Glycidyl (meth)acrylate materials and methods of use

Abstract

A material is provided comprising a (meth)acrylic acid glycidyl ester 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 R1is independently hydrogen or methyl, each X is independently -O-, -COO-, -S-, piperazinyl, or -NR2-, R2is hydrogen, aryl, heteroaryl, C 1‑6 alkylaryl, C 1‑6 alkylheteroaryl, or C 1‑6 alkyl, each Y is independently optionally present and is -NR3- or optionally substituted C 1‑6 alkyl, R3is hydrogen or C 1‑6 alkyl, each Z is independently aryl, heteroaryl, or C 2‑6 heterocyclyl, each of which is optionally substituted, and each * independently represents hydrogen, a terminal group, or a bond to the 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 an sp3-sp3 carbon-carbon bond.

Description

[0001] Cross-references to related applications

[0002] This patent application claims the benefit of U.S. Provisional Patent Application No. 63 / 546,966, filed November 2, 2023, which is incorporated herein by reference. Background Technology

[0003] Membrane-based liquid handling processes have been used in many industries. For example, direct flow filtration (DFF) and tangential flow filtration (TFF), including microfiltration, ultrafiltration, nanofiltration, and percolation, can be used to separate dissolved molecules or suspended particles.

[0004] However, removing small soluble particles (such as metal ions) from aqueous and / or organic solutions remains a challenge. Therefore, materials and methods for removing one or more metal ions from solution are still needed. This invention provides such materials and methods. These and other advantages of the invention (e.g., simple and clean coupling, uniform coupling, rotational mobility of ligands, efficient deprotonation, and / or easy chelation / coordination of ligands) and other inventive features will become apparent from the description of the invention provided herein. Summary of the Invention

[0005] This invention provides a material comprising glycidyl (meth)acrylate of formula (I):

[0006]

[0007] Formula (I),

[0008] Or its salts, wherein m is an integer from 1 to 10000, n is an integer from 0 to 10000, each R1 is independently hydrogen or methyl, each X is independently -O-, -COO-, -S-, piperazine- or -NR2-, and R2 is hydrogen, aryl, heteroaryl, C 1-6 alkylaryl, C 1-6 alkyl heteroaryl or C 1-6 Alkyl group, each Y being independently present and optionally substituted with -NR3- or C. 1-6 Alkyl group, R3 is hydrogen or C 1-6 Alkyl groups, each Z being independently aryl (e.g., haloaryl), heteroaryl, or C. 2-6 Heterocyclic groups, each of which is optionally substituted, and each * independently represents a hydrogen, a terminal group, or a bond with the remainder of the material, provided that at least one * is a bond with the remainder of the material, and wherein the remainder of the material is bonded via sp3-sp3 carbon-carbon bonds.

[0009] The present invention also provides a method for preparing the material described herein, the method comprising (i) (a) irradiating (e.g., radiation) a polymer support with an irradiation (e.g., radiation) source, followed by impregnation of the polymer support with glycidyl methacrylate or a polymer thereof, or (b) generating free radicals on the polymer support in the presence of glycidyl methacrylate or a polymer thereof, wherein the polymer support comprises one or more CH aliphatic bonds to graft glycidyl methacrylate or a polymer thereof onto the polymer support via one or more sp3-sp3 carbon-carbon bonds, and (ii) modifying the grafted glycidyl methacrylate or a polymer thereof with one or more compounds of the formula X'-Y'-Z', wherein X' is HO-, HOOC-, HS-, piperazine-, or HNR2-, and R2 is hydrogen, aryl, heteroaryl, C 1-6 alkylaryl, C 1-6 alkyl heteroaryl or C 1-6 Alkyl group, Y' is optional and is -NR3- or optionally substituted C 1-6 Alkyl group, R3 is hydrogen or C 1-6 Alkyl, and Z' is aryl (e.g., haloaryl), heteroaryl, or C. 2-6 Heterocyclic groups, each of which is optionally substituted.

[0010] The present invention also provides a method for removing one or more metal ions from a solution, the method comprising passing the solution through or contacting the solution with the material described herein. Attached Figure Description

[0011] Figure 1A A scanning electron microscope (SEM) image of the top surface of the 3-aminomethylpyridine-modified glycidyl methacrylate-grafted high-density polyethylene (HDPE) prepared in Example 1 is provided.

[0012] Figure 1B A scanning electron microscope (SEM) image of the cross section of HDPE grafted with 3-aminomethylpyridine-modified glycidyl methacrylate prepared in Example 1 is provided.

[0013] Figure 2 A bar chart is provided showing the percentage of metal removal efficiency (MRE) of HDPE grafted with 3-aminomethylpyridine modified glycidyl methacrylate prepared in Example 2, as described in Example 3, for the removal of titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc and silver ions from cyclohexanone (CHN) solvent.

[0014] Figure 3A bar chart is provided showing the percentage of metal removal efficiency (MRE) of HDPE grafted with 3-aminomethylpyridine modified glycidyl methacrylate prepared in Example 2, as described in Example 3, for the removal of titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc and silver ions from propylene glycol methyl ether (PGME) solvent.

[0015] Figure 4 A bar chart is provided showing the percentage of metal removal efficiency (MRE) of HDPE grafted with 3-aminomethylpyridine modified glycidyl methacrylate prepared in Example 2, as described in Example 3, for the removal of titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc and silver ions from propylene glycol methyl ether acetate (PGMEA) / ethyl lactate (EL) solvent.

[0016] Figure 5 A bar chart is provided showing the percentage of metal removal efficiency (MRE) of HDPE grafted with 4-fluorobenzylamine modified with glycidyl methacrylate prepared in Example 4, as described in Example 5, for the removal of titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc and silver ions from cyclohexanone (CHN) solvent.

[0017] Figure 6 A bar chart is provided showing the percentage of metal removal efficiency (MRE) of HDPE grafted with 4-fluorobenzylamine modified glycidyl methacrylate prepared in Example 4, as described in Example 5, for the removal of titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc and silver ions from propylene glycol methyl ether (PGME) solvent.

[0018] Figure 7 A bar chart is provided showing the percentage of metal removal efficiency (MRE) of HDPE grafted with 4-fluorobenzylamine modified with glycidyl methacrylate prepared in Example 4, as described in Example 5, for the removal of titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc and silver ions from propylene glycol methyl ether acetate (PGMEA) / ethyl lactate (EL) solvent.

[0019] Figure 8A A bar chart is provided showing the percentage of metal removal efficiency (MRE) for removing titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc and silver ions from cyclohexanone (CHN) solvent, as exhibited by a composite material having an orientation of a layer of HDPE coating material of Example 2 on top and a layer of HDPE coating material of Example 4 on the bottom, as described in Example 6.

[0020] Figure 8BA bar chart is provided showing the percentage of metal removal efficiency (MRE) for removing titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc and silver ions from cyclohexanone (CHN) solvent, as exhibited by a composite material having an orientation of a layer of HDPE coating material of Example 4 on top and a layer of HDPE coating material of Example 2 on the bottom, as described in Example 6.

[0021] Figure 9A A bar chart is provided showing the percentage of metal removal efficiency (MRE) for removing titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc and silver ions from propylene glycol methyl ether (PGME) solvent, as described in Example 6, from a composite material having an orientation of a layer of HDPE coating material of Example 2 on top and a layer of HDPE coating material of Example 4 on the bottom.

[0022] Figure 9B A bar chart is provided showing the percentage of metal removal efficiency (MRE) for removing titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc and silver ions from propylene glycol methyl ether (PGME) solvent, as described in Example 6, from a composite material having an orientation of a layer of HDPE coating material of Example 4 on top and a layer of HDPE coating material of Example 2 on the bottom.

[0023] Figure 10A A bar chart is provided showing the percentage of metal removal efficiency (MRE) for removing titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc and silver ions from propylene glycol methyl ether acetate (PGMEA) / ethyl lactate (EL) solvent, as described in Example 6, from a composite material having an orientation of a layer of HDPE coating material of Example 2 on top and a layer of HDPE coating material of Example 4 on the bottom.

[0024] Figure 10B A bar chart is provided showing the percentage of metal removal efficiency (MRE) for removing titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc and silver ions from propylene glycol methyl ether acetate (PGMEA) / ethyl lactate (EL) solvent, as described in Example 6, from a composite material having an orientation of a layer of HDPE coating material of Example 4 on top and a layer of HDPE coating material of Example 2 on the bottom.

