogen, each Y is R2 or MS, provided that at least one Y is MS, and each MS is independently a macromolecular carrier selected from membranes, fibrous media, polymer coatings or materials, metal-organic frameworks, monoliths, beads, filter media or resins.
[0111] (13) The material of any one of embodiments (10)-(12) is present in embodiment (13), wherein each m is independently an integer from 1 to 4.
[0112] (14) The material of any one of embodiments (10)-(13) is present in embodiment (14), wherein each m is independently an integer selected from 1 or 2.
[0113] (15) The material of any one of embodiments (10)-(14) is present in embodiment (15), wherein each m is 2.
[0114] (16) The material of any one of embodiments (10)-(15) is present in embodiment (16), wherein each R2 is independently hydrogen or C 1-6 alkyl.
[0115] (17) The material of embodiment (16) is present in embodiment (17), wherein each R2 is hydrogen.
[0116] (18) The material of embodiment (16) is present in embodiment (18), wherein each R2 is C 1-6 alkyl.
[0117] (19) The material of any one of embodiments (10)-(18) is present in embodiment (19), wherein the macromolecular carrier comprises gelatin, alginate / ester, starch, polyethylene, polypropylene, nylon, polyvinylidene fluoride, polyethylene oxide, polypropylene oxide, polyethylene / polypropylene oxide, polyacrylonitrile, poly(meth)acrylate, poly(meth)acrylamide, polyamide, polyimide, polyester, cellulose, polystyrene or a combination thereof.
[0118] (20) In embodiment (20), there is a method for preparing the material of any one of embodiments (10)-(19), the method comprising:
[0119] (i) Reacting a benzo crown ether or a dibenzo crown ether with an aminobenzoic acid compound to form (a) a crown ether of formula (V):
[0120]
[0121] (b) a crown ether of formula (VI):
[0122]
[0123] (ii) React a crown ether of formula (V) or a crown ether of formula (VI) with a macromolecular carrier selected from a membrane, a fibrous medium, a polymer coating or material, a metal-organic framework, a monolithic support, beads, a filter material or a resin to form at least one C-N bond or C=N bond.
[0124] (21) The method of embodiment (20) is present in embodiment (21), wherein the aminobenzoic acid is 4-aminobenzoic acid, 4-(methylamino)benzoic acid, 4-(dimethylamino)benzoic acid or a combination thereof.
[0125] (22) A method for removing one or more metal ions from a solution is present in embodiment (22), comprising flowing the solution through the material of any one of embodiments (1)-(19) or a salt thereof.
[0126] (23) The method of embodiment (22) is present in embodiment (23), wherein the solution is an aqueous solution.
[0127] (24) The method of embodiment (22) or embodiment (23) is present in embodiment (24), 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.
[0128] (25) The method of embodiment (22) or embodiment (23) is present in embodiment (25), 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.
[0129] (26) The method of embodiment (22) or embodiment (23) is present in embodiment (26), 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.
[0130] Examples
[0131] The following examples further illustrate the invention but should of course not be construed as limiting its scope in any way.
[0132] Example 1
[0133] This example provides an exemplary experimental procedure for preparing the crown ether of formula (V) described herein, which is summarized in Scheme 1.
[0134] Scheme 1.
[0135]
[0136] Benzocrown ether 1 (5 g, 18.6 mmol, 1 eq) 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 eq) 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 allowing the resulting solid product to dry on the filter, the product was recrystallized from ethanol to give 2.23 g (31%) of aminobenzocrown ether 3.
[0137] Example 2
[0138] This example provides an exemplary experimental procedure for preparing the crown ether of formula (V) described herein, which is summarized in Scheme 2.
[0139] Scheme 2.
[0140]
[0141] 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 eq) was added and the reaction was heated at 50 °C for 4 h. The resulting mixture was poured onto ice, filtered and washed with water. After allowing the resulting solid product to dry on the filter, 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 remaining mass being a mixture of starting material 4 and the di-addition product.
[0142] Example 3
[0143] This example provides an exemplary experimental procedure for preparing the crown ether of formula (VI) described herein, which is summarized in Scheme 3.
[0144] Scheme 3.
[0145]
[0146] Dibenzocrown ether 4 (5.0 g, 13.8 mmol, 1 eq) was dissolved in Eaton's reagent (35 g) at 50 °C. Once completely dissolved, 4-aminobenzoic acid 2 (4.16 g, 30.4 mmol, 2.2 eq) was added and the reaction was heated at 50 °C for 4 h. The resulting mixture was poured onto ice, filtered and washed with water. After allowing the resulting solid product to dry on the filter, the product was recrystallized from ethanol to give 4.1 g (50%) of diamino-dibenzocrown ether 7.
