Hydrophobized ion exchange resins and methods of making

Abstract

An ion exchange resin is of Formula 1: where Y is a polystyrenic scaffold or polyacrylic scaffold; Y1 is -H or the same or a different polystyrenic scaffold or polyacrylic scaffold as Y; R1, R2, R3, and R4 are independently a substituted or unsubstituted compound having a functionality of alkyl, alkylene, alkyne, alkenyl, alkynyl, aryl, alkylaryl, arylalkylene, arylalkyne, arylalkenyl, arylalkynyl, cyclic, cycloaliphatic, or polycyclic moieties, which may optionally independently contain at least one heteroatom, at least one active hydrogen containing component, at least one quaternized nitrogen moiety, at least one fluorine moiety, or at least one carbonyl-containing component or where R4 is -H; X is a chloride, bromide, iodide, fluoride, sulfate, nitrate, acetate, hydroxide, or formate counterion; and n is a positive integer.

Description

FP0025-W001TITLE OF THE INVENTION HYDROPHOBIZED ION EXCHANGE RESINS AND METHODS OF MAKING CROSS REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of priority of U.S. Provisional Application No. 63 / 746,519 filed January 17, 2025, the disclosure of which is incorporated herein by reference in its entirety.FIELD

[0002] The present disclosure is related to the field of per- and polyfluoroalkyl substances (PFAS) removal. More specifically, the present disclosure is related to hydrophobized ion exchange (I EX) resins, methods of forming such I EX resins, methods of PFAS removal with such I EX resins, and resulting compositions having reduced PFAS levels.BACKGROUND

[0003] Polymerization aids are utilized in the production of many useful fluoropolymers. Fluoropolymers have a wide variety of beneficial uses including, for example, in fuel cells and batteries and as coatings for materials, such as, for example, medical devices, electrical insulation, chemical containers, and cookware. After production of the fluoropolymer, it may be beneficial to remove the polymerization aid from the fluoropolymer product.

[0004] Commercial I EX resins have been leveraged to remove residuals, such as fluorinated organic constituents (FOC), which may include PFAS, in aqueous systems and fluoropolymer dispersions. A PFAS typically contains a hydrophilic head group, such as a sulfonic acid or carboxylic acid, and a fluorinated tail.Commonly, certain IEX resins containing a trialkylammonium functional group are utilized for their ability to electrostatically attract hydrophilic PFAS head groups. Commercial IEX resins include polystyrenic and polyacrylic scaffolds and both gel and porous types. Select examples of commercial ion exchange resins for removal of FOC include Purolite® Purofine PFA 300 strong base polystyrenic-divinylbenzene type II quaternary ammonium anion exchange gel resin (Purolite Company, King of Prussia, PA), AmberLite™ PSR2 Plus strong base polystyrenic-divinylbenzene tributyl ammonium anion exchange gel resin (DuPont de Nemours, Inc., Wilmington,FP0025-W001DE), and DIAION™ SAF12A strong base polystyrenic-divinylbenzene type I trimethylammonium anion exchange gel resin (Mitsubishi Chemical Corporation, Tokyo, Japan).

[0005] As described in U.S. Patent No. 2,559,752, fluorosurfactants are used as non-telogenic dispersing agents in the manufacture of aqueous fluoropolymer dispersions and thus, unless removed, fluorosurfactants are normally present in aqueous fluoropolymer dispersions. Due to environmental concerns, it is frequently desirable to reduce the fluorosurfactant content and content of other FOC in fluoropolymer dispersions.

[0006] Other fluorinated residuals of manufactured fluoropolymers include certain FOC impurities from the manufacturing process [see, for example, Sworen et al., Journal of Chromatography A, Vol. 1736, Article 465369, (2024)], including, but not limited to, per- and polyfluoroalkyl carboxylic acids (PFCA), per- and polyfluorosulfonic acids (PFSA), H-capped carboxylic acids or H-capped sulfonic acids, and diacids. FOC vary in chain length and functionality, therefore it is critical to develop I EX resins for the abatement of this broad class of chemicals.

[0007] Although commercial I EX resins are effective at significantly reducing FOC, increased regulatory scrutiny and public awareness surrounding synthetic organofluorine compounds serve as motivation to improve residual removal efficiency.