[0025] Figure 11 A bar chart is provided showing the percentage of metal removal efficiency (MRE) of HDPE grafted with glycidyl methacrylate modified with 3-aminomethylpyridine and 4-fluorobenzylamine prepared in Example 7, as described in Example 8, for the removal of titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc and silver ions from cyclohexanone (CHN) solvent.

[0026] Figure 12A bar chart is provided showing the percentage of metal removal efficiency (MRE) of HDPE grafted with glycidyl methacrylate modified with 3-aminomethylpyridine and 4-fluorobenzylamine prepared in Example 7, as described in Example 8, for the removal of titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc and silver ions from propylene glycol methyl ether (PGME) solvent.

[0027] Figure 13 A bar chart is provided showing the percentage of metal removal efficiency (MRE) of HDPE grafted with glycidyl methacrylate modified with 3-aminomethylpyridine and 4-fluorobenzylamine prepared in Example 7, as described in Example 8, for the removal of titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc and silver ions from propylene glycol methyl ether acetate (PGMEA) / ethyl lactate (EL) solvent. Detailed Implementation

[0028] One aspect of the present invention provides a material comprising glycidyl (meth)acrylate of formula (I):

[0029]

[0030] Formula (I),

[0031] Or its salts, wherein m is an integer from 1 to 10000, n is an integer from 0 to 10000, each R1 is independently hydrogen or methyl, each X is independently -O-, -COO-, -S-, piperazine- or -NR2-, and R2 is hydrogen, aryl, heteroaryl, C 1-6 alkylaryl, C 1-6 alkyl heteroaryl or C 1-6 Alkyl group, each Y being independently present and optionally substituted with -NR3- or C. 1-6 Alkyl group, R3 is hydrogen or C 1-6 Alkyl groups, each Z being independently aryl (e.g., haloaryl), heteroaryl, or C. 2-6 Heterocyclic groups, each of which is optionally substituted, and each * independently represents a hydrogen, a terminal group, or a bond with the remainder of the material, provided that at least one * is a bond with the remainder of the material, and wherein the remainder of the material is bonded via sp3-sp3 carbon-carbon bonds.

[0032] In some embodiments, the material comprises glycidyl (meth)acrylate of formula (Ia):

[0033]

[0034] Equation (Ia),

[0035] Or its salts, wherein m is an integer from 1 to 10000, n is an integer from 0 to 10000, each R1 is independently hydrogen or methyl, each X is independently -O-, -COO-, -S-, piperazine- or -NR2-, and R2 is hydrogen, aryl, heteroaryl, C 1-6 alkylaryl, C 1-6 alkyl heteroaryl or C 1-6 Alkyl group, each Y being independently present and optionally substituted with -NR3- or C. 1-6 Alkyl group, R3 is hydrogen or C 1-6 Alkyl groups, each Z being independently aryl (e.g., haloaryl), heteroaryl, or C. 2-6 Heterocyclic groups, each of which is optionally substituted, and each * independently represents a hydrogen, a terminal group, or a bond with the remainder of the material, provided that at least one * is a bond with the remainder of the material, and wherein the remainder of the material is bonded via sp3-sp3 carbon-carbon bonds.

[0036] As used herein, the term "(meth)acrylate" refers to acrylate or methacrylate. Therefore, in any embodiment of the materials described herein, each R1 is independently hydrogen or methyl. In some embodiments, each R1 is methyl. In other embodiments, each R1 is hydrogen.

[0037] In any embodiment of the materials 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 some embodiments, m is 1, meaning that the glycidyl methacrylate monomer is grafted onto the remainder of the material. In other embodiments, m is greater than 1, meaning that the glycidyl methacrylate polymer is grafted onto the remainder of the material.

[0038] In any embodiment of the materials 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 (meth)acrylate glycidyl monomer, labeled with the variable n, is optionally present. In some embodiments, n is an integer from 0 to 1000. In some embodiments, the unmodified (meth)acrylate glycidyl monomer is present in a form 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.

[0039] In any embodiment of the materials described herein, each X is independently -O-, -COO-, -S-, piperazine-, or -NR2-, wherein R2 is hydrogen, aryl, heteroaryl, C 1-6 alkylaryl, C 1-6 alkyl heteroaryl or C 1-6 Alkyl groups (e.g., straight-chain or branched methyl, ethyl, propyl, butyl, pentyl, or hexyl). In some embodiments, each X is independently -NR2-, and R2 is hydrogen, aryl, heteroaryl, C 1-6 alkylaryl, C 1-6 alkyl heteroaryl or C 1-6 Alkyl groups (e.g., straight-chain or branched methyl, ethyl, propyl, butyl, pentyl, or hexyl). In some embodiments, each X is -S-.

[0040] In any embodiment of the materials described herein, each Y is independently present and is -NR3- or optionally replaced by C. 1-6 Alkyl groups (e.g., straight-chain or branched methyl, ethyl, propyl, butyl, pentyl, or hexyl), wherein R3 is hydrogen or C 1-6 Alkyl groups (e.g., straight-chain or branched methyl, ethyl, propyl, butyl, pentyl, or hexyl). In some embodiments, each Y is independently -NR3-, where R3 is hydrogen or C. 1-6 Alkyl groups (e.g., straight-chain or branched methyl, ethyl, propyl, butyl, pentyl, or hexyl). In other embodiments, each Y is independently a optionally substituted C. 1-6 Alkyl groups (e.g., straight-chain or branched methyl, ethyl, propyl, butyl, pentyl, or hexyl).

[0041] In any embodiment of the materials described herein, each Z is independently aryl, heteroaryl, or C. 2-6Heterocyclic groups, each of which is optionally substituted. For example, Z can be phenyl, furanyl, benzofuranyl, thiophenyl, benzothiophenyl, pyrrolyl, indolyl, isoindolyl, azaindolyl, pyridyl, quinolinyl, isoquinolinyl, oxazolyl, isoxazolyl, benzoxazolyl, pyrazolyl, imidazolyl, benzimidazolyl, thiazolyl, benzothiazolyl, isothiazolyl, pyridazinyl, pyrazinyl, triazinyl, cenolinyl, phthalazinyl, quinazolinyl, morpholinyl, pyrrolidone, pyrrolylalkyl, piperidinyl, hydantoinyl, valeramide, ethylene oxide, oxacyclobutyl, tetrahydrofuranyl, tetrahydropyranyl, tetrahydropyridyl, tetrahydropyrimidinyl, tetrahydrothiophenyl, tetrahydrothiaranyl, tetrahydropyrimidinyl, tetrahydrothiaranyl, tetrahydrothiaranyl, tetrahydrothiaranyl, piperazinyl, or dihydropyrimidinyl, each of which may be optionally substituted. In some embodiments, at least one Z is a haloaryl (e.g., a fluorinated aryl) or a haloheteroaryl (e.g., a fluorinated heteroaryl). Alternatively or otherwise, at least one Z is an optionally substituted pyridyl group. In some embodiments, at least one Z is an optionally substituted pyridyl group.

[0042] In some implementations, each Z is independently selected from the following:

[0043] , , , , , , , , , , , , , , , , , , , and Each of them is optional to replace.

[0044] As used herein, the term "optionally substituted" refers to a group selected from halogens (e.g., fluorine, chlorine, bromine, or iodine), cyano, nitro, trifluoromethyl, sulfonyl (e.g., sulfate esters, sulfonates, sulfoxides, etc.), hydroxyl, amino (e.g., primary, secondary, or tertiary amines having 1 to 8 carbons), C 1-8 Alkyl, C 1-8 Alkoxy, C 1-8 aminoalkyl, C 1-8 Hydroxyl alkyl groups and any combination thereof with one or more optional substituents. Alternatively or otherwise, when referring to optionally substituted aryl, heteroaryl, or C... 2-6When referring to heterocyclic groups, the term "optionally substituted" can refer to fused or bridged aryl, heteroaryl, or C-aryl groups. 2-6 Heterocyclic group.

[0045] In some implementations, each part XYZ is independently selected from the following:

[0046] , , , , , , , , , , , , , , , , , , , , , , , , , and .

[0047] In any embodiment of the materials described herein, each * independently represents a hydrogen, a terminal group, or a bond with the remainder of the material, provided that at least one * is a bond with the remainder of the material, and wherein the remainder of the material is bonded via sp3-sp3 carbon-carbon bonds. As used herein, the term "terminal group" refers to any chemical portion remaining after free radical quenching. Common terminal groups will be apparent to those skilled in the art. In some embodiments of the materials described herein, each * independently represents a hydrogen or a bond with the remainder of the material, provided that at least one * is a bond with the remainder of the material, and wherein the remainder of the material is bonded via sp3-sp3 carbon-carbon bonds. In some embodiments, the material comprising glycidyl methacrylate of formula (I) or glycidyl methacrylate of formula (Ia) has more than one C-C bond with the remainder of the material. Alternatively or otherwise, the material may comprise more than one glycidyl methacrylate of formula (I) or glycidyl methacrylate of formula (Ia).

