Hydroxylated glycidyl (METH)acrylate material and methods of use

Abstract

A material is provided comprising a glycidyl (meth)acrylate of Formula (I) or Formula (II), or a salt thereof, a method of making the material, and a method of using the material.

Description

Leydig 7739851HYDROXYLATED GLYCIDYL (METH)ACRYLATE MATERIAL AND METHODS OF USECROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This patent application claims the benefit of U.S. Provisional Patent Application No. 63 / 691,472, filed September 6, 2024, which is incorporated by reference.BACKGROUND OF THE INVENTION

[0002] Membrane-based liquid treatment processes have been utilized in a number of industries. For example, the direct flow filtration (DFF) and tangential flow filtration (TFF), including micro-, ultra-, nano-filtration and diafiltration, can be used for separation of dissolved molecules or suspended particulates.

[0003] However, removing small soluble particulates, such as metal ions, from aqueous and / or organic solutions remains a challenge. Functionalized membranes including grafted glycidyl-methacrylate (GMA)-heterocyclic ligands have emerged as an effective method for removing / capturing transition metals from / in organic fluids (e.g.. PGMEA / EL. CHN, PGME, and HBM). However, grafted glycidyl-methacrylate (GMA)-heterocyclic ligands are positively charged membranes, making them undesirable for removing / capturing appreciable amounts of alkali and alkaline earth metals in acid-sensitive fluids. Also, their active sites for metal capture can be protonated easily, compromising the removal efficiency of the membranes. Ion exchange membranes can be effective in removing / capturing alkali and alkaline earth metals. Nonetheless, release of protons from the active membrane sites due to metal capturing limits the use of ion exchange membranes in removing / capturing alkali and alkaline earth metals from acid-sensitive solutions.

[0004] Thus, there remains a need for materials and methods for removing one or more alkali and alkaline earth metal ions from an acid-sensitive solution while eliminating proton release. The invention provides such materials and methods. These and other advantages (e.g., simple and clean conjugation, uniform conjugation, rotational mobility of ligand, efficient interactions, and / or accessible chelation / coordination of the ligand) of the invention, as well as additional inventive features, will be apparent from the description of the invention provided herein.Leydig 7739852BRIEF SUMMARY OF THE INVENTION

[0005] The invention provides a material comprising a glycidyl (meth)acrylate of Formula (I):Formula (I), or a salt thereof, wherein m is an integer from 1 to 10000, n is an integer from 0 to 10000, each Ri independently is hydrogen or methyl, each X independently is -NR2- or -S-, each R2 independently is (a) hydrogen or (b) a C1-10 alkyl group, C2-10 alkenyl group, C2-10 alkynyl group, Ci-10 heteroalkyl group, C3-10 cycloalkyd group, C3-10 heterocycloalkyl group, C3-10 aryl group, C2-10 heteroaryl group, or a combination thereof, each of which is optionally substituted, each Y independently is a Ci-10 alkyl group. C2-10 alkenyl group, C2-10 alkynyl group, Ci-10 heteroalkyl group. C3-10 cycloalky 1 group, C3-10 heterocycloalkyl group, C3-10 and group, C2-10 heteroaryl group, or a combination thereof, comprising from 1-10 (e g., 1-8, 1-6, 1-4, 2-8, 4-8, or 4-10) hydroxyl substituents, and each * independently represents hydrogen, a terminating group, or a bond to a remainder of the material, provided that at least one * is a bond to the remainder of the material, and wherein the remainder of the material is bound via a sp3-sp3 carbon-carbon bond.

[0006] The invention further provides a material comprising a glycidyl (meth)acrydate of Formula (II):Leydig 773985Formula (II), or a salt thereof, wherein m is an integer from 1 to 10000. n is an integer from 0 to 10000, each Ri independently is hydrogen or methyl, each Y independently is (a) hydrogen or (b) a Ci-io alkyl group, C2-10 alkenyl group, C2-10 alkynyl group, C1-10 heteroalkyl group, C3-10 cycloalkyl group, C3-10 heterocycloalkyl group, C3-10 aryl group, C2-10 heteroaryl group, or a combination thereof, comprising from 1-10 (e.g., 1-8, 1-6, 1-4. 2-8, 4-8, or 4-10) hydroxyl substituents, and each * independently represents hydrogen, a terminating group, or a bond to a remainder of the material, provided that at least one * is a bond to the remainder of the material, and wherein the remainder of the material is bound via a sp3-sp3 carbon-carbon bond.

[0007] The invention further provides a method of making a material described herein, the method comprising (i) (a) irradiating (e.g., radiating) a polymeric support with an irradiation source and subsequently impregnating the polymeric support with glycidyl (meth)acrylate or a polymer thereof or (b) generating radicals on a polymeric support in the presence of glycidyl (meth)acrylate or a polymer thereof, wherein the polymeric support comprises one or more C-H aliphatic bonds, to graft the glycidyl (meth)acrylate or a polymer thereof on the polymeric support via one or more sp3-sp3 carbon-carbon bonds, and (ii) modifying the grafted glycidyl (meth)acrylate or a polymer thereof with one or more compounds of formula X’-Y’, wherein X' is HNR2-, HS-, or HO-, R2 is (a) hydrogen or (b) a Ci-10 alkyl group. C2-10 alkenyl group, C2-10 alkynyl group, C1-10 heteroalkyl group, C3-10 cycloalkyd group, C3-10 heterocycloalkyl group, C3-10 aryl group, C2-10 heteroaryl group, or a combination thereof, each of which is optionally substituted, and Y’ is (a) hydrogen or (b) aLeydig 7739854Ci-io alky l group, C2-10 alkenyl group, C2-10 alkynyl group, C1-10 heteroalkyl group. C3-10 cycloalkyl group, C3-10 heterocycloalkyl group, C3-10 aryl group, C2-10 heteroaryl group, or a combination thereof, comprising from 1-10 (e.g., 1-8, 1-6, 1-4, 2-8, 4-8, or 4-10) hydroxyl substituents.

[0008] The invention further provides a method of removing one or more metal ions from a solution comprising passing the solution through a material described herein or contacting the solution with the material described herein.BRIEF DESCRIPTION OF THE DRAWINGS

[0009] FIG. 1 A provides a scanning electron microscope (SEM) image of a top surface of Material 3 prepared in Example 4.

[0010] FIG. IB provides a scanning electron microscope (SEM) image of a cross-section of Material 3 prepared in Example 4.

[0011] FIG. 2 provides a bar graph showing the metal removal efficiency (MRE) percentage of removing lithium, sodium, potassium, magnesium, calcium, and barium ions from cyclohexanone (CHN) solvent exhibited by Material 3 prepared in Example 4, as described in Example 5.

[0012] FIG. 3 provides a bar graph showing the metal removal efficiency (MRE) percentage of removing lithium, sodium, magnesium, aluminum, potassium, calcium, and barium ions from propylene glycol methyl ether (PGME) solvent exhibited by Material 3 prepared in Example 4, as described in Example 5.

[0013] FIG. 4 provides a bar graph showing the metal removal efficiency (MRE) percentage of removing lithium, sodium, potassium, magnesium, calcium, and barium ions from propylene glycol methyl ether acetate (PGMEA) / ethyl lactate (EL) solvent exhibited by Material 3 prepared in Example 4, as described in Example 5.DETAILED DESCRIPTION OF THE INVENTION

[0014] An aspect of the invention provides a material comprising a glycidyl (meth)acrylate of Formula (I):Leydig 773985Formula (I), or a salt thereof, wherein m is an integer from 1 to 10000, n is an integer from 0 to 10000, each Ri independently is hydrogen or methyl, each X independently is -NR2- or -S-, each R2 independently is (a) hydrogen or (b) a C1-10 alkyl group, C2-10 alkenyl group, C2-10 alkynyl group, Ci-10 heteroalkyl group. C3-10 cycloalkyl group, C3-10 heterocycloalkyl group, C3-10 aryl group, C2-10 heteroaryl group, or a combination thereof, each of which is optionally substituted, each Y independently is a C1-10 alk l group, C2-10 alkenyl group, C2-10 alkynyl group, Ci-10 heteroalkyl group, C3-10 cycloalkyl group, C3-10 heterocycloalkyd group, C3-10 aryl group, C2-10 heteroaryl group, or a combination thereof, comprising from 1-10 (e g., 1-8, 1-6, 1-4, 2-8, 4-8. or 4-10) hydroxyl substituents, and each * independently represents hydrogen, a terminating group, or a bond to a remainder of the material, provided that at least one * is a bond to the remainder of the material, and wherein the remainder of the material is bound via a sp3-sp3 carbon-carbon bond.