[0147] Example 4
[0148] This example provides an exemplary experimental procedure for preparing the material of formula (III) described herein, which is summarized in Scheme 4.
[0149] Scheme 4.
[0150]
[0151] Aminodibenzo-18-crown-6 (30 g, 60 mmol, 1.67 eq) was added to a solution of chloromethylated polystyrene: 1% divinylbenzene copolymer beads 8 (15 g, 36 mmol, 2.4 mmol / g) 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 allowing the resulting solid product to dry on the filter, aminodibenzo-18-crown-6 modified polystyrene / divinylbenzene resin 9 (22.94 g, ~0.7 mole eq / g) was obtained.
[0152] Example 5
[0153] This example shows the metal removal efficiency of the material of formula (III) described herein.
[0154] The metal removal efficiency (MRE) test was carried out using 100 mg of the crown ether amine resin of Example 4, which had been cleaned with 5% HCl solution and deionized water. Nitrogen was used to pass an aqueous solution (50 mL) containing 6% LiOH and sodium, potassium, calcium, magnesium or nickel at the initial concentrations listed in Table 1 through the resin at a rate of 7 mL / min at a temperature maintained at 94 °C in an oven. The challenge solution was collected in vials and the resulting metal ion concentration was measured by inductively coupled plasma - optical emission spectrometry (ICP - OES). The metal ion concentrations for three separate trials (n = 1 - 3) are listed in Table 1 and the metal removal efficiency (i.e., the percentage concentration removed) was calculated. The metal removal efficiency results are listed in Table 1 and plotted in the figures.
[0155] Table 1. Metal removal efficiency results of the crown ether amine resin
[0156]
[0157] It can be clearly seen from the results listed in Table 1 and the figures that: the crown ether amine resin of Example 4 removes more than 50% of magnesium and nickel at 94 °C, while selectively allowing ions such as lithium, sodium, potassium and calcium to flow through. In other words, the crown ether amine resin of Example 4 is more effective in removing divalent cations than monovalent cations at 94 °C.
[0158] All citations referred to herein, including publications, patent applications, and patents, are incorporated herein by reference to the extent that each citation is individually and specifically indicated to be incorporated by reference and is set forth in its entirety herein.
[0159] In the context of describing the present invention (especially in the context of the following claims), the use of the terms "a", "an", "the", "at least one", and similar referents should be construed to cover both the singular and the plural, unless otherwise indicated herein or clearly contradicted by the context. The use of the term "at least one" followed by a list of one or more items (e.g., "at least one of A and B") should be construed to mean either one of the listed items (A or B) or any combination of two or more of the listed items (A and B), unless otherwise indicated herein or clearly contradicted by the context. The terms "comprising", "having", "including", and "containing" should be construed as open-ended terms (i.e., meaning "including but not limited to"), unless otherwise specified. The recitation of a range of values herein is merely intended to be a shorthand method of referring individually to each value falling within the range, unless otherwise indicated herein, and each individual value is incorporated into the specification as if it were set forth herein individually. All methods described herein can be performed in any suitable order, unless otherwise indicated herein or clearly contradicted by the context. The use of any and all examples or exemplary language (e.g., "such as") provided herein is merely intended to better illuminate the invention and does not impose a limitation on the scope of the invention, unless otherwise stated. No language in the specification should be construed as indicating any non-recited element as essential to the practice of the invention.
[0160] Preferred embodiments of the invention are described herein, including the best mode known to the inventors for carrying out the invention. Variations of these preferred embodiments will become apparent to those skilled in the art when the above description is read. The inventors expect skilled artisans to employ such variations as appropriate, and the inventors intend the invention to be practiced otherwise than as specifically described herein. Accordingly, the invention includes all modifications and equivalents of the subject matter recited in the claims appended hereto as permitted by applicable law. In addition, the invention covers any combination of all viable variations of the elements described above, unless otherwise indicated herein or clearly contradicted by the context.
Claims
1. A material, comprising: (i) a crown ether of formula (I): and / or (ii) a crown ether of formula (II): or their salts, wherein each m is independently an integer from 1 to 8, each designates 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 - , provided that at least one X is -N*(R1), -N**, -N*(R1)2 + Z - or -N**(R1) + Z - , wherein each R1 is independently hydrogen or C 1-6 alkyl, each Z is optionally present and independently an anti-ion to balance the charge on the nitrogen, and * represents a bond connecting to the remainder of the material.
2. The material according to claim 1, wherein the material comprises a crown ether of formula (I): or a salt thereof, wherein each m is independently an integer from 1 to 8, each designates an optionally present bond and / or structure, and X is -N*(R1), -N**, -N*(R1)2 + Z - or -N**(R1) + Z - , wherein each R1 is independently hydrogen or C 1-6 alkyl, Z is an optionally present counterion to balance the charge on the nitrogen, and * represents the bond connecting to the remainder of the material.