[0008] As a part of environmental stewardship and high-quality manufacturing processes, technology has been developed for the reduction of residual FOC in polymer products including efficient, cost effective, practical processes for residuals reduction in aqueous workstreams.FP0025-W001SUMMARY

[0009] In some embodiments, an I EX resin is of Formula 1:Y is a polystyrenic scaffold or polyacrylic scaffold. Y1is -H or the same or a different polystyrenic scaffold or polyacrylic scaffold as Y. R1, R2, and R3are independently a substituted or unsubstituted compound having a functionality of alkyl, alkylene, alkyne, alkenyl, alkynyl, aryl, alkylaryl, arylalkylene, arylalkyne, arylalkenyl, arylalkynyl, cyclic, cycloaliphatic, or polycyclic moieties, which may optionally independently contain at least one heteroatom, at least one active hydrogen containing component, at least one quaternized nitrogen moiety, at least one fluorine moiety, or at least one carbonyl-containing component. R4is -H, a substituted or unsubstituted compound having a functionality of alkyl, alkylene, alkyne, alkenyl, alkynyl, aryl, alkylaryl, arylalkylene, arylalkyne, arylalkenyl, arylalkynyl, cyclic, cycloaliphatic, or polycyclic moieties, which may optionally independently contain at least one heteroatom, at least one active hydrogen containing component, at least one quaternized nitrogen moiety, at least one fluorine moiety, or at least one carbonyl-containing component. X is a chloride, bromide, iodide, fluoride, sulfate, nitrate, acetate, hydroxide, or formate counterion, n is a positive integer.

[0010] In one embodiment of the IEX resin, the scaffold is polystyrenic.

[0011] In another embodiment of the IEX resin, the scaffold is polyacrylic.

[0012] In another embodiment of the IEX resin, R3has the structure:FP0025-W001

[0013] In another embodiment of the I EX resin, R3has a structure selected from - CH2-C(OH)(CF3)2 and -CH2-C(O )(CF3)2.

[0014] In another embodiment of the I EX resin, the I EX resin is a weak base.

[0015] In some embodiments, a process of forming a hydrophobized I EX resin includes contacting a first I EX resin and a hydrophobizing reagent under conditions to react the at least one reactive group of the first IEX resin with the hydrophobizing reagent to form the hydrophobized IEX resin; where the first IEX resin has a scaffold selected from polystyrenic and polyacrylic.

[0016] In one embodiment of the process of forming a hydrophobized IEX resin, the conditions include a solvent selected from the group consisting of diglyme, acetonitrile, A / , / V-dimethylformamide, / V,A / -dimethylacetamide, methanol, ethanol, and water.

[0017] In another embodiment of the process of forming a hydrophobized IEX resin, the conditions include a nitrogen atmosphere of at least 20 psig.

[0018] In another embodiment of the process of forming a hydrophobized IEX resin, the conditions include a temperature of least 50 °C and a time of at least 8 hours.

[0019] In another embodiment of the process of forming a hydrophobized IEX resin, the hydrophobized IEX resin has the structure of Formula 1:Y is a polystyrenic scaffold or polyacrylic scaffold. Y1is -H or the same or a different polystyrenic scaffold or polyacrylic scaffold as Y. R1, R2, and R3are independently a substituted or unsubstituted compound having a functionality of alkyl, alkylene, alkyne, alkenyl, alkynyl, aryl, alkylaryl, arylalkylene, arylalkyne, arylalkenyl, arylalkynyl, cyclic, cycloaliphatic, or polycyclic moieties, which may optionally independently contain at least oneFP0025-W001heteroatom, at least one active hydrogen containing component, at least one quaternized nitrogen moiety, at least one fluorine moiety, or at least one carbonyl-containing component. R4is -H, a substituted or unsubstituted compound having a functionality of alkyl, alkylene, alkyne, alkenyl, alkynyl, aryl, alkylaryl, arylalkylene, arylalkyne, arylalkenyl, arylalkynyl, cyclic, cycloaliphatic, or polycyclic moieties, which may optionally independently contain at least one heteroatom, at least one active hydrogen containing component, at least one quaternized nitrogen moiety, at least one fluorine moiety, or at least one carbonyl-containing component. X is a chloride, bromide, iodide, fluoride, sulfate, nitrate, acetate, hydroxide, or formate counterion, n is a positive integer.

[0020] In another embodiment of the process of forming a hydrophobized IEX resin, the scaffold is polystyrenic.

[0021] In another embodiment of the process of forming a hydrophobized IEX resin, the scaffold is polyacrylic.