[0015] In some embodiments, the material comprises a glycidyl (meth)aci late of Formula (la):Leydig 773985Formula (la), or a salt thereof, wherein m is an integer from 1 to 10000. n is an integer from 0 to 10000, each Ri independently is hydrogen or methyl, each X independently is -NR2- or -S-, each R2 independently is (a) hydrogen or (b) a C1-10 alkyl group, C2-10 alkenyl group, C2-10 alkynyl group, Ci-10 heteroalkyl group. C3-10 cycloalkyl group, C3-10 heterocycloalkyl group, C3-10 aryl group, C2-10 heteroaryl group, or a combination thereof, each of which is optionally substituted, each Y independently is a C1-10 alk l group, C2-10 alkenyl group, C2-10 alkynyl group, Ci-10 heteroalkyl group, C3-10 cycloalkyd group, C3-10 heterocycloalkyl group, C3-10 aryl group, C2-10 heteroaryl group, or a combination thereof, comprising from 1-10 (e g., 1-8, 1-6, 1-4, 2-8, 4-8. or 4-10) hydroxyl substituents, and each * independently represents hydrogen, a terminating group, or a bond to a remainder of the material, provided that at least one * is a bond to the remainder of the material, and wherein the remainder of the material is bound via a sp3-sp3 carbon-carbon bond.

[0016] In any of the embodiments of the material of Formula (I) (e.g., the material of Formula (la)), described herein, each X independently is -NR2- or -S-, each R2 independently is (a) hydrogen or (b) a C1-10 alk l group, C2-10 alkenyl group, C2-10 alkynyl group, Ci-10 heteroalkyl group, C3-10 cycloalky l group, C3-10 heterocycloalkyd group, C3-10 aryl group, C2-10 heteroary 1 group, or a combination thereof, each of which is optionally- substituted. In some embodiments, each X independently is -NR2-, each R2 independently is (a) hydrogen or (b) a C1-10 alkyd group, C2-10 alkenyl group, C2-10 alkynyl group, C 1-10 heteroalkyl group, C3-10 cycloalkyl group, C3-10 heterocycloalkyd group, C3-10 aryl group, C2-10Leydig 7739857 heteroaryl group, or a combination thereof, each of which is optionally substituted. In other embodiments, each X independently is -S-.

[0017] In any of the embodiments of the material of Formula (I) (e.g., the material of Formula (la)), described herein, each Y independently is a C1-10 alkyl group, C2-10 alkenyl group, C2-10 alkynyl group, C1-10 heteroalkyl group, C3-10 cycloalkyl group, C3-10 heterocycloalkyl group, C3-10 aryl group, C2-10 heteroaryl group, or a combination thereof, comprising from 1-10 (e.g., 1-8, 1-6, 1-4, 2-8, 4-8, or 4-10) hydroxyl substituents.

[0018] In some embodiments, the material comprises a glycidy l (meth)acrylate of Formula (II):Formula (II), or a salt thereof, wherein m is an integer from 1 to 10000, n is an integer from 0 to 10000, each Ri independently is hydrogen or methyl, each Y independently is (a) hydrogen or (b) a Ci-io alkyl group, C2-10 alkenyl group. C2-10 alkynyl group, C1-10 heteroalkyl group, C3-10 cycloalkyl group, C3-10 heterocycloalkyl group, C3-10 aryl group, C2-10 heteroaryl group, or a combination thereof, comprising from 1-10 (e.g., 1-8, 1-6, 1-4, 2-8, 4-8, or 4-10) hydroxyl substituents, and each * independently represents hydrogen, a terminating group, or a bond to a remainder of the material, provided that at least one * is a bond to the remainder of the material, and wherein the remainder of the material is bound via a sp3-sp3 carbon-carbon bond.

[0019] In some embodiments, the material comprises a glycidyl (meth)acrylate of Formula (Ila):Leydig 7739858Formula (Ila), or a salt thereof, wherein m is an integer from 1 to 10000, n is an integer from 0 to 10000, each Ri independently is hydrogen or methyl, each Y independently is (a) hydrogen or (b) a Ci-io alkyl group, C2-10 alkenyl group. C2-10 alkynyl group, C1-10 heteroalkyl group, C3-10 cycloalkyl group, C3-10 heterocycloalkyl group, C3-10 aryl group, C2-10 heteroaryl group, or a combination thereof, comprising from 1-10 (e.g., 1-8, 1-6, 1-4, 2-8, 4-8, or 4-10) hydroxyl substituents, and each * independently represents hydrogen, a terminating group, or a bond to a remainder of the material, provided that at least one * is a bond to the remainder of the material, and wherein the remainder of the material is bound via a sp3-sp3 carbon-carbon bond.

[0020] In any of the embodiments of the material of Formula (II) (e.g., the material of Formula (Ila)), described herein, each Y independently is hydrogen, a C1-10 alkyl group, C2-10 alkenyl group, C2-10 alkynyl group, C1-10 heteroalkyl group, C3-10 cycloalkyl group, C3-10 heterocycloalkyl group, C3-10 aryl group, C2-10 heteroaryl group, or a combination thereof, comprising from 1-10 (e g., 1-8, 1-6, 1-4, 2-8, 4-8, or 4-10) hydroxyl substituents. In certain embodiments, each Y is hydrogen.

[0021] In some embodiments of the material of Formula (I) or the material of Formula (II) (e.g., the material of Formula (la) or the material of Formula (Ila)), each Y independently is selected from:Leydig 7739859

[0022] As used herein, the term “(meth)acrylate” refers to an acrylate or a methacrylate. Thus, in any of the embodiments of the material described herein, each Ri independently is hydrogen or methyl. In some embodiments, each Ri is methyl. In other embodiments, each Ri is hydrogen.

[0023] In any of the embodiments of the material, described herein, m is an integer from 1 to 10000 (e.g., 1 to 5000, 1 to 1000, 1 to 500, 1 to 100, 10 to 50, or 1 to 10). In some embodiments, m is an integer from 1 to 1000. In certain embodiments, m is 1, i.e., glycidyl (meth)acrylate monomer is grafted on the remainder of the material. In other embodiments, m is greater than 1, i.e., glycidyl (meth)acrylate polymer is grafted on the remainder of the material.

[0024] In any of the embodiments of the material, described herein, n is an integer from 0 to 10000 (e.g., 0 to 5000, 0 to 1000, 0 to 500, 0 to 100, 0 to 50, or 0 to 10). In other words, the unmodified glycidyl (meth)acrylate monomer, designated with variable n, is optionally present. In some embodiments, n is an integer from 0 to 1000. In certain embodiments, the unmodified glycidyl (meth)acrylate monomer is present such that n is an integer from 1 to 10000 (e.g., 1 to 5000, 1 to 1000, 1 to 500, 1 to 100, 10 to 50, or 1 to 10). In some embodiments, n is an integer from 1 to 1000.

[0025] As used herein, the term “optionally substituted” refers to one or more optional substituents selected from halo (e.g.. fluoro, chloro, bromo, or iodo), cyano, nitro, trifluoromethyl, sulfo (e.g., sulfates, sulfonates, sulfoxides, etc.), hydroxyl, amino (e.g., a primary, secondary , or tertiary' amine having 1 to 8 carbons), Ci-io alky l, Ci-io alkoxy, Ci-io aminoalkyl, Ci-io hydroxyalkyl, and any combination thereof. Alternatively, or additionally, when referring to an optionally substituted aryl, heteroaryl, or C2-10 heterocyclyl. the term “optionally substituted” can refer to a fused or bridged aryl, heteroaryl, or C2-10 heterocyclyl.

[0026] As used herein, the term “alkyl group” refers to a saturated hydrocarbon group, having the specified number of carbon atoms, usually from 1 to about 10 carbon atoms. Examples of alkyl groups include methyl, ethyl, propyl (e.g., isopropyl or n-propyl), butyl (e.g., isobutyl, n-butyl, tert-butyl, or sec-butyl), pentyl, hexyl, heptyl, octyl, nonyl, or decyl.

[0027] As used herein, the term “alkenyl group” refers to an alkyd group described herein comprising at least one unsaturated double bond, and having the specified number of carbon atoms, usually from 2 to about 8 or 2 to about 10 carbon atoms.Leydig 77398510

[0028] As used herein, the term “alkynyl group’7refers to an alkyl group described herein comprising at least one unsaturated triple bond, and having the specified number of carbon atoms, usually from 2 to about 8 or 2 to about 10 carbon atoms.

[0029] As used herein, the term “heteroalkyl group’’ refers to an alkyl group described herein further containing from 1 to about 5 heteroatoms chosen from N, O, and S, with remaining substituent atoms being carbon, usually from about 1 to about 8 or 1 to about 10 carbon atoms. Examples of heteroalkyl groups are alkoxy groups, ethereal groups, thioalkyl groups, or thioethereal groups.

[0030] As used herein, the term “cycloalkyl group” refers to a saturated hydrocarbon ring group, having the specified number of carbon atoms, usually from 3 to about 10 carbon atoms. Examples of cycloalkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, or cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, or cyclodecyl.

[0031] As used herein, the term “heterocyclyl group” refers to a cycloalkyl group, described herein, containing from 1 to about 4 heteroatoms chosen from N. O, and S, with remaining ring atoms being carbon. Examples of heterocyclyl groups include piperazine groups, furan groups, thiazole groups and the like.