[0048] Glycidyl methacrylate of formula (I) or formula (Ia) can be incorporated into any suitable material (e.g., a compound or a medium) provided that the glycidyl methacrylate of formula (I) or formula (Ia) is bonded to the remainder of the material via at least one carbon atom marked with an asterisk (*) in formulas (I) and (Ia), wherein the remainder of the material is bonded via sp3-sp3 carbon-carbon bonds. Those skilled in the art will readily understand that glycidyl methacrylate of formula (I) or formula (Ia) can be incorporated into the material at any number of positions and any number of times. Therefore, the material can be any suitable material (e.g., a compound or a medium) containing aliphatic CH bonds that can be used for sp3-sp3 carbon-carbon bonds. In some embodiments, the material is porous, allowing liquids or fluids to pass through it.

[0049] In some embodiments, the remainder of the material combined with glycidyl methacrylate of formula (I) or glycidyl methacrylate of formula (Ia) is a macromolecular carrier selected from the following: membranes (e.g., porous or permeable membranes), fibrous media, polymer coatings (e.g., laminates 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 oxide / polypropylene oxide, polyacrylonitrile, poly(meth)acrylate, poly(meth)acrylamide, polyamide, polyimide, polyester, cellulose, polystyrene, etc.), metal-organic frameworks, monolithic carriers (e.g., catalyst carriers), beads (e.g., polymer beads), filters, or resins (e.g., chromatographic resins). In some embodiments, the macromolecular carrier includes gelatin, alginate, starch, polyethylene (e.g., high-density polyethylene), polypropylene, nylon, polyvinylidene fluoride, polyethylene oxide, polypropylene oxide, polyethylene oxide / polypropylene oxide, polyacrylonitrile, poly(meth)acrylate, poly(meth)acrylamide, polyamide (e.g., nylon), polyimide, polyester, cellulose, polystyrene, or combinations thereof. In some embodiments, the macromolecular carrier includes polyethylene, polypropylene, nylon, polyvinylidene fluoride, polyethylene oxide, polypropylene oxide, polyethylene oxide / polypropylene oxide, polyacrylonitrile, cellulose, or combinations thereof. In a preferred embodiment, the macromolecular carrier includes polyvinylidene fluoride, polyethylene (e.g., high-density polyethylene), polypropylene, nylon, or combinations thereof.

[0050] Therefore, in some embodiments, the material has formula (II):

[0051] ,

[0052] Or formula (IIa):

[0053]

[0054] Or its salts, wherein m is an integer from 1 to 10000, n is an integer from 0 to 10000, each R1 is independently hydrogen or methyl, each X is independently -O-, -COO-, -S-, piperazine- or -NR2-, and R2 is hydrogen, aryl, heteroaryl, C 1-6 alkylaryl, C 1-6 alkyl heteroaryl or C 1-6 Alkyl group, each Y being independently present and optionally substituted with -NR3- or C. 1-6 Alkyl group, R3 is hydrogen or C 1-6 Alkyl group, each Z being independently aryl, heteroaryl, or C. 2-6 Heterocyclic groups, each of which may be optionally substituted, and each Q independently being a hydrogen, a terminal group, or an MS, provided that at least one Q is an MS, and each MS independently being a macromolecular support selected from membranes, fibrous media, polymer coatings or materials, metal-organic frameworks, monolithic carriers, beads, filters, or resins, and wherein the MS is linked via sp3-sp3 carbon-carbon bonds. All other definitions and embodiments regarding the variables m, n, R1, X, Y, Z, and macromolecular supports are as described herein with respect to the inventive material.

[0055] In any embodiment of the materials described herein, each Q is independently hydrogen, a terminal group, or MS, provided that at least one Q is MS, wherein the MS is bonded via sp3-sp3 carbon-carbon bonds. In some embodiments of the materials described herein, each Q is independently hydrogen or MS, provided that at least one Q is MS, wherein the MS is bonded via sp3-sp3 carbon-carbon bonds. In some embodiments, the materials of formula (II) or (IIa) have more than one C-MS bond.

[0056] In some embodiments, the material comprises 3-aminomethylpyridine-modified glycidyl methacrylate, 4-fluorobenzylamine-modified glycidyl methacrylate, 2-aminomethylpyridine-modified glycidyl methacrylate, 1-(3-aminopropyl)imidazolium-modified glycidyl methacrylate, or combinations thereof. In this respect, the materials disclosed herein may comprise one or more -XYZ portions as defined herein. For example, the material may comprise 3-aminomethylpyridine-modified glycidyl methacrylate, 4-fluorobenzylamine-modified glycidyl methacrylate, 2-aminomethylpyridine-modified glycidyl methacrylate, or 1-(3-aminopropyl)imidazolium-modified glycidyl methacrylate, or any combination of these modifications. In some embodiments, the material comprises a combination of 3-aminomethylpyridine-modified glycidyl methacrylate and 4-fluorobenzylamine-modified glycidyl methacrylate.

[0057] In some embodiments, the materials described herein are present as a membrane (e.g., a thin film). The membrane may have any suitable thickness. For example, the membrane may 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 materials described herein may comprise multiple membranes (e.g., thin films) stacked to form a composite material (e.g., a composite membrane). Thus, in some embodiments, the materials described herein are layered (e.g., stacked) to provide a composite material comprising one or more layers of the materials described herein. Thus, each layer of the composite material may comprise a material of formula (I) or (Ia) or formula (II) or (IIa) containing one or more XYZ portions. In some embodiments, one or more XYZ portions of each layer are identical. In other embodiments, one or more XYZ portions of each layer are different.

[0058] The present invention also provides one aspect of a method for preparing the material described herein, the method comprising:

[0059] (i) (a) Irradiating a polymer support with an irradiation (e.g., radiation) source, followed by impregnation of the polymer support with glycidyl methacrylate or a polymer thereof, or (b) generating free radicals on the polymer support in the presence of glycidyl methacrylate or a polymer thereof, wherein the polymer support contains one or more CH aliphatic bonds to graft glycidyl methacrylate or a polymer thereof onto the polymer support via one or more sp3-sp3 carbon-carbon bonds, and

[0060] (ii) Modifying the grafted glycidyl (meth)acrylate or its polymer with one or more compounds of the formula X'-Y'-Z', wherein X' is HO-, HOOC-, HS-, piperazine-, or HNR2-, and R2 is hydrogen, aryl, heteroaryl, C 1-6 alkylaryl, C 1-6 alkyl heteroaryl or C 1-6 Alkyl group, Y' is optional and is -NR3- or optionally substituted C 1-6 Alkyl group, R3 is hydrogen or C 1-6 Alkyl, and Z' is aryl, heteroaryl or C 2-6 Heterocyclic groups, each of which may be optionally substituted. All other definitions and embodiments regarding the variables m, n, R1, X, Y, Z, and macromolecular carriers are as described herein with respect to the material of the invention. In some embodiments, step (i) is carried out in an anaerobic 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, step (ii) is carried out in an anaerobic 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, steps (i) and (ii) are carried out in an anaerobic 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 some embodiments, steps (i) and / or steps (ii) are carried out in oxygen in an anaerobic environment having 0 to 10 ppm O2, 0 to 5 ppm O2, 2 to 10 ppm O2, or 2 to 5 ppm O2.

[0061] The method includes (a) irradiating (e.g., radiation) a polymer support with an irradiation (e.g., radiation) source, followed by impregnation of the polymer support with glycidyl methacrylate or a polymer thereof, or (b) generating free radicals on the polymer support in the presence of glycidyl methacrylate or a polymer thereof, wherein the polymer support contains one or more CH aliphatic bonds to graft glycidyl methacrylate or a polymer thereof onto the polymer support via one or more sp3-sp3 carbon-carbon bonds. Therefore, the polymer support can be irradiated or activated (e.g., by generating free radicals) in the presence or absence of glycidyl methacrylate or a polymer thereof. If the polymer support is irradiated or activated (e.g., by generating free radicals) in the absence of glycidyl methacrylate or a polymer thereof, then glycidyl methacrylate or a polymer thereof can subsequently be impregnated onto the polymer support.