[0022] In another embodiment of the process of forming a hydrophobized IEX resin, the hydrophobizing reagent is selected from the group consisting of epoxides, alkyl halides, acid halides, hydroxyl inclusive hydrophobizing reagents, nitrogen inclusive hydrophobizing reagents, nitrogen and hydroxyl inclusive hydrophobizing reagents, and activated ester inclusive hydrophobizing reagents.

[0023] In another embodiment of the process of forming a hydrophobized IEX resin, the hydrophobizing reagent is selected from the group consisting of 2-(trifluoromethyl)oxirane, 2,2-bis(trifluoromethyl)oxirane, hexafluoropropene oxide, 1-bromooctane, 1 -bromoperfluorohexane, and the following compound:

[0024] In some embodiments, a process of reducing an amount of FOC in an aqueous system includes contacting the aqueous system having a first cumulative concentration of FOC with a hydrophobized IEX resin of Formula 1 :FP0025-W001Y is a polystyrenic scaffold or polyacrylic scaffold. Y1is -H or the same or a different polystyrenic scaffold or polyacrylic scaffold as Y. R1, R2, and R3are independently a substituted or unsubstituted compound having a functionality of alkyl, alkylene, alkyne, alkenyl, alkynyl, aryl, alkylaryl, arylalkylene, arylalkyne, arylalkenyl, arylalkynyl, cyclic, cycloaliphatic, or polycyclic moieties, which may optionally independently contain at least one heteroatom, at least one active hydrogen containing component, at least one quaternized nitrogen moiety, at least one fluorine moiety, or at least one carbonyl-containing component. R4is -H, a substituted or unsubstituted compound having a functionality of alkyl, alkylene, alkyne, alkenyl, alkynyl, aryl, alkylaryl, arylalkylene, arylalkyne, arylalkenyl, arylalkynyl, cyclic, cycloaliphatic, or polycyclic moieties, which may optionally independently contain at least one heteroatom, at least one active hydrogen containing component, at least one quaternized nitrogen moiety, at least one fluorine moiety, or at least one carbonyl-containing component. X is a chloride, bromide, iodide, fluoride, sulfate, nitrate, acetate, hydroxide, or formate counterion, n is a positive integer. The contacting removes at least 95%, by weight, of the FOC from the aqueous system.

[0025] In one embodiment of the process of reducing an amount of FOC in an aqueous system, the contacting removes at least 98%, by weight, of the FOC from the aqueous system.

[0026] In another embodiment of the process of reducing an amount of FOC in an aqueous system, the contacting removes at least 99%, by weight, of the FOC from the aqueous system.

[0027] In another embodiment of the process of reducing an amount of FOC in an aqueous system, the aqueous system is a fluoropolymer dispersion.FP0025-W001

[0028] In another embodiment of the process of reducing an amount of FOC in an aqueous system, the aqueous system is waste water.

[0029] In another embodiment of the process of reducing an amount of FOC in an aqueous system, the aqueous system is drinking water.

[0030] In some embodiments, a fluoropolymer dispersion includes particles of fluoropolymer dispersed in an aqueous liquid. The fluoropolymer dispersion has a solids content of at least 20 wt% and a total concentration of FOC of about 500 parts-per-bil lion or less.

[0031] In one embodiment of the fluoropolymer dispersion, the total concentration of FOC is about 100 parts-per-billion or less.DETAILED DESCRIPTION

[0032] Provided are processes of forming hydrophobized IEX resins, hydrophobized IEX resins, processes of reducing FOC concentration in a composition, and compositions with reduced FOC levels.

[0033] It has been surprisingly found that FOC can more easily be removed by certain IEX resins that have been hydrophobized.

[0034] In some embodiments, the hydrophobized IEX resin has the chemical structure of Compound 1 :(D where Y is a polystyrenic scaffold or polyacrylic scaffold; Y1is -H or the same or a different polystyrenic scaffold or polyacrylic scaffold as Y; R1, R2, and R3are independently a substituted or unsubstituted compound having a functionality of alkyl, alkylene, alkyne, alkenyl, alkynyl, aryl, alkylaryl, arylalkylene, arylalkyne, arylalkenyl, arylal kynyl, cyclic, cycloaliphatic, or polycyclic moieties, which may optionally independently contain at least one heteroatom, at least one activeFP0025-W001hydrogen containing component, at least one quaternized nitrogen moiety, at least one fluorine moiety, or at least one carbonyl-containing component; R4is -H, a substituted or unsubstituted compound having a functionality of alkyl, alkylene, alkyne, alkenyl, alkynyl, aryl, alkylaryl, arylalkylene, arylalkyne, arylalkenyl, arylalkynyl, cyclic, cycloaliphatic, or polycyclic moieties, which may optionally independently contain at least one heteroatom, at least one active hydrogen containing component, at least one quaternized nitrogen moiety, at least one fluorine moiety, or at least one carbonyl-containing component; X is a chloride, bromide, iodide, fluoride, sulfate, nitrate, acetate, hydroxide, or formate counterion; and n is a positive integer.