[0032] As used herein, the term “aryl group” refers to a stable monocyclic or polycyclic, substituted or unsubstituted aromatic ring having 3 to 10 ring carbon atoms, e.g., phenyl, tolyl, xylyl, or naphthyl.

[0033] As used herein, the term “heteroaryl group” refers to a stable monocyclic aromatic ring having the indicated number of ring atoms which contains from 1 to 3, or in some aspects, from 1 to 2, heteroatoms chosen from N, O, and S, with remaining ring atoms being carbon, or a stable bicyclic or tricyclic system containing at least one 5- to 7-membered aromatic ring which contains from 1 to 3, or in some aspects, from 1 to 2, heteroatoms chosen from N, O, and S, with remaining ring atoms being carbon. Monocyclic heteroaryl groups typically have from 5 to 7 ring atoms, in some aspects, bicyclic heteroaryl groups are 9- to 10-membered heteroaryl groups, that is, groups containing 9 or 10 ring atoms in which one 5- to 7-member aromatic ring is fused to a second aromatic or non-aromatic ring. Exemplary heteroary l groups include, but are not limited to, oxazolyl, piperazinyl, pyranyl, pyrazinyl, pyrazolopyrimidinyl, pyrazolyl, pyridizinyl, pyridyl, pyrimidinyl, pyrrolyl, quinolinyl, tetrazolyl, thiazolyl, thienylpyrazolyl, thiophenyl, triazolyl, henzofrij oxazolyl, benzofuranyl. benzothiazolyl, benzolhiophenyl, benzoxadiazolyl, dihydrobenzodioxynyl. furanyl, imidazolyl, indolyl, isothiazolyl, and isoxazolyl.Leydig 77398511

[0034] In any of the embodiments of the material, described herein, each * independently represents hydrogen, a terminating group, or a bond to a remainder of the material, provided that at least one * is a bond to the remainder of the material, and wherein the remainder of the material is bound via a sp3-sp3 carbon-carbon bond. As used herein, the term "a terminating group” refers to any chemical moiety remaining as a result of quenching a free radical. Common terminating groups will be readily apparent to a person of ordinary skill in the art. In some of the embodiments of the material described herein, each * independently represents hydrogen or a bond to a remainder of the material, provided that at least one * is a bond to the remainder of the material, and wherein the remainder of the material is bound via a sp3-sp3 carbon-carbon bond. In some embodiments, the material comprising a glycidyl (meth)acrylate of Formula (I) or a glycidyl (meth)acrylate of Formula (II) (e.g., the material of Formula (la) or the material of Formula (Ila)) has more than one C-C bond with the remainder of the material. Alternatively, or additionally, the material can comprise more than one glycidyl (meth)acrylate of Formula (I) or glycidyl (meth)acrylate of Formula (II) (e.g.. the material of Formula (la) or the material of Formula (Ila)).

[0035] The glycidyl (meth)acrylate of Formula (I) or glycidyl (meth )acr l ate of Formula (II) (e.g., the material of Formula (la) or the material of Formula (Ila)) can be incorporated into any suitable material (e.g., chemical compound or media) so long as the glycidyl (meth)acrylate of Formula (I) or glycidyl (meth)acrylate of Formula (II) (e.g., the material of Formula (la) or the material of Formula (Ila)) is bound to the remainder of the material via at least one carbon designated with an * in Formulae (I) and (II) (e.g., the material of Formula (la) or the material of Formula (Ila)), wherein the remainder of the material is bound via a sp3-sp3 carbon-carbon bond. It will be readily understood to a person of ordinary skill in the art that the glycidyl (meth)acrylate of Formula (I) or glycidyl (meth)acrylate of Formula (II) (e.g., the material of Formula (la) or the material of Formula (Ila)) can be incorporated into the material any number of times at any number of locations. Thus, the material can be any suitable material (e.g., chemical compound or media) comprising an aliphatic C-H bond available for a sp3-sp3 carbon-carbon bond. In some embodiments, the material is porous such that a liquid or fluid can be passed through the material.

[0036] In some embodiments, the remainder of the material to which the glycidyl (meth)acrylate of Formula (I) or glycidyl (meth)acrylate of Formula (II) (e.g., the material of Formula (la) or the material of Formula (Ila)) is bound is a macromolecular support selected from a membrane (e.g., a porous membrane or a permeable membrane), a fibrous media, aLeydig 77398512 polymeric coating (e.g., a laminate or sealant such as a polyurethane coating, an epoxy coating, an acrylic coating, etc.) or material (e.g., gelatin, alginate, starch, polyethylene, polypropylene, nylon, polyvinylidene fluoride, polyethylene oxide, polypropylene oxide, polyethylene / polypropylene oxide, polyacrylonitrile, poly(meth)acrylate, poly(meth)acrylamide. polyamide, polyimide, polyester, cellulose, polystyrene, etc.), a metal organic framework, a monolith support (e.g., a catalyst support), a bead (e.g., a polymeric bead), a filter, or a resin (e.g., a chromatographic resin). In some embodiments, the macromolecular support comprises gelatin, alginate, starch, polyethylene (e.g., high density7polyethylene), 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 macromolecular support comprises polyethylene, polypropylene, nylon, polyvinylidene fluoride, polyethylene oxide, polypropylene oxide, polyethylene / polypropylene oxide, polyacrylonitrile, cellulose, or a combination thereof. In preferred embodiments, the macromolecular support comprises polyvinylidene fluoride, polyethylene (e.g., high density polyethylene), polypropylene, nylon, or a combination thereof.

[0037] Thus, in some embodiments, the material is of formula (III):or formula (Illa):Leydig 77398513or a salt thereof, wherein m is an integer from 1 to 10000, n is an integer from 0 to 10000, each Ri independently is hydrogen or methyl, each X independently is -NR2- or -S-, each R2 independently is (a) hydrogen or (b) a C1-10 alkyl group, C2-10 alkenyl group, C2-10 alkynyl group, Ci-10 heteroalkyl group. C3-10 cycloalkyl group, C3-10 heterocycloalkyl group, C3-10 ar l group, C2-10 heteroaryl group, or a combination thereof, each of which is optionally substituted, each Y independently is a C1-10 alky l group, C2-10 alkenyl group, C2-10 alkynyl group, Ci-10 heteroalkyl group, C3-10 cycloalkyl group, C3-10 heterocycloalkyl group, C3-10 aryl group, C2-10 heteroaryl group, or a combination thereof, comprising from 1-10 (e g., 1-8, 1-6, 1-4, 2-8, 4-8. or 4-10) hydroxyl substituents, and each Q independently is hydrogen, a terminating group, or MS, provided that at least one Q is MS, and each MS independently is a macromolecular support selected from a membrane, a fibrous media, a polymeric coating or material, a metal organic framework, a monolith support, a bead, a filter, or a resin, and wherein MS is bound via an sp3-sp3 carbon-carbon bond. All other definitions and embodiments, with respect to variables m, n, Ri, X, and Y, and the macromolecular support are as described herein with respect to the inventive material.

[0038] In other embodiments, the material is of formula (IV):Leydig 77398514or formula (IV a):or a salt thereof, wherein m is an integer from 1 to 10000, n is an integer from 0 to 10000, each Ri independently is hydrogen or methyl, each Y independently is (a) hydrogen or (b) a Ci-io alkyl group, C2-10 alkenyl group. C2-10 alkynyl group, C1-10 heteroalkyl group. C3-10 cycloalkyl group, C3-10 heterocycloalkyl group, C3-10 aryl group, C2-10 heteroaryl group, or a combination thereof, comprising from 1-10 (e.g., 1-8, 1-6, 1-4, 2-8, 4-8, or 4-10) hydroxyl substituents, and each Q independently is hydrogen, a terminating group, or MS, provided that at least one Q is MS, and each MS independently is a macromolecular support selected from a membrane, a fibrous media, a polymeric coating or material, a metal organic framework, a monolith support, a bead, a filter, or a resin, and wherein MS is bound via an sp3-sp3 carbon-carbon bond. All other definitions and embodiments, with respect toLeydig 77398515 variables m, n. Ri, and Y, and the macromolecular support are as described herein with respect to the inventive material.

[0039] In any of the embodiments of the material described herein, each Q independently is hydrogen, a terminating group, or MS, provided that at least one Q is MS, wherein MS is bound via an sp3-sp3 carbon-carbon bond. In some embodiments of the material described herein, each Q independently is hydrogen or MS, provided that at least one Q is MS, wherein MS is bound via an sp3-sp3 carbon-carbon bond. In certain embodiments, the material of formula (III), formula (Illa), formula (IV), or formula (IV a) has more than one C-MS bond.

[0040] In some embodiments, the material described herein exists as a film (e.g., a thin film). The film can have any suitable thickness. For example, the film can have a thickness of about 2 mil to about 20 mil, about 2 mil to about 15 mil, about 2 mil to about 10 mil, about 5 mil to about 20 mil, about 5 mil to about 15 mil, about 5 mil to about 10 mil, about 7 mil to about 20 mil. about 7 mil to about 15 mil, or about 7 mil to about 10 mil. Alternatively, or additionally, the material described herein can comprise multiple films (e.g., thin films) that are stacked to form a composite material (e.g., a composite film).