[0062] Polymer supports can be irradiated or activated (e.g., by generating free radicals) in any suitable manner. For example, polymer supports can be irradiated or activated (e.g., by generating free radicals) using electron beam irradiation, gamma irradiation, X-ray irradiation, UV light, plasma, corona discharge, chemical initiators, or combinations thereof. In some embodiments, the method includes irradiating the polymer support with electron beam irradiation, gamma irradiation, X-ray irradiation, or combinations thereof, followed by impregnation of the polymer support with glycidyl methacrylate or a polymer thereof. In other embodiments, the method includes generating free radicals on the polymer support using UV light, plasma, corona discharge, chemical initiators, or combinations thereof in the presence of glycidyl methacrylate or a polymer thereof.

[0063] Glycidyl methacrylate or its polymers can be grafted onto a polymer support using any suitable method and at any suitable temperature. For example, an irradiated or activated (e.g., by generating free radicals) polymer support can be immersed in a solution containing glycidyl methacrylate or its polymers (e.g., a monomer solution), or the irradiated or activated (e.g., by generating free radicals) polymer support can be sprayed with a solution containing glycidyl methacrylate or its polymers (e.g., a monomer solution), or the polymer support can be irradiated or activated (e.g., by generating free radicals) while immersed in a solution containing glycidyl methacrylate or its polymers (e.g., a monomer solution). Glycidyl methacrylate or its polymers can be grafted onto the polymer support at temperatures of 0°C to 100°C, 0°C to 50°C, 10°C to 30°C, or 20°C to 30°C. Typically, glycidyl methacrylate or its polymers are grafted onto the polymer support at room temperature (e.g., about 25°C). In some embodiments, the polymer carrier, or the irradiated or activated (e.g., by generating free radicals) polymer carrier, is in roll form, which can be wound or unwound during any stage of the process.

[0064] Solutions containing glycidyl methacrylate or polymers thereof (e.g., monomer solutions) may contain any suitable solvent. For example, solutions containing glycidyl methacrylate or polymers thereof (e.g., monomer solutions) may contain organic solvents such as alcohols (e.g., ethanol or methanol), sulfoxides, sulfides, acetates, ethers, amides, nitriles, or combinations thereof. In some embodiments, solutions containing glycidyl methacrylate or polymers thereof (e.g., monomer solutions) contain alcohols such as methanol as solvents. In some embodiments, solutions containing glycidyl methacrylate or polymers thereof (e.g., monomer solutions) also contain allyl glycidyl ether, 1,2-epoxy-5-hexene, 3,4-epoxy-1-butene, allyl 2,3-epoxypropyl ether, or combinations thereof.

[0065] This method involves modifying the grafted glycidyl (meth)acrylate or its polymer with one or more compounds of the formula X'-Y'-Z', wherein X' is HO-, HOOC-, HS-, piperazine-, or HNR2-, and R2 is hydrogen, aryl, heteroaryl, C 1-6 alkylaryl, C 1-6 alkyl heteroaryl or C 1-6 Alkyl groups (e.g., straight-chain or branched methyl, ethyl, propyl, butyl, pentyl, or hexyl), Y' is optionally present and is -NR3- or optionally substituted C 1-6 Alkyl groups (e.g., straight-chain or branched methyl, ethyl, propyl, butyl, pentyl, or hexyl), where R3 is hydrogen or C.1-6 Alkyl (e.g., straight-chain or branched methyl, ethyl, propyl, butyl, pentyl, or hexyl), and Z' is aryl, heteroaryl, or C. 2-6 Heterocyclic groups, each of which is optionally substituted.

[0066] In some embodiments of compounds of formula X'-Y'-Z', X' is -NHR2, and R2 is hydrogen, aryl, heteroaryl, C 1-6 alkylaryl, C 1-6 alkyl heteroaryl or C 1-6 Alkyl groups (e.g., straight-chain or branched methyl, ethyl, propyl, butyl, pentyl, or hexyl). In some embodiments of compounds of the formula X'-Y'-Z', X' is -SH.

[0067] In some embodiments of compounds of formula X'-Y'-Z', Y' is -NR3-, where R3 is hydrogen or C. 1-6 Alkyl (e.g., straight-chain or branched methyl, ethyl, propyl, butyl, pentyl, or hexyl). In other embodiments of compounds of formula X'-Y'-Z', Y' is optionally substituted C. 1-6 Alkyl groups (e.g., straight-chain or branched methyl, ethyl, propyl, butyl, pentyl, or hexyl).

[0068] In some embodiments of compounds of formula X'-Y'-Z', Z' is aryl, heteroaryl, or C. 2-6 Heterocyclic groups, each of which is optionally substituted. For example, Z can be phenyl, furanyl, benzofuranyl, thiophenyl, benzothiophenyl, pyrrolyl, indolyl, isoindolyl, azaindolyl, pyridyl, quinolinyl, isoquinolinyl, oxazolyl, isoxazolyl, benzoxazolyl, pyrazolyl, imidazolyl, benzimidazolyl, thiazolyl, benzothiazolyl, isothiazolyl, pyridazinyl, pyrazinyl, triazinyl, cenolinyl, phthalazinyl, quinazolinyl, morpholinyl, pyrrolidone, pyrrolylalkyl, piperidinyl, hydantoinyl, valeramide, ethylene oxide, oxacyclobutyl, tetrahydrofuranyl, tetrahydropyranyl, tetrahydropyridyl, tetrahydropyrimidinyl, tetrahydrothiophenyl, tetrahydrothiaranyl, tetrahydropyrimidinyl, tetrahydrothiaranyl, tetrahydrothiaranyl, tetrahydrothiaranyl, piperazinyl, or dihydropyrimidinyl, each of which may be optionally substituted. In some embodiments, Z' is a haloaryl (e.g., a fluorinated aryl) or a haloheteroaryl (e.g., a fluorinated heteroaryl). In some embodiments, Z' is optionally a substituted pyridyl group.

[0069] In some embodiments, the compounds of formula X'-Y'-Z' are selected from the following compounds:

[0070] , , , , , , , , , , , , , , , , , , , , , , , , , and .

[0071] Grafted glycidyl methacrylate or its polymers can be modified with one or more compounds of formula X'-Y'-Z' in any suitable manner and at any suitable temperature. For example, the grafted glycidyl methacrylate or its polymers can be modified by mixing, contacting, immersing, etc., with a solution containing one or more compounds of formula X'-Y'-Z' or multiple solutions containing compounds of formula X'-Y'-Z'. The solution containing one or more compounds of formula X'-Y'-Z' may contain a solvent, such as, for example, water, an alcohol (e.g., ethanol or methanol), sulfoxide, sulfide, acetate, ether, amide, nitrile, or combinations thereof. In some embodiments, the solution containing one or more compounds of formula X'-Y'-Z' may contain dimethylformamide (DMF), N-methyl-2-pyrrolidone (NMP), N,N-dimethylacetamide (DMAc), and / or dimethyl sulfoxide (DMSO), optionally in combination with water. Grafted glycidyl methacrylate or its polymers can be modified at temperatures ranging from 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, and 50°C to 100°C. Typically, glycidyl methacrylate or its polymers are grafted onto a polymer support at temperatures ranging from about 75°C to 100°C.

[0072] A solution containing one or more compounds of the formula X'-Y'-Z' may contain any suitable amount of one or more compounds of the formula X'-Y'-Z'. For example, a solution containing one or more compounds of the formula X'-Y'-Z' may contain 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 one or more compounds of the formula X'-Y'-Z'.

[0073] Modification of grafted glycidyl methacrylate or its polymers can be promoted by acids (e.g., Brønsted acids or Lewis acids) or bases (e.g., Brønsted bases or Lewis bases). In some embodiments, modification of grafted glycidyl methacrylate or its polymers is promoted by amine bases (e.g., trimethylamine, trimethylamine, diisopropylethylamine, etc.).

[0074] Modified grafted glycidyl (meth)acrylate or its polymers (i.e., the materials described herein) can be washed with water, organic solvents (e.g., alcohols such as ethanol or methanol, sulfoxides, sulfides, acetates, ethers, amides, nitriles, or combinations thereof), acidic solutions (e.g., aqueous solutions of hydrochloric acid or sulfuric acid), alkaline solutions (e.g., aqueous solutions of tetramethylammonium hydroxide or ammonium hydroxide), or combinations thereof. In some embodiments, the modified grafted glycidyl (meth)acrylate or its polymers (i.e., the materials described herein) is washed with an acidic solution (e.g., aqueous solutions of hydrochloric acid or sulfuric acid) followed by an alkaline solution (e.g., aqueous solutions of tetramethylammonium hydroxide or ammonium hydroxide).

[0075] Modified grafted glycidyl (meth)acrylate or its polymers (i.e., the materials described herein) or intermediates thereof can be dried by any suitable method. For example, modified grafted glycidyl (meth)acrylate or its polymers (i.e., the materials described herein) or intermediates thereof can be dried by air, desiccant, sieve, or a combination thereof.