[0035] In some embodiments, the hydrophobized I EX resin of Formula 1 is zwitterionic and includes one or more zwitterion pairs. In some embodiments, one or more of R1, R2, R3, and R4contributes to the zwitterionic nature of the hydrophobized I EX resin.

[0036] As used herein, the term “alkyl” refers to a saturated linear or branched hydrocarbon group of 1 to 50 carbons.

[0037] As used herein, the term “alkylene” refers to an unsaturated, linear or branched hydrocarbon group of 1 to 50 carbon atoms with one or more carboncarbon double bonds.

[0038] As used herein, the term “alkyne” refers to an unsaturated, linear or branched hydrocarbon group of 1 to 50 carbon atoms with one or more carboncarbon triple bonds.

[0039] As used herein, the term “aryl” refers to a mono- or polynuclear aromatic hydrocarbon group including carbocyclic and heterocyclic aromatic groups.

[0040] As used herein, the terms “alkyl,” “alkylene,” “alkyne,” and “aryl” can be combined to form combinations thereof.

[0041] As used herein, the term “hydrophobic”, “hydrophobized”, or “hydrophobically modified” refers to a structure containing at least one alkyl, alkylene, alkyne, aryl, and / or cycloaliphatic group, optionally containing at least one fluorine atom.FP0025-W001

[0042] As used herein, the term “nitrogen inclusive” refers to an alkyl, alkylene, alkyne, aryl, and / or cycloaliphatic group with at least one nitrogen moiety.

[0043] As used herein, the term “hydroxyl inclusive” refers to an alkyl, alkylene, alkyne, aryl, and / or cycloaliphatic group with at least one hydroxyl moiety.

[0044] As used herein, the term “nitrogen and hydroxyl inclusive” refers to an alkyl, alkylene, alkyne aryl, and / or cycloaliphatic group with at least one nitrogen moiety and at least one hydroxyl moiety.

[0045] As used herein, the term “active hydrogen containing component” refers to any component including -OH, -SH, -NH2, or -NHR1.

[0046] In some embodiments, the hydrophobized I EX resin includes both tertiary amines and quaternary amines. Appropriate ratios of tertiary amines to quaternary amines may include, but are not limited to, 50:1 , 20:1 , 9:1, 15:1 , 4:1 , 3:1 , 2:1 , 1:1, 1:2, 1:3, 1:4, 1:9, 1:15, 1:20, 1:50, or any value, range, or sub-range therebetween.

[0047] In some embodiments, the hydrophobized I EX resin is formed by modifying a first IEX resin with a hydrophobizing reagent.

[0048] In some embodiments, the hydrophobized IEX resin has a greater ability to remove FOC from a composition than the first IEX resin.

[0049] As used herein, the term “per- and polyfluoroalkyl substances” or “PFAS” refers to any chemical compound that includes at least one -CF3 or -CF2- group and having a molecular weight of less than 3,000 g / mol. PFAS include, but are not limited to, per- and polyfluoroalkyl carboxylic acids and per- and polyfluoroalkyl sulfonic acids.

[0050] As used herein, the term “fluorinated organic constituents” or “FOC” refers to any organic compound that includes at least one fluorine atom having a molecular weight of less than 3,000 g / mol. FOC include, but are not limited to, PFAS.

[0051] As used herein, the term “waste water” refers to an aqueous effluent stream from a commercial process or research and development process which utilizes FOC or may produce FOC.

[0052] In some embodiments, the hydrophobized IEX resin reduces the FOC to a level at least 45% lower, alternatively at least 50% lower, alternatively at least 60%FP0025-W001lower, alternatively at least 70% lower, or alternatively at least 70% lower, than the first IEX resin does under the same conditions.