[0041] In some embodiments, the material described herein is layered (e.g., stacked) to provide a composite material comprising one or more layers of the material described herein. Thus, each of the layers of the composite material can comprise a material of formula (I) or (II) comprising one or more X-Y. In some embodiments, the one or more X-Y moieties of each layer is the same. In other embodiments, the one or more X-Y moieties of each layer is different.

[0042] The invention also provides an aspect of a method of making a material described herein, the method comprising:(i) (a) irradiating a polymeric support with an irradiation source and subsequently impregnating the polymeric support with glycidyl (meth)acrylate or a polymer thereof or (b) generating radicals on a polymeric support in the presence of glycidyl (meth)acr late or a polymer thereof, wherein the polymeric support comprises one or more C-H aliphatic bonds, to graft the glycidyl (meth)acrylate or a polymer thereof on the polymeric support via one or more sp3-sp3 carbon-carbon bonds, and(ii) modifying the grafted glycidyl (meth)acrylate or a polymer thereof with one or more compounds of formula X’-Y’, wherein X' is HNR2- or HS-, R2 is (a) hydrogen or (b) a Ci-10 alkyl group, C2-10 alkenyl group, C2-10 alkynyl group, C1-10 heteroalkyl group. C3-10 cycloalkyl group, C3-10 heterocycloalkyl group, C3-10 aryl group, C2-10 heteroaryl group, or aLeydig 77398516 combination thereof, each of which is optionally substituted, and Y?is a Ci-io alkyl group, C2- 10 alkenyl group, C2-10 alkynyl group, C1-10 heteroalkyl group, C3-10 cycloalkyl group, C3-10 heterocycloalkyl group, C3-10 aryl group, C2-10 heteroaryl group, or a combination thereof, comprising from 1-10 (e.g., 1-8, 1-6, 1-4, 2-8, 4-8, or 4-10) hydroxyl substituents. All other definitions and embodiments, with respect to variables m. n, Ri, X, and Y, and the macromolecular support are as described herein with respect to the inventive material.

[0043] The invention also provides an aspect of a method of making a material described herein, the method comprising:(i) (a) irradiating a polymeric support with an irradiation source and subsequently impregnating the polymeric support with glycidyl (meth)acrylate or a polymer thereof or (b) generating radicals on a polymeric support in the presence of glycidyl (meth)acrylate or a polymer thereof, wherein the polymeric support comprises one or more C-H aliphatic bonds, to graft the glycidyl (meth)acrylate or a polymer thereof on the polymeric support via one or more sp3-sp3 carbon-carbon bonds, and(ii) modifying the grafted glycidyl (meth)acrylate or a polymer thereof with one or more compounds of formula X’-Y’, wherein X’ is HO-, and Y’ is (a) hydrogen or (b) a C1-10 alkyl group, C2-10 alkenyl group, C2-10 alkynyl group, C1-10 heteroalkyl group. C3-10 cycloalkyl group, C3-10 heterocycloalkyl group, C3-10 aryl group, C2-10 heteroaryl group, or a combination thereof, comprising from 1-10 (e.g.. 1-8, 1-6, 1-4. 2-8, 4-8, or 4-10) hydroxyl substituents. All other definitions and embodiments, with respect to variables m, n, Ri, and Y, and the macromolecular support are as described herein with respect to the inventive material.

[0044] In some embodiments of the method of making a material described herein, step (i) is performed in an oxygen-free environment (e.g.. less than 50 ppm O2. less than 40 ppm O2. less than 30 ppm O2, less than 20 ppm O2, less than 10 ppm O2, or less than 5 ppm O2). In some embodiments of the method of making a material described herein, step (ii) is performed in an oxygen-free environment (e.g., less than 50 ppm O2, less than 40 ppm O2, less than 30 ppm O2, less than 20 ppm O2, less than 10 ppm O2, or less than 5 ppm O2). In certain embodiments of the method of making a material described herein, steps (i) and (ii) are performed in an oxygen-free environment (e.g., less than 50 ppm O2, less than 40 ppm O2, less than 30 ppm O2, less than 20 ppm O2, or less than 10 ppm O2). In certain embodiments, step (i) and / or step (ii) is performed in an oxygen in an oxygen free environment having from 0 to 10 ppm O2, 0 to 5 ppm O2, 2 to 10 ppm O2. or from 2 to 5 ppm O2.Leydig 77398517

[0045] The method comprises (a) irradiating (e.g., radiating) a polymeric support with an irradiation (e g., a radiation) source and subsequently impregnating the polymeric support with glycidyl (meth)acrylate or a polymer thereof or (b) generating radicals on a polymeric support in the presence of glycidyl (meth)acrylate or a polymer thereof, wherein the polymeric support comprises one or more C-H aliphatic bonds, to graft the glycidyl (meth)acrylate or a polymer thereof on the polymeric support via one or more sp3-sp3 carbon-carbon bonds. Thus, the polymeric support can be irradiated or activated (e.g., by generating radicals) in the presence or absence of the glycidyl (meth)acrylate or a polymer thereof. If the polymeric support is irradiated or activated (e.g.. by generating radicals) in the absence of the glycidyl (meth)acrylate or a polymer thereof, the glycidyl (meth)acrylate or a polymer thereof can be subsequently impregnated on the polymeric support.

[0046] The polymeric support can be irradiated or activated (e.g., by generating radicals) by any suitable means. For example, the polymeric support can be irradiated or activated (e.g., by generating radicals) with E-beam irradiation, gamma irradiation. X-ray irradiation, UV light, plasma, corona discharge, a chemical initiator, or a combination thereof. In some embodiments, the method comprises irradiating the polymeric support with E-beam irradiation, gamma irradiation, X-ray irradiation, or a combination thereof and subsequently impregnating the polymeric support with glycidyl (meth)acrylate or a polymer thereof. In other embodiments, the method comprises generating radicals on the polymenc support with UV light, plasma, corona discharge, a chemical initiator, or a combination thereof in the presence of glycidyl (meth)acr late or a polymer thereof.

[0047] The glycidyl (meth)acrylate or a polymer thereof can be grafted on the polymeric support using any suitable means at any suitable temperature. For example, the irradiated or activated (e.g., by generating radicals) polymeric support can be dipped in a solution (e.g., a monomer solution) containing glycidyl (meth)acrylate or a polymer thereof, the irradiated or activated (e.g., by generating radicals) polymeric support can be spray coated with a solution (e.g., a monomer solution) containing glycidyl (meth)acrylate or a polymer thereof, or the polymeric support can be irradiated or activated (e.g., by generating radicals) while submersed in a solution (e.g., a monomer solution) containing glycidyl (meth)acrylate or a polymer thereof. The glycidyl (meth)acrylate or a polymer thereof can be grafted on the polymeric support at a temperature of 0 °C to 100 °C, 0 °C to 50 °C, 10 °C to 30 °C, or 20 °C to 30 °C. Typically, the glycidyl (meth)acrylate or a polymer thereof is grafted on the polymeric support at room temperature (e.g., approximately 25 °C). In some embodiments,Leydig 77398518 the polymeric support or irradiated or activated (e.g., by generating radicals) polymeric support is in the form of a roll, which can be wound or unwound during any stage of the process.

[0048] The solution (e.g., a monomer solution) containing glycidyl (meth)acrylate or a polymer thereof can contain any suitable solvent. For example, the solution (e.g., a monomer solution) containing glycidyl (meth)acrylate or a polymer thereof can comprise an organic solvent such as, for example, alcohols (e.g., ethanol or methanol), sulfoxides, sulfides, acetates, ethers, amides, nitriles, or a combination thereof. In some embodiments, the solution (e.g., a monomer solution) containing glycidyl (meth)acrylate or a polymer thereof comprises an alcohol such as, for example, methanol as a solvent. In certain embodiments, the solution (e.g., a monomer solution) containing glycidyl (meth)acrylate or a polymer thereof further comprises allyl glycidyl ether, l,2-epoxy-5-hexene, 3, 4-epoxy-l -butene, allyl 2,3 -epoxy propyl ether, or a combination thereof.

[0049] In some embodiments, the method comprises modifying the grafted glycidyl (meth)acrylate or a polymer thereof with one or more compounds of formula X’-Y’, wherein X’ is HNR2- or HS-, R2 is (a) hydrogen or (b) a C 1-10 alkyl group, C2-10 alkenyl group, C2-10 alkynyl group, C1-10 heteroalkyl group, C3-10 cycloalkyl group, C3-10 heterocycloalkyl group, C3-10 aryl group, C2-10 heteroaryl group, or a combination thereof, each of which is optionally substituted, and Y’ is a C1-10 alkyl group, C2-10 alkenyl group. C2-10 alky nyl group, C1-10 heteroalkyl group, C3-10 cycloalkyl group, C3-10 heterocycloalkyl group, C3-10 aryl group, C2-10 heteroaryl group, or a combination thereof, comprising from 1-10 (e.g., 1-8, 1-6, 1-4, 2-8, 4- 8, or 4-10) hydroxyl substituents.