[0076] 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., microelectronics) applications, papermaking applications, pharmaceutical applications, biomedical applications, energy applications (e.g., as a separator in a fuel cell or battery), or metallurgical applications. Typically, the materials described herein are used to selectively remove one or more metal ions from a fluid (i.e., a solution). The fluid can be any suitable liquid containing a solvent (e.g., water, alcohol, sulfoxide, sulfide, acetate, ether, ketone, amide, nitrile, or a combination thereof) and one or more metal ions. In some embodiments, the fluid (i.e., the solution) is an aqueous solution. In some embodiments, the fluid (i.e., the solution) contains an organic solvent, such as, for example, an alcohol (e.g., ethanol or methanol), sulfoxide, sulfide, acetate, ether, ketone, amide, nitrile, or a combination thereof. In some embodiments, the fluid contains cyclohexanone (CHN), propylene glycol methyl ether (PGME), propylene glycol methyl ether acetate (PGMEA), ethyl lactate, or a combination thereof.

[0077] 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 (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, etc., through which a solution passes or contacts to remove one or more metal ions. Therefore, the present invention also provides a method for removing one or more metal ions from a solution, the method comprising (i) passing the solution through a material comprising glycidyl methacrylate of formula (I), formula (Ia), formula (II), or formula (IIa), or (ii) contacting the solution with it. In some embodiments, the present invention provides a method for removing one or more metal ions from a solution, the method comprising (i) passing the solution through one or more materials comprising glycidyl methacrylate of formula (I), formula (Ia), formula (II), or formula (IIa), or (ii) contacting the solution with it.

[0078] This method can be used to remove any suitable ions. Alternatively or otherwise, this method can be used to allow any suitable ions to pass through the material. For example, this method can be used to selectively remove one or more metal ions selected from the group consisting of sodium, magnesium, aluminum, potassium, calcium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, arsenic, zirconium, molybdenum, silver, cadmium, tin, barium, tungsten, strontium, lead, or combinations thereof. Alternatively or otherwise, this method can be used to selectively allow one or more metal ions selected from the group consisting of sodium, magnesium, aluminum, potassium, calcium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, arsenic, zirconium, molybdenum, silver, cadmium, tin, barium, tungsten, strontium, lead, or combinations thereof. In some embodiments, this method selectively allows lithium to pass through the material and removes one or more metal ions selected from the group consisting of sodium, magnesium, aluminum, potassium, calcium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, arsenic, zirconium, molybdenum, silver, cadmium, tin, barium, tungsten, strontium, lead, or combinations thereof.

[0079] This method can remove any suitable amount of one or more metal ions from a solution. For example, the method can remove at least 40% of one or more metal ions from a solution, at least 50% of one or more metal ions from a solution, at least 60% of one or more metal ions from a solution, at least 70% of one or more metal ions from a solution, at least 80% of one or more metal ions from a solution, or at least 90% of one or more metal ions from a solution. In some embodiments, the method removes at least 50% of one or more metal ions selected from the group consisting of sodium, magnesium, aluminum, potassium, calcium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, arsenic, zirconium, molybdenum, silver, cadmium, tin, barium, tungsten, strontium, lead, or combinations thereof. In some embodiments, the method removes at least 60% of one or more metal ions selected from the group consisting of sodium, magnesium, aluminum, potassium, calcium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, arsenic, zirconium, molybdenum, silver, cadmium, tin, barium, tungsten, strontium, lead, or combinations thereof. In a preferred embodiment, the method removes at least 70% of one or more metal ions selected from the group consisting of sodium, magnesium, aluminum, potassium, calcium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, arsenic, zirconium, molybdenum, silver, cadmium, tin, barium, tungsten, strontium, lead, or combinations thereof.

[0080] In some embodiments, the solution that has passed through or come into contact with the material is the desired product of the methods described herein. Therefore, in such embodiments, the method may also include recovering solutions (e.g., aqueous or organic solutions) that have passed through or come into contact with the material. Without wishing to be bound by any particular theory, it is believed that the recovered solution would be the desired product when smaller metal ions such as lithium and / or sodium are required, as smaller metal ions such as lithium and / or sodium are more likely to pass through the material described herein.

[0081] In other embodiments, one or more metal ions removed from the solution are the desired products of the methods described herein. Therefore, in these embodiments, the method may also include recovering one or more metal ions removed from the solution. One or more metal ions can be recovered by any suitable means. For example, materials containing one or more metal ions can be washed with a recovery solution. Without wishing to be bound by any particular theory, it is believed that when larger metal ions such as magnesium, aluminum, potassium, calcium, manganese, iron, barium, etc., are needed, these desired metal ions will remain in the material because larger metal ions are unlikely to pass through the materials described herein.

[0082] The aspects of the invention described herein (including embodiments) may be advantageous, alone or in combination with one or more other aspects or embodiments. Without limiting the foregoing description, certain non-limiting embodiments of this disclosure, numbered 1-24, are provided below. As will be apparent to those skilled in the art upon reading this disclosure, each embodiment of the individually numbered embodiments may be used or combined with any embodiment of the preceding or following individually numbered embodiments. This is intended to support all such combinations of embodiments and is not limited to combinations of embodiments explicitly provided below:

[0083] Implementation Plan

[0084] (1) In embodiment (1), a material is proposed comprising glycidyl (meth)acrylate of formula (I):

[0085]

[0086] Formula (I),

[0087] Or its salts, wherein m is an integer from 1 to 10000, n is an integer from 0 to 10000, each R1 is independently hydrogen or methyl, each X is independently -O-, -COO-, -S-, piperazine- or -NR2-, and R2 is hydrogen, aryl, heteroaryl, C 1-6 alkylaryl, C 1-6 alkyl heteroaryl or C 1-6 Alkyl group, each Y being independently present and optionally substituted with -NR3- or C. 1-6 Alkyl group, R3 is hydrogen or C 1-6 Alkyl group, each Z being independently aryl, heteroaryl, or C. 2-6 Heterocyclic groups, each of which is optionally substituted, and each * independently represents a hydrogen, a terminal group, or a bond with the remainder of the material, provided that at least one * is a bond with the remainder of the material, and wherein the remainder of the material is bonded via sp3-sp3 carbon-carbon bonds.

[0088] (2) In embodiment (2), a material as described in embodiment (1) is provided, wherein the material comprises glycidyl (meth)acrylate of formula (Ia):

[0089]

[0090] Equation (Ia),

[0091] Or its salts, wherein m is an integer from 1 to 10000, n is an integer from 0 to 10000, each R1 is independently hydrogen or methyl, each X is independently -O-, -COO-, -S-, piperazine- or -NR2-, and R2 is hydrogen, aryl, heteroaryl, C 1-6 alkylaryl, C 1-6 alkyl heteroaryl or C 1-6 Alkyl group, each Y being independently present and optionally substituted with -NR3- or C. 1-6 Alkyl group, R3 is hydrogen or C 1-6 Alkyl group, each Z being independently aryl, heteroaryl, or C. 2-6 Heterocyclic groups, each of which is optionally substituted, and each * independently represents a hydrogen, a terminal group, or a bond with the remainder of the material, provided that at least one * is a bond with the remainder of the material, and wherein the remainder of the material is bonded via sp3-sp3 carbon-carbon bonds.

[0092] (3) The material described in the implementation scheme (1) or the implementation scheme (2) is proposed in the implementation scheme (3), wherein each R1 is methyl.

[0093] (4) The materials described in any one of the embodiments (1)-(3) are provided in the implementation scheme (4), wherein m is an integer from 1 to 1000.

[0094] (5) The implementation scheme (5) provides the materials as described in any one of the implementation schemes (1)-(4), where n is an integer from 1 to 1000.

[0095] (6) The embodiment (6) provides a material as described in any one of embodiments (1)-(5), wherein each X is independently -NR2- and R2 is hydrogen, aryl, heteroaryl, C 1-6 alkylaryl, C 1-6 alkyl heteroaryl or C 1-6 alkyl.

[0096] (7) The implementation scheme (7) provides the material as described in any one of the implementation schemes (1)-(5), wherein each X is -S-.