3. The material according to claim 1, wherein the material comprises a crown ether of formula (II): or a salt thereof, wherein each m is independently an integer from 1 to 8, and each X is independently -N(R1)2, -N*(R1), -N**, -N*(R1)2 + Z - or -N**(R1) + Z - , provided that at least one X is -N*(R1), -N**, -N*(R1)2 + Z - or -N**(R1) + Z - , wherein each R1 is independently hydrogen or C 1-6 alkyl, each Z is optionally present and is independently a counterion to balance the charge on the nitrogen, and * represents a bond to the remainder of the material.
4. The material according to any one of claims 1 - 3, wherein each m is independently an integer from 1 to 4.
5. The material according to any one of claims 1 - 4, wherein each m is independently an integer selected from 1 or 2.
6. The material according to any one of claims 1 - 5, wherein each m is 2.
7. The material according to any one of claims 1-6, wherein each X is independently -N(R1)2, -N*(R1) or -N**, provided that at least one X is -N*(R1) or -N**, wherein each R1 is independently hydrogen or C 1-6 alkyl, and * represents a bond connecting to the remainder of the material.
8. The material according to claim 1, wherein the material has the following: Formula (III): or Formula (IV): or a salt thereof, wherein each m is independently an integer from 1 to 8, each R2 is optionally present and independently is hydrogen or C 1-6 alkyl, each designating an optionally present bond and / or structure, each R3 is optionally present and independently is hydrogen, C 1-6 alkyl or MS, each Z is optionally present and independently is a counterion to balance the charge on the nitrogen, each Y is R2 or MS, provided that at least one Y is MS, and each MS is independently a macromolecular support selected from membranes, fibrous media, polymer coatings or materials, metal-organic frameworks, monoliths, beads, filter media or resins.
9. The material according to claim 8, wherein the material has formula (III): 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, each designates an optionally present bond and / or structure, R3 is optionally present and is hydrogen, C 1-6 alkyl or MS, Z is optionally present and is a counterion to balance the charge on the nitrogen, and each MS is independently a macromolecular carrier selected from membranes, fibrous media, polymer coatings or materials, metal-organic frameworks, monoliths, beads, filter media or resins.
10. The material according to claim 8, wherein the material has formula (IV): or a salt thereof, wherein each m is independently an integer from 1 to 8, each R2 is optionally present and is independently hydrogen or C 1-6 alkyl, each designating an optionally present bond and / or structure, each R3 is optionally present and is independently hydrogen, C 1-6 alkyl or MS, each Z is optionally present and is independently a counterion to balance the charge on the nitrogen, each Y is R2 or MS, provided that at least one Y is MS, and each MS is independently a macromolecular carrier selected from membranes, fibrous media, polymer coatings or materials, metal-organic frameworks, monolithic supports, beads, filter media or resins.
11. The material according to any one of claims 8 - 10, wherein each m is independently an integer from 1 to 4.
12. The material according to any one of claims 8 - 11, wherein each m is independently an integer selected from 1 or 2.
13. The material according to any one of claims 8 - 12, wherein each m is 2.
14. The material according to any one of claims 8 - 13, wherein each R2 is independently hydrogen or C 1-6 alkyl group.
15. The material according to any one of claims 8 - 14, wherein the macromolecular carrier comprises gelatin, alginate / ester, starch, polyethylene, polypropylene, nylon, polyvinylidene fluoride, polyethylene oxide, polypropylene oxide, polyethylene / polypropylene oxide, polyacrylonitrile, poly(meth)acrylate, poly(meth)acrylamide, polyamide, polyimide, polyester, cellulose, polystyrene or a combination thereof.
16. A method for preparing the material according to any one of claims 8 - 15, the method comprising: (i) reacting a benzo crown ether or a dibenzo crown ether with an aminobenzoic acid compound to form (a) a crown ether of formula (V): or (b) a crown ether of formula (VI): and (ii) reacting the crown ether of formula (V) or the crown ether of formula (VI) with a macromolecular carrier selected from a membrane, a fibrous medium, a polymer coating or material, a metal - organic framework, a monolithic support, beads, a filter material or a resin to form at least one C - N bond or C=N bond.
17. The method according to claim 16, wherein the aminobenzoic acid 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 passing the solution through the material according to any one of claims 1 - 15 or a salt thereof.
19. The method according to claim 18, wherein the solution is an aqueous solution.
20. The method according to claim 18 or claim 19, wherein the method removes at least 50% of one or more metal ions selected from sodium, magnesium, aluminum, potassium, calcium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, molybdenum, cadmium, tin, barium, tungsten, lead or a combination thereof.