[0050] In some embodiments, the method comprises modifying the grafted glycidyl (meth)acrylate or a polymer thereof with one or more compounds of formula X’-Y’, wherein X’ is HO-, and Y’ is (a) hydrogen or (b) a C 1-10 alkyd group, C2-10 alkenyl group, C2-10 alkynyl group, C1-10 heteroalkyl group, C3-10 cycloalky 1 group, C3-10 heterocycloalkyl group, C3-10 aryl group, C2-10 heteroaryl group, or a combination thereof, comprising from 1-10 (e.g., 1-8, 1-6, 1-4, 2-8, 4-8, or 4-10) hydroxyl substituents.

[0051] The grafted glycidyl (meth)acrylate or a polymer thereof can be modified with one or more compounds of formula X’-Y’ by any suitable means at any suitable temperature. For example, the grafted glycidyl (meth)acry late or a polymer thereof can be modified by mixing, contacting, submersing, or the like, the grafted glycidyl (meth)acrylate or a polymer thereof with a solution comprising the one or more compounds of formula X’-Y’ or multipleLeydig 77398519 solutions comprising a compound of formula X’-Y’. The solution comprising the one or more compounds of formula X’-Y’ can comprise a solvent such as, for example, water, alcohols (e.g., ethanol or methanol), sulfoxides, sulfides, acetates, ethers, amides, nitriles, or a combination thereof. In some embodiments, the solution comprising the one or more compounds of formula X’-Y’ comprises dimethylformamide (DMF). N-methyl-2- pyrrolidone (NMP), N,N-dimethylacetamide (DMAc), and / or dimethyl sulfoxide (DMSO), optionally in combination with water. The grafted glycidyl (meth)acrylate or a polymer thereof can be modified at a temperature of 25 °C to 200 °C, 25 °C to 150 °C, 25 °C to 100 °C, 50 °C to 200 °C, 50 °C to 150 °C, 50 °C to 100 °C. Typically, the glycidyl (meth)acrylate or a polymer thereof is grafted on the polymeric support at a temperature of about 75 °C to 100 °C.

[0052] The solution comprising the one or more compounds of formula X’-Y’ can comprise any suitable amount of the one or more compounds of formula X’-Y’. For example, the solution comprising the one or more compounds of formula X’-Y’ can comprise from about 0.1 wt.% to about 50 wt.%, about 0. 1 wt.% to about 40 wt.%, about 0. 1 wt.% to about 30 wt.%, about 0. 1 wt.% to about 20 wt.%, about 1 wt.% to about 50 wt.%, about 1 wt.% to about 40 wt.%, about 1 wt.% to about 30 wt.%, about 1 wt.% to about 20 wt.%, about 5 wt.% to about 50 wt.%, about 5 wt.% to about 40 wt.%, about 5 wt.% to about 30 wt.%. or about 5 wt.% to about 20 wt.% of the one or more compounds of formula X’-Y’.

[0053] The modification of the grafted glycidyl (meth)aciylate or a polymer thereof can be facilitated by an acid (e.g., a Bronsted acid or a Lewis acid) or a base (e.g., a Bronsted base or a Lewis base). In some embodiments, the modification of the grafted glycidyl (meth)acrylate or a polymer thereof is facilitated by an amine base (e.g., trimethylamine, tri methyl amine, diisopropylethylamine, or the like).

[0054] The modified grafted glycidyl (meth)acrylate or a polymer thereof (i.e. , the material described herein) can be washed with water, an organic solvent (e.g., an alcohol such as ethanol or methanol, a sulfoxide, a sulfide, an acetate, an ether, an amide, a nitrile, or a combination thereof), an acidic solution (e.g., aqueous hydrochloric acid or aqueous sulfuric acid), a basic solution (e.g., aqueous tetramethylammonium hydroxide or aqueous ammonium hydroxide), or a combination thereof.

[0055] The modified grafted glycidyl (meth)acrylate or a polymer thereof (i.e., the material described herein), or an intermediate thereof, can be dried by any suitable means. For example, the modified grafted glycidyl (meth)acrylate or a polymer thereof (i.e., theLeydig 77398520 material described herein), or an intermediate thereof, can be dried by air, elevated temperatures, a desiccant, sieves, or a combination thereof

[0056] The materials described herein can be used in any suitable industrial application for any suitable purpose. For example, the materials described herein can be used in water purification applications, wastewater treatment applications, organic solvent treatment applications, mining applications, electronic (e.g., microelectronic) applications, papermaking applications, pharmaceutical applications, biomedical applications, energy applications (e.g., as separators in fuel cells or batteries), or metallurgy applications. Generally, the materials described herein are used to selectively remove one or more metal ions from a fluid (i.e., solution). The fluid can be any suitable liquid containing a solvent (e.g., water, alcohols, sulfoxides, sulfides, acetates, ethers, ketones, amides, nitriles, or a combination thereof) and one or more metal ions. In certain embodiments, the fluid (i.e., solution) is an aqueous solution. In some embodiments, the fluid (i.e., solution) comprises an organic solvent such as, for example, alcohols (e.g.. ethanol or methanol), sulfoxides, sulfides, acetates, ethers, ketones, amides, nitriles, or a combination thereof. In certain embodiments, the fluid comprises cyclohexanone (CHN), propylene glycol methyl ether (PGME), propylene glycol methyl ether acetate (PGMEA), ethyl lactate, or a combination thereof.

[0057] In some embodiments, the materials described herein can be used in a method of removing one or more metal ions from a solution comprising (i) passing the solution through the material or (ii) contacting the solution with the material. For example, the material can be used as a filter, porous media, chromatographic resin, membrane, or the like through which the solution passes or is contacted with to remove one or more metal ions. Thus, the invention further provides a method of removing one or more metal ions from a solution comprising (i) passing the solution through or (ii) contacting the solution with a material comprising a glycidyl (meth)acrylate of Formula (I), Formula (II), Formula (III), or Formula (IV) (e.g., a glycidyl (meth)acrylate of Formula (la), Formula (Ila), Formula (Illa), or Formula (IVa)). In some embodiments, the invention provides a method of removing one or more metal ions from a solution comprising (i) passing the solution through or (ii) contacting the solution with one or more materials comprising a glycidyl (meth)acrylate of Formula (I), Formula (II), Formula (III), or Formula (IV) (e.g.. a glycidyl (meth)acrylate of Formula (la), Formula (Ila), Formula (Illa), or Formula (IVa)).Leydig 77398521

[0058] The method can be used to remove any suitable ion. Alternatively, or additionally, the method can be used to allow any suitable ion to pass through the material. For example, the method can used to selectively remove one or more alkali and alkaline earth metals selected from lithium, sodium, magnesium, aluminum, potassium, calcium, barium, or a combination thereof.

[0059] The method can remove any suitable amount of the one or more metal ions from the solution. For example, the method can remove at least 40% of the one or more metal ions from the solution, at least 50% of the one or more metal ions from the solution, at least 60% of the one or more metal ions from the solution, at least 70% of the one or more metal ions from the solution, at least 80% of the one or more metal ions from the solution, or at least 90% of the 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 lithium, sodium, magnesium, aluminum, potassium, calcium, barium, or a combination thereof. In certain embodiments, the method removes at least 60% of one or more metal ions selected from lithium, sodium, magnesium, aluminum, potassium, calcium, barium, or a combination thereof. In preferred embodiments, the method removes at least 70% of one or more metal ions selected from lithium, sodium, magnesium, aluminum, potassium, calcium, barium, or a combination thereof.

[0060] In some embodiments, the solution that passes through or is contacted with the material is the desirable product of the methods described herein. Thus, in such embodiments, the method can further comprise recovering the solution (e.g., aqueous solution or organic solution) that has been passed through or contacted with the material.

[0061] In other embodiments, the one or more metal ions removed from the solution are the desirable product of the method described herein. Thus, in these embodiments, the method can further comprise 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 a recovery solution.