[0097] (8) The embodiment (8) provides for the material as described in any one of embodiments (1)-(7), wherein each Z is independently phenyl, furanyl, benzofuranyl, thienyl, benzothienyl, pyrroleyl, indolyl, isoyindolyl, azaindolyl, pyridinyl, quinolinyl, isoquinolinyl, oxazolyl, isoxazolyl, benzoxazolyl, pyrazolyl, imidazoleyl, benzimidazoleyl, thiazolyl, benzothiazolyl, isothiazolyl, pyridazinyl The group may be pyrimidinyl, pyrazinyl, triazinyl, cyclolinyl, phthalazinyl, quinazolinyl, morpholinyl, pyrrolidone, pyrrolylalkyl, piperidinyl, hydantoinyl, valeronyl, ethylene oxide, oxacyclobutyl, tetrahydrofuranyl, tetrahydropyranyl, tetrahydropyridinyl, tetrahydropyrimidinyl, tetrahydrothiophenyl, tetrahydrothiophenyl, tetrahydropyrimidinyl, tetrahydrothiophenyl, piperazinyl or dihydropyrimidinyl, each of which may be optionally substituted.

[0098] (9) The embodiment (9) provides the material as described in any one of the embodiments (1)-(8), wherein at least one Z is a haloaryl or haloheteroaryl.

[0099] (10) The embodiment (10) provides a material as described in any one of the embodiments (1)-(9), wherein at least one Z is a fluorinated aryl or a fluorinated heteroaryl.

[0100] (11) The material as described in any one of embodiments (1)-(10) is provided in embodiment (11), wherein at least one Z is optionally substituted pyridinyl.

[0101] (12) The embodiment (12) provides a material as described in any one of embodiments (1)-(11), wherein the bond with the remainder of the material is a bond with a macromolecular carrier selected from membranes, fibrous media, polymer coatings or materials, metal-organic frameworks, monolithic carriers, beads, filters or resins, and wherein the macromolecular carrier is bonded via sp3-sp3 carbon-carbon bonds.

[0102] (13) The embodiment (13) proposes the material as described in embodiment (12), wherein the macromolecular carrier includes gelatin, alginate, starch, polyethylene, polypropylene, nylon, polyvinylidene fluoride, polyethylene oxide, polypropylene oxide, polyethylene oxide / polypropylene oxide, polyacrylonitrile, poly(meth)acrylate, poly(meth)acrylamide, polyamide, polyimide, polyester, cellulose, polystyrene or combinations thereof.

[0103] (14) The embodiment (14) proposes the material as described in the embodiment (12), wherein the macromolecular carrier includes polyvinylidene fluoride, polyethylene, polypropylene, nylon or combinations thereof.

[0104] (15) A method for preparing the material as described in any one of embodiments (1)-(14) is provided in embodiment (15), the method comprising:

[0105] (i) (a) Irradiating a polymer support with an irradiation (e.g., radiation) source, followed by impregnation of the polymer support with glycidyl methacrylate or a polymer thereof, or (b) generating free radicals on the polymer support in the presence of glycidyl methacrylate or a polymer thereof, wherein the polymer support contains one or more CH aliphatic bonds to graft glycidyl methacrylate or a polymer thereof onto the polymer support via one or more sp3-sp3 carbon-carbon bonds, and

[0106] (ii) Modifying the grafted glycidyl (meth)acrylate or its polymer with one or more compounds of the formula X'-Y'-Z', wherein X' is HO-, HOOC-, HS-, piperazine-, or HNR2-, and R2 is hydrogen, aryl, heteroaryl, C 1-6 alkylaryl, C 1-6 alkyl heteroaryl or C 1-6 Alkyl group, Y' is optional and is -NR3- or optionally substituted C 1-6 Alkyl group, R3 is hydrogen or C 1-6 Alkyl, and Z' is aryl, heteroaryl or C 2-6 Heterocyclic groups, each of which is optionally substituted.

[0107] (16) The method described in embodiment (15) is proposed in embodiment (16), wherein the method comprises irradiating (e.g., radiation) the polymer carrier with electron beam irradiation, gamma irradiation, X-ray irradiation or a combination thereof, and then impregnating the polymer carrier with glycidyl (meth)acrylate or a polymer thereof.

[0108] (17) The method described in embodiment (15) is proposed in embodiment (17), wherein the method comprises generating free radicals on the polymer support by UV light, plasma, corona discharge, chemical initiator or combination thereof in the presence of glycidyl methacrylate or a polymer thereof.

[0109] (18) The method of any one of the embodiments (15)-(17) is proposed in embodiment (18), wherein steps (i) and / or (ii) are carried out in an environment with an O2 concentration of 50 ppm or lower.

[0110] (19) A method for removing one or more metal ions from a solution is provided in embodiment (19), the method comprising (i) passing the solution through a material as described in any one of embodiments (1)-(14), or (ii) contacting the solution with a material as described in any one of embodiments (1)-(14).

[0111] (20) The method described in embodiment (19) is proposed in embodiment (20), wherein the solution is an aqueous solution.

[0112] (21) The method described in embodiment (19) or embodiment (20) is proposed in embodiment (21), wherein the solution contains an organic solvent.

[0113] (22) The implementation scheme (22) proposes a method as described in any one of the implementation schemes (19)-(21), wherein the method removes at least 50% of one or more metal ions selected from the group consisting of sodium, magnesium, aluminum, potassium, calcium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, arsenic, zirconium, molybdenum, silver, cadmium, tin, barium, tungsten, strontium, lead or combinations thereof.

[0114] (23) The implementation scheme (23) proposes a method as described in any one of the implementation schemes (19)-(21), wherein the method removes at least 60% of one or more metal ions selected from the group consisting of sodium, magnesium, aluminum, potassium, calcium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, arsenic, zirconium, molybdenum, silver, cadmium, tin, barium, tungsten, strontium, lead or combinations thereof.

[0115] (24) The implementation scheme (24) provides a method as described in any one of the implementation schemes (19)-(21), wherein the method removes at least 70% of one or more metal ions selected from the group consisting of sodium, magnesium, aluminum, potassium, calcium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, arsenic, zirconium, molybdenum, silver, cadmium, tin, barium, tungsten, strontium, lead or combinations thereof.

[0116] Example

[0117] The following embodiments further illustrate the invention, but should not be construed as limiting its scope in any way.

[0118] Example 1

[0119] This embodiment provides an exemplary experimental procedure for preparing glycidyl methacrylate-grafted rolls, which is summarized in Scheme 1.

[0120] Option 1.

[0121]

[0122] High-density polyethylene (HDPE) (1 μm) substrate was fed into an electron beam, irradiated, co-wound with a release liner, immersed in a coating solution containing glycidyl methacrylate, and rewound to form a glycidyl methacrylate-grafted roll. The coating solution was prepared by dissolving 2 kg of glycidyl methacrylate in 18 kg of methanol and mixing for 10 minutes to form a 10% by weight solution of glycidyl methacrylate in methanol. The electron beam and grafting conditions are listed in Table 1 below.

[0123] Table 1. Electron beam and grafting conditions

[0124] Process parameters Specification Linear velocity (ft / min) 34 Dosage (mRad) 12 Unwinding tension (lb) 3.5 Rewinding tension (lb) 8.0 Pressure roller setting (psi) Both sides are 5.5 <![CDATA[O2 (ppm) at the peeling point]]> <50 <![CDATA[Rewinding area O2 (ppm]]> <50 <![CDATA[O2 (ppm) at the window]]> <50

[0125] As indicated in Table 1, all unwinding, irradiation, monomer impregnation, and rewinding processes were performed in an environment with an O2 level <50 ppm. Weight change, critical water surface tension (CWST), and FTIR were used to confirm the grafting of glycidyl methacrylate onto the HDPE substrate.

[0126] The glycidyl methacrylate-grafted rolls were washed with methanol for 4 hours using a cyclic rinsing process, followed by rinsing with deionized water for 6 hours to remove any residual ungrafted monomers, oligomers, and polymers. After drying the glycidyl methacrylate-grafted rolls, the glycidyl methacrylate absorption was determined to be approximately 100-140% by weight based on the HDPE substrate.

[0127] Example 2

[0128] This embodiment provides an exemplary experimental procedure for preparing materials of formula (I) as described herein, which is summarized in Scheme 2.

[0129] Option 2.

[0130]

[0131] 10 g of 3-aminomethylpyridine was dissolved in 90 g of water / DMSO (1:1), and the resulting solution was added to a 12'' × 12'' strip of glycidyl methacrylate-grafted HDPE. The mixture was heated to 85°C and held for 24 hours. After cooling the glycidyl methacrylate-grafted HDPE and removing the remaining solution, the resulting medium was washed several times with isopropanol and water. The washed medium was then dried in an oven at 65°C for 2 hours. The absorption of 3-aminomethylpyridine was determined to be approximately 10-30% by weight.