[0062] Aspects, including embodiments, of the invention described herein may be beneficial alone or in combination, with one or more other aspects or embodiments. Without limiting the foregoing description, certain non-limiting embodiments of the disclosure numbered 1-20 are provided below. As will be apparent to those of skill in the art upon reading this disclosure, each of the individually numbered embodiments may be used or combined with any of the preceding or following individually numbered embodiments. ThisLeydig 77398522 is intended to provide support for all such combinations of embodiments and is not limited to combinations of embodiments explicitly provided below:EMBODIMENTS

[0063] (1) In embodiment (1) is presented a material comprising a glycidyl(meth)acrylate of Formula (I):Formula (I), or a salt thereof, wherein m is an integer from 1 to 10000. n is an integer from 0 to 10000, each Ri independently is hydrogen or methyl, each X independently is -NR.2- or -S-. each R2 independently is (a) hydrogen or (b) a C1-10 al k l group, C2-10 alkenyl group, C2-10 alkynyl group, Ci-10 heteroalkyl group, C3-10 cycloalkyd group, C3-10 heterocycloalkyd group, C3-10 aryl group, C2-10 heteroary 1 group, or a combination thereof, each of which is optionally substituted, each Y independently is a C1-10 alkyl group, C2-10 alkenyl group, C2-10 alkynyl group. C1-10 heteroalkyl group, C3-10 cycloalkyl group, C3-10 heterocycloalkyl group, C3-10 aryl group, C2-10 heteroary ! group, or a combination thereof, comprising from 1-10 hydroxyl substituents, and each * independently represents hydrogen, a terminating group, or a bond to a remainder of the material, provided that at least one * is a bond to the remainder of the material, and wherein the remainder of the material is bound via a sp3-sp3 carbon-carbon bond.

[0064] (2) In embodiment (2) is presented the material of embodiment (1), wherein the material comprises a glycidyl (meth)acrydate of Formula (la):Leydig 77398523Formula (la), or a salt thereof, wherein m is an integer from 1 to 10000. n is an integer from 0 to 10000, each Ri independently is hydrogen or methyl, each X independently is -NR2- or -S-, each R2 independently is (a) hydrogen or (b) a C1-10 alkyl group, C2-10 alkenyl group, C2-10 alkynyl group, Ci-10 heteroalkyl group, C3-10 cycloalkyd group, C3-10 heterocycloalkyd group, C3-10 aryl group, C2-10 heteroaryl group, or a combination thereof, each of which is optionally substituted, each Y independently is a Ci-io alkyl group, C2-10 alkenyl group, C2-10 alkynyl group. C1-10 heteroalkyl group, C3-10 cycloalkyl group, C3-10 heterocycloalkyl group, C3-10 aryl group, C2-10 heteroary ! group, or a combination thereof, comprising from 1-10 hydroxyl substituents, and each * independently represents hydrogen, a terminating group, or a bond to a remainder of the material, provided that at least one * is a bond to the remainder of the material, and wherein the remainder of the material is bound via a sp3-sp3 carbon-carbon bond.

[0065] (3) In embodiment (3) is presented the material of embodiment (1) or embodiment(2), wherein each Ri is methyl.

[0066] (4) In embodiment (4) is presented the material of any one of embodiments (1)-(3). wherein m and n are each independently an integer from 1 to 1000.

[0067] (5) In embodiment (5) is presented the material of any one of embodiments (1)-(4), wherein the bond to a remainder of the material is a bond to a macromolecular support selected from a membrane, a fibrous media, a polymeric coating or material, a metal organic framework, a monolith support, a bead, a filter, or a resin, and wherein the macromolecular support is bound via a sp3-sp3 carbon-carbon bond.Leydig 77398524

[0068] (6) In embodiment (6) is presented the material of embodiment (5), wherein the macromolecular 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.

[0069] (7) In embodiment (7) is presented a method of making a material of any one of embodiments (1 )-(6), the method comprising:(i) (a) irradiating a polymeric support with an irradiation source and subsequently impregnating the polymeric support with glycidyl (meth)acrylate or a polymer thereof or (b) generating radicals on a polymeric support in the presence of glycidyl (meth)acrylate or a polymer thereof, wherein the polymeric support comprises one or more C-H aliphatic bonds, to graft the glycidyl (meth)acrylate or a polymer thereof on the polymeric support via one or more sp3-sp3 carbon-carbon bonds, and(ii) modifying the grafted glycidyl (meth)acrylate or a polymer thereof with one or more compounds of formula X’-Y’, wherein X’ is HNR2- or HS-, R2 is (a) hydrogen or (b) a Ci-10 alkyl group, C2-10 alkenyl group, C2-10 alkynyl group, C1-10 heteroalkyl group, C3-10 cycloalkyl group, C3-10 heterocycloalkyl group, C3-10 aryl group, C2-10 heteroaryl group, or a combination thereof, each of which is optionally substituted, and Y?is a C1-10 alkyl group. C2- 10 alkenyl group, C2-10 alkynyl group, C1-10 heteroalkyl group, C3-10 cycloalkyl group, C3-10 heterocycloalkyl group, C3-10 aryl group, C2-10 heteroaryl group, or a combination thereof, comprising from 1-10 hydroxyl substituents.

[0070] (8) In embodiment (8) is presented the method of embodiment (7), wherein the method comprises irradiating the polymeric support with E-beam irradiation, gamma irradiation, X-ray irradiation, or a combination thereof and subsequently impregnating the polymeric support with glycidyl (meth)acrylate or a polymer thereof.

[0071] (9) In embodiment (9) is presented a method of removing one or more metal ions from a solution comprising (i) passing the solution through a material of embodiment (1) or (ii) contacting the solution with a material of any one of embodiments (l)-(6).

[0072] (10) In embodiment (10) is presented the method of embodiment (9), wherein the method removes at least 50% of one or more metal ions selected from lithium, sodium, magnesium, aluminum, potassium, calcium, barium, or a combination thereof.Leydig 77398525

[0073] (11) In embodiment (11) is presented a material comprising a glycidyl(meth)acrylate of Formula (II):Formula (II), or a salt thereof, wherein m is an integer from 1 to 10000, n is an integer from 0 to 10000, each Ri independently is hydrogen or methyl, each Y independently is (a) hydrogen or (b) a Ci-io alkyl group, C2-10 alkenyl group, C2-10 alkynyl group, C1-10 heteroalkyl group. C3-10 cycloalkyl group, C3-10 heterocycloalkyl group, C3-10 aryl group, C2-10 heteroaryl group, or a combination thereof, comprising from 1-10 hydroxyl substituents, and each * independently represents hydrogen, a terminating group, or a bond to a remainder of the material, provided that at least one * is a bond to the remainder of the material, and wherein the remainder of the material is bound via a sp3-sp3 carbon-carbon bond.

[0074] (12) In embodiment (12) is presented the material of embodiment (11), wherein the material comprises a glycidyl (meth)acrylate of Formula (Ila):Leydig 77398526or a salt thereof, wherein m is an integer from 1 to 10000, n is an integer from 0 to 10000, each Ri independently is hydrogen or methyl, each Y independently is (a) hydrogen or (b) a Ci-io alkyl group, C2-10 alkenyl group, C2-10 alkynyl group, C1-10 heteroalkyl group. C3-10 cycloalkyl group, C3-10 heterocycloalkyl group, C3-10 aryl group, C2-10 heteroaryl group, or a combination thereof, comprising from 1-10 hydroxyl substituents, and each * independently represents hydrogen, a terminating group, or a bond to a remainder of the material, provided that at least one * is a bond to the remainder of the material, and wherein the remainder of the material is bound via a sp3-sp3 carbon-carbon bond.

[0075] (13) In embodiment (13) is presented the material of embodiment (11) or embodiment (12), wherein each Ri is methyl.

[0076] (14) In embodiment (14) is presented the material of any one of embodiments(11 )-( 13), wherein m and n are each independently an integer from 1 to 1000.

[0077] (15) In embodiment (15) is presented the material of any one of embodiments(11)-(14), wherein the bond to a remainder of the material is a bond to a macromolecular support selected from a membrane, a fibrous media, a polymeric coating or material, a metal organic framework, a monolith support, a bead, a filter, or a resin, and wherein the macromolecular support is bound via a sp3-sp3 carbon-carbon bond.

[0078] (16) In embodiment (16) is presented the material of embodiment (15), wherein the macromolecular support comprises gelatin, alginate, starch, polyethylene, polypropylene, nylon, polyvinylidene fluoride, polyethylene oxide, polypropylene oxide. polyethylene / polypropylene oxide, polyacrylonitrile, poly(meth)acrylate.Leydig 77398527 poly(meth)acrylamide. polyamide, polyimide, polyester, cellulose, polystyrene, or a combination thereof.

[0079] (17) In embodiment (17) is presented a method of making a material of any one of embodiments (11)-(16), the method comprising:(i) (a) irradiating a polymeric support with an irradiation source and subsequently impregnating the polymeric support with glycidyl (meth)acrylate or a polymer thereof or (b) generating radicals on a polymeric support in the presence of glycidyl (meth)acrylate or a polymer thereof, wherein the polymeric support comprises one or more C-H aliphatic bonds, to graft the glycidyl (meth)acrylate or a polymer thereof on the polymeric support via one or more sp3-sp3 carbon-carbon bonds, and(ii) modifying the grafted glycidyl (meth)acrylate or a polymer thereof with one or more compounds of formula X’-Y’, wherein X' is HO-, and Y’ is (a) hydrogen or (b) a Ci-io alkyl group, C2-10 alkenyl group, C2-10 alkynyl group, C1-10 heteroalkyl group, C3-10 cycloalkyl group, C3-10 heterocycloalkyl group. C3-10 aryl group, C2-10 heteroaryl group, or a combination thereof, comprising from 1-10 hydroxyl substituents.