[0132] The surface-modified media was then cleaned by immersing it in methanol for 30 minutes, in 50% isopropanol or methanol for 30 minutes, and in deionized water for 2 hours. After immersion in various solvents, the surface-modified media was then immersed in 1% hydrochloric acid for 2 hours and rinsed with deionized water to obtain a pH of 7. The protonated functional groups on the media were then deprotonated by immersing the media in tetramethylammonium hydroxide (1%) for 2 hours and rinsing with deionized water to obtain a pH of 7. The resulting material was then rinsed with deionized water for 1 hour and dried in an oven at 65°C for 2 hours. The absorption of 3-aminomethylpyridine was determined to be approximately 10-30% by weight after cleaning.

[0133] 3-Aminomethylpyridine-modified glycidyl methacrylate-grafted HDPE was analyzed by scanning electron microscopy (SEM), and the top surface image and cross-sectional image are shown below. Figure 1A and Figure 1B middle.

[0134] Example 3

[0135] This embodiment demonstrates the metal removal efficiency of the material in Example 2 described herein.

[0136] Metal removal efficiency (MRE) tests were performed using a 47 mm punched disk of the HDPE-coated material from Example 2. 20–30 mL solutions 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., titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, and silver) were passed through the disk, and the resulting metal ion concentrations were measured by inductively coupled plasma mass spectrometry (ICP-MS). The metal removal efficiency (i.e., percentage concentration removed) for each of the solvents (a)–(c) was calculated for three separate tests, and the results were plotted separately. Figures 2 to 4 middle.

[0137] from Figures 2 to 4 The results clearly show that the HDPE coating material of Example 2 removes more than 80% of titanium, chromium, manganese, iron, cobalt, nickel, copper, zinc, and silver from various solvents, and in some cases, vanadium. Furthermore, the HDPE coating material of Example 2 is particularly effective in removing chromium, manganese, iron, cobalt, nickel, copper, and zinc from all tested solvents, exhibiting an MRE greater than 90% in all cases.

[0138] Example 4

[0139] This embodiment provides an exemplary experimental procedure for preparing materials of formula (I) as described herein, which is summarized in Scheme 3.

[0140] Option 3.

[0141]

[0142] 10 g of 4-fluorobenzylamine was dissolved in 90 g of DMSO, and the resulting solution was added to a 12'' × 12'' strip of glycidyl methacrylate-grafted HDPE. The mixture was heated to 85°C and held for 24 hours. After cooling the glycidyl methacrylate-grafted HDPE and removing the remaining solution, the resulting medium was washed several times with isopropanol and water. The washed medium was then dried in an oven at 65°C for 2 hours. The absorption of 4-fluorobenzylamine was determined to be approximately 10-30% by weight.

[0143] The surface-modified media was then cleaned by immersing it in methanol for 30 minutes, in 50% isopropanol or methanol for 30 minutes, and in deionized water for 2 hours. After immersion in various solvents, the surface-modified media was then immersed in 1% hydrochloric acid for 2 hours and rinsed with deionized water to obtain a pH of 7. The protonated functional groups on the media were then deprotonated by immersing the media in tetramethylammonium hydroxide (1%) for 2 hours and rinsing with deionized water to obtain a pH of 7. The resulting material was then rinsed with deionized water for 1 hour and dried in an oven at 65°C for 2 hours. The absorption of 4-fluorobenzylamine was determined to be approximately 10-30% by weight after cleaning.

[0144] HDPE grafted with 4-fluorobenzylamine-modified glycidyl methacrylate was confirmed by scanning electron microscopy (SEM).

[0145] Example 5

[0146] This embodiment demonstrates the metal removal efficiency of the material in Example 4 described herein.

[0147] Metal removal efficiency (MRE) tests were performed using a 47 mm punched disk of the HDPE-coated material from Example 4. 20–30 mL solutions 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., titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, and silver) were passed through the disk, and the resulting metal ion concentrations were measured by inductively coupled plasma mass spectrometry (ICP-MS). The metal removal efficiency (i.e., percentage concentration removed) for each of the solvents (a)–(c) was calculated for three separate tests, and the results were plotted separately. Figures 5 to 7 middle.

[0148] from Figures 5 to 7 The results clearly show that the HDPE coating material of Example 4 removes more than 80% of titanium, chromium, manganese, iron, cobalt, nickel, copper, zinc, and silver from various solvents, and in some cases, vanadium. Furthermore, the HDPE coating material of Example 4 is particularly effective in removing titanium, chromium, manganese, iron, cobalt, nickel, copper, and zinc from all tested solvents, exhibiting an MRE greater than 90% in all cases.

[0149] Example 6

[0150] This embodiment demonstrates the metal removal efficiency of a composite material comprising the materials of Embodiment 2 and Embodiment 4 described herein.

[0151] Metal removal efficiency (MRE) tests were performed using a double-layered 47 mm punched disk, comprising one layer of HDPE coating material from Example 2 and one layer of HDPE coating material from Example 4. 20–30 mL solutions 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., titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, and silver) were passed through the disk, and the resulting metal ion concentrations were measured by inductively coupled plasma mass spectrometry (ICP-MS). The metal removal efficiency (i.e., percentage concentration removed) for each of the solvents (a)–(c) was calculated for three separate trials, and the results are plotted in Figures 8–10. Figures 8–10, marked with “A”, represent… Figure 8A , Figure 9A and Figure 10A The orientation of the HDPE coating material of Example 2 on top and the HDPE coating material of Example 4 on the bottom is such that the solution first passes through the HDPE coating material of Example 2. Figures 8 to 10, marked with "B", show this. Figure 8B , Figure 9B and Figure 10BThe solution has an orientation with a layer of HDPE coating material of Example 4 on top and a layer of HDPE coating material of Example 2 on the bottom, i.e., the solution first passes through a layer of HDPE coating material of Example 4.

[0152] The results shown in Figures 8 to 10 clearly demonstrate that the composite material containing the materials of Example 2 and Example 4 provides MRE with performance consistent with that of the materials of Example 2 and Example 4.

[0153] Example 7

[0154] This embodiment provides an exemplary experimental procedure for preparing materials of formula (I) as described herein, which is summarized in Scheme 4.

[0155] Option 4.

[0156]

[0157] 3-Aminomethylpyridine (5 g) and 4-fluorobenzylamine (5 g) were dissolved in 90 g water / DMSO (1:1), and the resulting solution was added to a 12'' × 12'' strip of glycidyl methacrylate-grafted HDPE. The mixture was heated to 85°C and held for 24 hours. After cooling the glycidyl methacrylate-grafted HDPE and removing the remaining solution, the resulting medium was washed several times with isopropanol and water. The washed medium was then dried in an oven at 65°C for 2 hours. The absorption of 3-aminomethylpyridine and 4-fluorobenzylamine was determined to be approximately 10-30% by weight.

[0158] The surface-modified media was then cleaned by immersing it in methanol for 30 minutes, in 50% isopropanol or methanol for 30 minutes, and in deionized water for 2 hours. After immersion in various solvents, the surface-modified media was then immersed in 1% hydrochloric acid for 2 hours and rinsed with deionized water to obtain a pH of 7. The protonated functional groups on the media were then deprotonated by immersing the media in tetramethylammonium hydroxide (1%) for 2 hours and rinsing with deionized water to obtain a pH of 7. The resulting material was then rinsed with deionized water for 1 hour and dried in an oven at 65°C for 2 hours. The absorption of 3-aminomethylpyridine and 4-fluorobenzylamine was determined to be approximately 10-30% by weight after cleaning.

[0159] HDPE grafted with glycidyl methacrylate modified with 3-aminomethylpyridine and 4-fluorobenzylamine was confirmed by scanning electron microscopy (SEM).

[0160] Example 8

[0161] This embodiment demonstrates the metal removal efficiency of the material described in Example 7 of this document.

[0162] Metal removal efficiency (MRE) tests were performed using a 47 mm punched disk of the HDPE-coated material described in Example 7. 20–30 mL solutions 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., titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, and silver) were passed through the disk, and the resulting metal ion concentrations were measured by inductively coupled plasma mass spectrometry (ICP-MS). The metal removal efficiency (i.e., percentage concentration removed) for each of the solvents (a)–(c) was calculated for three separate tests, and the results were plotted separately. Figures 11 to 13 middle.

[0163] from Figures 11 to 13 The results clearly show that the HDPE coating material of Example 7 removes more than 80% of titanium, chromium, manganese, iron, cobalt, nickel, copper, zinc, and silver from various solvents, and in some cases, vanadium. Furthermore, the HDPE coating material of Example 7 is particularly effective in removing titanium, manganese, iron, cobalt, nickel, copper, zinc, and silver from all tested solvents, exhibiting an MRE greater than 90% in all cases.