[0080] (18) In embodiment (18) is presented the method of embodiment (17), wherein the method comprises irradiating the polymeric support with E-beam irradiation, gamma irradiation, X-ray irradiation, or a combination thereof and subsequently impregnating the polymeric support with glycidyl (meth)acrylate or a polymer thereof.

[0081] (19) In embodiment (19) is presented a method of removing one or more metal ions from a solution comprising (i) passing the solution through a material of embodiment (11) or (ii) contacting the solution with a material of embodiment (11 )-(l 6).

[0082] (20) In embodiment (20) is presented the method of embodiment (19), wherein the method removes at least 50% of one or more metal ions selected from lithium, sodium, magnesium, aluminum, potassium, calcium, barium, or a combination thereof.EXAMPLES

[0083] These following examples further illustrate the invention but, of course, should not be construed as in any way limiting its scope.EXAMPLE 1

[0084] This example provides an exemplary experimental procedure for the preparation of a glycidyl methacrylate grafted roll, which is summarized in Scheme 1.Leydig 77398528Scheme 1.

[0085] A substrate (e.g., HDPE) was fed into an E-Beam where it was irradiated, cowound with the interleaf, and dipped into a coating solution containing glycidyl methacrylate, and rewound to form a glycidyl methacrylate grafted roll. The coating solution was prepared by dissolving glycidyl methacrylate (E5 kg) in methanol (13.5 kg) and mixed for 10 minutes to form a 10 wt.% solution of glycidyl methacrylate in methanol. The E-beam and grafting conditions are set forth in Table 1 below.Table 1. E-Beam and Grafting Conditions

[0086] As noted in Table 1, all unwind, irradiation, monomer impregnation, and rewind processes were executed in an environment with an O2 level of <50 ppm. Weight change, critical water surface tension (CWST), and FTIR were used to confirm grafting of glycidyl methacrylate on the substrate.

[0087] The glycidyl methacrylate grafted roll was w ashed with methanol using a recycled trickle wash for 4 hours followed by a deionized water trickle w ash for 6 hours to remove any residual non-grafted monomer, oligomer, and polymer. After drying the glycidylLeydig 77398529 methacrylate grafted roll, the glycidyl methacrylate uptake was determined to be approximately 100-140 percent by' weight based on the HDPE substrate.EXAMPLE 2

[0088] This example provides an exemplary' experimental procedure for the preparation of Material 1, described herein, which is summarized in Scheme 2.Scheme 2.

[0089] 2-amino-2-(hydroxymethyl)propane-1.3-diol (10 g) was dissolved in 90 g water / DMSO (1: 1) or DMSO and the resulting solution was added to a 12” by 12” strip of the glycidyl methacrylate grafted HDPE and the combination was heated to 85 °C for 24 hours. After cooling the glycidyl methacrylate grafted HDPE and removing the remaining solution, the resulting media was washed with isopropanol and water several times. The washed media was then dried in an oven at 65 °C for 2 hours. The uptake of 2-amino-2- (hydroxymethyl)propane-l,3-diol was determined to be approximately 10-30 percent by weight.

[0090] The washed surface modified media was subsequently cleaned by soaking the media in methanol for 30 minutes. 50% isopropanol for 30 minutes, and deionized water for 1 hour. After soaking the surface modified media in isopropanol for 10 minutes, the surface modified media was soaked in 4% sulfuric acid at 60 °C for 4 hours and then rinsed with deionized w ater to obtain a pH of 7. The resulting material was then trickle washed with deionized water for 30 minutes and dried in an oven at 65 °C for 2 hours. The uptake of 2- amino-2-(hydroxymethyl)propane-l,3-diol after cleaning was determined to be approximately 10-30 percent by weight.Leydig 77398530EXAMPLE 3

[0091] This example provides an exemplary experimental procedure for the preparation of Material 2, described herein, which is summarized in Scheme 2.Scheme 2.

[0092] 6-aminohexane-l,2,3,4,5-pentaol (10 g) was dissolved in 90 g water / DMSO (1: 1) or DMSO and the resulting solution was added to a 12” by 12” strip of the glycidyl methacrylate grafted HDPE and the combination was heated to 85 °C for 24 hours. After cooling the glycidyl methacrylate grafted HDPE and removing the remaining solution, the resulting media was washed with isopropanol and water several times. The washed media was then dried in an oven at 65 °C for 2 hours. The uptake of 6-aminohexane-L2,3,4,5- pentaol was determined to be approximately 10-30 percent by weight.

[0093] The washed surface modified media was subsequently cleaned by soaking the media in methanol for 30 minutes, 50% isopropanol for 30 minutes, and deionized water for 1 hour. After soaking the surface modified media in isopropanol for 10 minutes, the surface modified media was soaked in 4% sulfuric acid at 60 °C for 4 hours and then rinsed with deionized water to obtain a pH of 7. The resulting material was then trickle washed with deionized water for 30 minutes and dried in an oven at 65 °C for 2 hours. The uptake of 6- aminohexane-l,2,3,4,5-pentaol after cleaning was determined to be approximately 10-30 percent by weight.EXAMPLE 4

[0094] This example provides an exemplar}' experimental procedure for the preparation of Material 3, described herein, which is summarized in Scheme 3.Scheme 3.Leydig 77398531

[0095] A 12” by 12” strip of the glycidyl methacrylate grafted HDPE was soaked in isopropanol for 10 minutes, then the media was soaked in 4% sulfunc acid at 60 °C for 4 hours and then rinsed with deionized water to obtain a pH of 7. The resulting material was then trickle washed with deionized water for 30 minutes and dried in an oven at 65 °C for 2 hours.EXAMPLE 5

[0096] This example demonstrates the metal removal efficiency of Material 3 of Example 4, described herein.

[0097] Metal removal efficiency (MRE) testing was performed using a punched 47 mm disc of the HDPE coated material of Example 4. A 20-30 mL solution of (a) cyclohexanone (CHN), (b) propylene glycol methyl ether (PGME), or (c) propylene glycol methyl ether acetate (PGMEA) / ethyl lactate (EL) containing 1 ppb of each metal impurity (i.e. , lithium, sodium, potassium, magnesium, calcium, and barium) was passed through the disc and the resulting metal ion concentrations were measured by inductively coupled plasma - mass spectrometry (ICP-MS). The metal removal efficiency (i.e., the percent concentration removed) for three separate trials for each of the solvents (a)-(c) were calculated and the results are plotted in FIGs. 2-4, respectively.

[0098] As is apparent from the results set forth in FIGs. 2-4, Material 3 of Example 4 removed greater than 90% of lithium, sodium, potassium, magnesium, calcium, and barium, from CHN and PGMEA / EL. In addition, Material 3 of Example 4 was effective at removing greater than 90% of lithium, magnesium, aluminum, calcium, and barium from PGME.

[0099] All references, including publications, patent applications, and patents, cited herein are hereby incorporated by reference to the same extent as if each reference were individually and specifically indicated to be incorporated by reference and were set forth in its entirety herein.Leydig 77398532

[0100] The use of the terms “a” and “an7’ and “the” and “at least one” and similar referents in the context of describing the invention (especially in the context of the following claims) are to be construed to cover both the singular and the plural, unless otherwise indicated herein or clearly contradicted by context. The use of the term “at least one” followed by a list of one or more items (for example, “at least one of A and B”) is to be construed to mean one item selected from the listed items (A or B) or any combination of two or more of the listed items (A and B), unless otherwise indicated herein or clearly contradicted by context. The terms “comprising,” “having,” “including,” and “containing” are to be construed as open-ended terms (i.e., meaning “including, but not limited to.”) unless otherwise noted. Recitation of ranges of values herein are merely intended to serve as a shorthand method of referring individually to each separate value falling within the range, unless otherwise indicated herein, and each separate value is incorporated into the specification as if it were individually recited herein. All methods described herein can be performed in any suitable order unless otherwise indicated herein or otherwise clearly contradicted by context. The use of any and all examples, or exemplary language (e.g., “such as”) provided herein, is intended merely to better illuminate the invention and does not pose a limitation on the scope of the invention unless otherwise claimed. No language in the specification should be construed as indicating any non-claimed element as essential to the practice of the invention.

[0101] Preferred embodiments of this invention are described herein, including the best mode know n to the inventors for carry ing out the invention. Variations of those preferred embodiments may become apparent to those of ordinary skill in the art upon reading the foregoing description. The inventors expect skilled artisans to employ such variations as appropriate, and the inventors intend for the invention to be practiced otherwise than as specifically described herein. Accordingly, this invention includes all modifications and equivalents of the subject matter recited in the claims appended hereto as permitted by applicable law. Moreover, any combination of the above-described elements in all possible variations thereof is encompassed by the invention unless otherwise indicated herein or otherwise clearly contradicted by context.