[0164] All references cited in this article (including publications, patent applications and patents) are incorporated herein by reference to the same extent that each reference is individually and explicitly indicated to be incorporated and presented in its entirety in this article.

[0165] In the context of describing the invention (particularly in the context of the following claims), the use of the terms “a,” “an,” “the,” and “at least one,” and similar designations, should be understood to cover both the singular and the plural, unless otherwise specified herein or obviously 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 understood 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 specified herein or obviously contradicted by the context. Unless otherwise specified, the terms “comprising,” “having,” “including,” and “containing” should be understood as open-ended terms (i.e., meaning “including but not limited to”). Unless otherwise specified herein, the description of numerical ranges herein is intended only as a way of abbreviating each individual value falling within the range, and each individual value is incorporated into this specification as if it were described separately herein. Unless otherwise specified herein or otherwise obviously contradicted by the context, all methods described herein can be performed in any suitable order. Unless otherwise stated, the use of any and all embodiments or exemplary language (e.g., "such as") provided herein is intended only to better illustrate the invention and not to limit the scope of the invention. No language in the specification should be construed as indicating that any element not protected by the claims is essential to the practice of the invention.

[0166] This document describes preferred embodiments of the invention, including the best modes known to the inventors for carrying out the invention. Variations of those preferred embodiments will become apparent to those skilled in the art upon reading the foregoing description. The inventors expect those skilled in the art to appropriately employ these variations, and the inventors intend for the invention to be practiced in ways other than those explicitly described herein. Therefore, the invention includes all modifications and equivalents of the subject matter set forth in the appended claims to the extent permitted by applicable law. Furthermore, unless otherwise indicated herein or otherwise clearly contradicted by the context, the invention covers any combination of the foregoing elements in all possible variations.

Claims

1. A material comprising glycidyl (meth)acrylate of formula (I): Formula (I), Or its salts, wherein m is an integer from 1 to 10000, n is an integer from 0 to 10000, each R1 is independently hydrogen or methyl, each X is independently -O-, -COO-, -S-, piperazine- or -NR2-, and R2 is hydrogen, aryl, heteroaryl, C 1-6 alkylaryl, C 1-6 alkyl heteroaryl or C 1-6 Alkyl group, each Y being independently present and optionally substituted with -NR3- or C. 1-6 Alkyl group, where R3 is hydrogen or C 1-6 Alkyl group, each Z being independently aryl, heteroaryl, or C. 2-6 Heterocyclic groups, each of which is optionally substituted, and each * independently represents a hydrogen, a terminal group, or a bond with the remainder of the material, provided that at least one * is a bond with the remainder of the material, and wherein the remainder of the material is bonded via sp3-sp3 carbon-carbon bonds.

2. The material of claim 1, wherein the material comprises glycidyl (meth)acrylate of formula (Ia): Equation (Ia), Or its salts, wherein m is an integer from 1 to 10000, n is an integer from 0 to 10000, each R1 is independently hydrogen or methyl, each X is independently -O-, -COO-, -S-, piperazine- or -NR2-, and R2 is hydrogen, aryl, heteroaryl, C 1-6 alkylaryl, C 1-6 alkyl heteroaryl or C 1-6 Alkyl group, each Y being independently present and optionally substituted with -NR3- or C. 1-6 Alkyl group, where R3 is hydrogen or C 1-6 Alkyl group, each Z being independently aryl, heteroaryl, or C. 2-6 Heterocyclic groups, each of which is optionally substituted, and each * independently represents a hydrogen, a terminal group, or a bond with the remainder of the material, provided that at least one * is a bond with the remainder of the material, and wherein the remainder of the material is bonded via sp3-sp3 carbon-carbon bonds.

3. The material as claimed in claim 1 or claim 2, wherein each R1 is a methyl group.

4. The material as described in any one of claims 1 to 3, wherein m is an integer from 1 to 1000.

5. The material as claimed in any one of claims 1 to 4, wherein n is an integer from 1 to 1000.

6. The material according to any one of claims 1 to 5, wherein each X is independently -NR2- and R2 is hydrogen, aryl, heteroaryl, C 1-6 alkylaryl, C 1-6 alkyl heteroaryl or C 1-6 alkyl.

7. The material as claimed in any one of claims 1 to 5, wherein each X is -S-.

8. The material according to any one of claims 1 to 7, wherein each Z is independently phenyl, furanyl, benzofuranyl, thiophenyl, benzothiophenyl, pyrroleyl, indolyl, isoindolyl, azaindolyl, pyridinyl, quinolinyl, isoquinolinyl, oxazolyl, isoxazolyl, benzoxazolyl, pyrazolyl, imidazoleyl, benzimidazoleyl, thiazolyl, benzothiazolyl, isothiazolyl, pyridazinyl, pyrazinyl, Triazinyl, terpineyl, phthalazinyl, quinazolinyl, morpholinyl, pyrrolidone, pyrrolylalkyl, piperidinyl, hydantoinyl, valeronyl, ethylene oxide, oxacyclobutyl, tetrahydrofuranyl, tetrahydropyranyl, tetrahydropyridyl, tetrahydropyrimidinyl, tetrahydrothiophenyl, tetrahydrothiophenyl, tetrahydropyrimidinyl, tetrahydrothiophenyl, tetrahydrothiophenyl, piperazinyl or dihydropyrimidinyl, each of which may be optionally substituted.

9. The material according to any one of claims 1 to 8, wherein at least one Z is a haloaryl or a haloheteroaryl.

10. The material according to any one of claims 1 to 9, wherein at least one Z is a fluorinated aryl or a fluorinated heteroaryl.

11. The material according to any one of claims 1 to 10, wherein at least one Z is an optionally substituted pyridyl group.

12. The material according to any one of claims 1 to 11, wherein the bond with the remainder of the material is a bond with a macromolecular carrier selected from membranes, fibrous media, polymer coatings or materials, metal-organic frameworks, monolithic carriers, beads, filters or resins, and wherein the macromolecular carrier is bonded via sp3-sp3 carbon-carbon bonds.

13. The material of claim 12, wherein the macromolecular carrier comprises gelatin, alginate, starch, polyethylene, polypropylene, nylon, polyvinylidene fluoride, polyethylene oxide, polypropylene oxide, polyethylene oxide / polypropylene oxide, polyacrylonitrile, poly(meth)acrylate, poly(meth)acrylamide, polyamide, polyimide, polyester, cellulose, polystyrene, or combinations thereof.

14. A method for preparing the material according to any one of claims 1 to 13, the method comprising: (i) (a) Irradiating a polymer support with an irradiation source, followed by impregnation of the polymer support with glycidyl methacrylate or a polymer thereof, or (b) generating free radicals on the polymer support in the presence of glycidyl methacrylate or a polymer thereof, wherein the polymer support comprises one or more CH aliphatic bonds to graft the glycidyl methacrylate or a polymer thereof onto the polymer support via one or more sp3-sp3 carbon-carbon bonds, and (ii) Modifying the grafted glycidyl (meth)acrylate or its polymer with one or more compounds of the formula X'-Y'-Z', wherein X' is HO-, HOOC-, HS-, piperazine-, or HNR2-, and R2 is hydrogen, aryl, heteroaryl, C 1-6 alkylaryl, C 1-6 alkyl heteroaryl or C 1-6 Alkyl group, Y' is optional and is -NR3- or optionally substituted C 1-6 Alkyl group, where R3 is hydrogen or C 1-6 Alkyl, and Z' is aryl, heteroaryl or C 2-6 Heterocyclic groups, each of which is optionally substituted.

15. The method of claim 14, wherein the method comprises irradiating the polymer carrier with electron beam irradiation, gamma irradiation, X-ray irradiation, or a combination thereof, and subsequently impregnating the polymer carrier with glycidyl (meth)acrylate or a polymer thereof.

16. The method of claim 14, wherein the method comprises generating free radicals on the polymer support by UV light, plasma, corona discharge, chemical initiator, or a combination thereof in the presence of glycidyl (meth)acrylate or a polymer thereof.

17. A method for removing one or more metal ions from a solution, the method comprising (i) passing the solution through a material as claimed in claim 1 or (ii) contacting the solution with a material as claimed in any one of claims 1 to 13.

18. The method of claim 17, wherein the solution is an aqueous solution.

19. The method of claim 17 or claim 18, wherein the solution comprises an organic solvent.

20. The method of any one of claims 17 to 19, wherein the method removes at least 50% of one or more metal ions selected from the group consisting of sodium, magnesium, aluminum, potassium, calcium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, arsenic, zirconium, molybdenum, silver, cadmium, tin, barium, tungsten, strontium, lead, or combinations thereof.

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