Claims

Leydig 77398533CLAIMS:

1. A material comprising a glycidyl (meth)acrylate of Formula (I):or a salt thereof, wherein m is an integer from 1 to 10000, n is an integer from 0 to 10000, each Ri independently is hydrogen or methyl, each X independently is -NR2- or -S-, each R2 independently is (a) hydrogen or (b) a C1-10 alkyl group, C2-10 alkenyl group, C2-10 alkynyl group, Ci-10 heteroalkyl group. C3-10 cycloalkyl group, C3-10 heterocycloalkyl group, C3-10 ary l group, C2-10 heteroaryl group, or a combination thereof, each of which is optionally substituted, each Y independently is a C1-10 alky l group, C2-10 alkenyl group, C2-10 alkynyl group, Ci-10 heteroalkyl group, C3-10 cycloalkyl group, C3-10 heterocycloalkyd group, C3-10 aryl group, C2-10 heteroary l group, or a combination thereof, comprising from 1-10 hydroxyl substituents, and each * independently represents hydrogen, a terminating group, or a bond to a remainder of the material, provided that at least one * is a bond to the remainder of the material, and wherein the remainder of the material is bound via a sp3-sp3 carbon-carbon bond.

2. The material of claim 1, wherein the material comprises a glycidyl (meth)acrydate of Formula (la):Leydig 77398534Formula (la), or a salt thereof, wherein m is an integer from 1 to 10000. n is an integer from 0 to 10000, each Ri independently is hydrogen or methyl, each X independently is -NR2- or -S-, each R2 independently is (a) hydrogen or (b) a C1-10 alkyl group, C2-10 alkenyl group, C2-10 alkynyl group, Ci-10 heteroalkyl group. C3-10 cycloalkyl group, C3-10 heterocycloalkyl group, C3-10 aryl group, C2-10 heteroaryl group, or a combination thereof, each of which is optionally substituted, each Y independently is a C1-10 alk l group, C2-10 alkenyl group, C2-10 alkynyl group, Ci-10 heteroalkyl group, C3-10 cycloalkyd group, C3-10 heterocycloalkyl group, C3-10 aryl group, C2-10 heteroaryl group, or a combination thereof, comprising from 1-10 hydroxyl substituents, and each * independently represents hydrogen, a terminating group, or a bond to a remainder of the material, provided that at least one * is a bond to the remainder of the material, and wherein the remainder of the material is bound via a sp3-sp3 carbon-carbon bond.

3. The material of claim 1 or claim 2, wherein each Ri is methyl.

4. The material of any one of claims 1-3, wherein m and n are each independently an integer from 1 to 1000.

5. The material of any one of claims 1-4, wherein the bond to a remainder of the material is a bond to a macromolecular support selected from a membrane, a fibrous media, a polymeric coating or material, a metal organic framework, a monolith support, a bead, aLeydig 77398535 filter, or a resin, and wherein the macromolecular support is bound via a sp3-sp3 carboncarbon bond.

6. The material of claim 5, wherein the macromolecular support comprises gelatin, alginate, starch, polyethylene, polypropylene, nylon, poly vinylidene fluoride, polyethylene oxide, polypropylene oxide, polyethylene / polypropylene oxide, polyacrylonitrile, poly(meth)acrylate, poly(meth)acrylamide, polyamide, polyimide, polyester, cellulose, polystyrene, or a combination thereof.

7. A method of making a material of any one of claims 1-6, the method comprising:(i) (a) irradiating a polymeric support with an irradiation source and subsequently- impregnating the polymeric support with glycidyl (meth)acrylate or a polymer thereof or (b) generating radicals on a polymeric support in the presence of glycidyl (meth)acrylate or a polymer thereof, wherein the polymeric support comprises one or more C-H aliphatic bonds, to graft the glycidyl (meth)acrylate or a polymer thereof on the polymeric support via one or more sp3-sp3 carbon-carbon bonds, and(ii) modifying the grafted glycidyl (meth)acrylate or a polymer thereof with one or more compounds of formula X’-Y’, wherein X' is HNR2- or HS-, R2 is (a) hydrogen or (b) a Ci-10 alkyl group, C2-10 alkenyl group, C2-10 alkynyl group, C1-10 heteroalkyl group. C3-10 cycloalkyl group, C3-10 heterocycloalkyl group, C3-10 aryl group, C2-10 heteroaryl group, or a combination thereof, each of which is optionally substituted, and Y’ is a C1-10 alkyl group, C2- 10 alkenyl group, C2-10 alkynyl group, C1-10 heteroalkyl group, C3-10 cycloalkyl group. C3-10 heterocycloalkyl group, C3-10 aryl group, C2-10 heteroaryl group, or a combination thereof, comprising from 1-10 hydroxyl substituents.

8. The method of claim 7, wherein the method comprises irradiating the polymeric support with E-beam irradiation, gamma irradiation, X-ray irradiation, or a combination thereof and subsequently impregnating the polymeric support with glycidyl (meth Jac r late or a polymer thereof.Leydig 773985369. A method of removing one or more metal ions from a solution comprising (i) passing the solution through a material of claim 1 or (ii) contacting the solution with a material of any one of claims 1-6.

10. The method of claim 9. wherein the method removes at least 50% of one or more metal ions selected from lithium, sodium, magnesium, aluminum, potassium, calcium, barium, or a combination thereof.

11. A material comprising a glycidyl (meth)acrylate of Formula (II):Formula (II). or a salt thereof, wherein m is an integer from 1 to 10000, n is an integer from 0 to 10000, each Ri independently is hydrogen or methyl, each Y independently is (a) hydrogen or (b) a Ci-io alkyl group, C2-10 alkenyl group, C2-10 alkynyl group, C1-10 heteroalkyl group. C3-10 cycloalkyl group, C3-10 heterocycloalkyl group, C3-10 aryl group, C2-10 heteroaryl group, or a combination thereof, comprising from 1-10 hydroxyl substituents, and each * independently represents hydrogen, a terminating group, or a bond to a remainder of the material, provided that at least one * is a bond to the remainder of the material, and wherein the remainder of the material is bound via a sp3-sp3 carbon-carbon bond.

12. The material of claim 11, wherein the material comprises a glycidyl (meth)acrylate of Formula (Ila):Leydig 77398537or a salt thereof, wherein m is an integer from 1 to 10000. n is an integer from 0 to 10000, each Ri independently is hydrogen or methyl, each Y independently is (a) hydrogen or (b) a Ci-io alkyl group, C2-10 alkenyl group, C2-10 alkynyl group, C1-10 heteroalkyd group, C3-10 cycloalky l group, C3-10 heterocycloalkyl group, C3-10 an 1 group, C2-10 heteroaryl group, or a combination thereof, comprising from 1-10 hydroxyl substituents, and each * independently represents hydrogen, a terminating group, or a bond to a remainder of the material, provided that at least one * is a bond to the remainder of the material, and wherein the remainder of the material is bound via a sp3-sp3 carbon-carbon bond.

13. The material of claim 11 or claim 12, wherein each Ri is methyl.

14. The material of any one of claims 11-13, wherein m and n are each independently an integer from 1 to 1000.

15. The material of any one of claims 11-14, wherein the bond to a remainder of the material is a bond to a macromolecular support selected from a membrane, a fibrous media, a polymeric coating or material, a metal organic framework, a monolith support, a bead, a filter, or a resin, and wherein the macromolecular support is bound via a sp3-sp3 carbon-carbon bond.Leydig 7739853816. The material of claim 15. wherein the macromolecular 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.

17. A method of making a material of any one of claims 11-16, the method comprising:(i) (a) irradiating a polymeric support with an irradiation source and subsequently impregnating the polymeric support with glycidyl (meth)acrylate or a polymer thereof or (b) generating radicals on a polymeric support in the presence of glycidyl (meth Jacr late or a polymer thereof, wherein the polymeric support comprises one or more C-H aliphatic bonds, to graft the glycidyl (meth)acrylate or a polymer thereof on the polymeric support via one or more sp3-sp3 carbon-carbon bonds, and(ii) modifying the grafted glycidyl (meth)acrylate or a polymer thereof with one or more compounds of formula X’-Y’. wherein X’ is HO-, and Y?is (a) hydrogen or (b) a Ci-io alkyl group, C2-10 alkenyl group, C2-10 alkynyl group, C1-10 heteroalkyl group, C3-10 cycloalkyl group, C3-10 heterocycloalkyl group, C3-10 aryl group, C2-10 heteroaryl group, or a combination thereof, comprising from 1-10 hydroxyl substituents.

18. The method of claim 17, wherein the method comprises irradiating the polymeric support with E-beam irradiation, gamma irradiation, X-ray irradiation, or a combination thereof and subsequently impregnating the polymeric support with glycidyl (meth)acrylate or a polymer thereof.

19. A method of removing one or more metal ions from a solution comprising (i) passing the solution through a material of claim 11 or (ii) contacting the solution with a material of any one of claims 11-16.

20. The method of claim 19, wherein the method removes at least 50% of one or more metal ions selected from lithium, sodium, magnesium, aluminum, potassium, calcium, barium, or a combination thereof.

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