[0053] In some embodiments, the first IEX resin includes a polystyrenic or a polyacrylic scaffold. In some embodiments, the scaffold is polystyrenic. In some embodiments, the scaffold is polyacrylic. In some embodiments, the scaffold includes at least one reactive group. Appropriate reactive groups may include, but are not limited to, -OH, -NH2, -NHR5, -NR5R6, polyamine, -CH2OH, -CH2CI, -CH2Br, -CH2NH2, -CH2NHR5, -CH2NR5R6, or-CH2-polyamine, where R5is a moiety selected from an alkyl-containing, alkenyl-containing, alkynyl-containing, aryl-containing, alkyl-containing quaternized, alkenyl-containing quaternized, alkynyl-containing quatemized, and aryl-containing quaternized, and R6and R7, when present, are moieties independently selected from an alkyl-containing, alkenyl-containing, alkynyl-containing, aryl-containing, alkyl-containing quaternized, alkenyl-containing quaternized, alkynyl-containing quaternized, and aryl-containing quaternized.

[0054] In some embodiments, the first IEX resin is a gel type resin. In some embodiments, the first IEX resin is a porous type, a highly porous type, or a macroporous type of resin. In some embodiments, the first IEX resin is a free based type or a weak base-type IEX resin. In some embodiments, the first IEX resin is an anion exchange resin. In some embodiments, the first IEX resin is a chelating resin.

[0055] In some embodiment, the first IEX resin is a synthetic IEX resin.

[0056] In some embodiment, the first IEX resin is a commercial IEX resin.

[0057] Appropriate commercial IEX resins may include, but are not limited to, Indion® 850 IEX resin (Ion Exchange (India) Ltd., Mumbai, India); CalRes2301 or CalRes2304 (Calgon Carbon Corporation, Pittsburgh, PA); DIAION™ WA21J or DIAION™ CR20 IEX resins (Mitsubishi Chemical Corporation, Tokyo, Japan);Lewatit™ MP 62 IEX resin (Lanxess Deutschland GmbH, Cologne, Germany); or Tulsion® CMB-6572 (D) IEX resin (Thermax Limited, Pune, India).

[0058] In some embodiments, the hydrophobizing reagent is Compound 2, 3, or 4:FP0025-W001where R8, R9, R10, and R11are independently selected from H; F; a fluorine-containing moiety; an alkyl-containing, alkenyl-containing, alkynyl-containing, oraryl-containing moiety; an alkyl-containing, alkenyl-containing, alkynyl-containing, oraryl-containing quaternized nitrogen moiety; or an alkyl, alkenyl, alkynyl, or aryl chain containing at least one fluorine moiety substitution; andwhere at least one of R8, R9, R10, and R11is a fluorine-containing moiety; an alkyl-containing, alkenyl-containing, alkynyl-containing, or aryl-containing moiety; an alkyl-containing, alkenyl-containing, alkynyl-containing, or aryl-containing quaternized nitrogen moiety; or an alkyl, alkenyl, alkynyl, or aryl chain containing at least one fluorine moiety substitution; orwhere R12is an alkyl-containing, alkenyl-containing, alkynyl-containing, or aryl-containing moiety; an alkyl-containing, alkenyl-containing, alkynyl-containing, or aryl-containing quaternized nitrogen moiety; or an alkyl, alkenyl, alkynyl, or aryl chain containing at least one fluorine moiety substitution; andZ is a leaving group such as bromide, iodide, chloride, ortriflate; orwhere R12is as defined above; andZ' is chloride or bromide.FP0025-W001

[0059] In some embodiments, the hydrophobizing reagent is Compound 2, 3, or 4, and the at least one reactive group is selected from -OH, -NH2, -NHR5, -NR5R6, polyamine, -CH2OH, -CH2NH2, -CH2NHR5, and -CH2NR5R6

[0060] In some embodiments, the hydrophobizing reagent is Compound 5:where R13, R14, and R15are independently selected from H; a fluorine-containing moiety; an alkyl-containing, alkenyl-containing, alkynyl-containing, or aryl-containing moiety; an alkyl-containing, alkenyl-containing, alkynyl-containing, or aryl-containing quaternized nitrogen moiety; an alkyl-containing, alkenyl-containing, alkynyl-containing, or aryl-containing nitrogen moiety; an alkyl, alkenyl, alkynyl, or aryl chain containing at least one fluorine moiety substitution; an alkyl-containing, alkenyl-containing, alkynyl-containing, or aryl-containing hydroxyl moiety; or alkyl-containing, alkenyl-containing, alkynyl-containing, or aryl-containing hydroxyl or nitrogen moieties; andwhere at least one of the R13, R14, and R15is a fluorine-containing moiety; an alkyl-containing, alkenyl-containing, alkynyl-containing, or aryl-containing moiety; an alkyl-containing, alkenyl-containing, alkynyl-containing, or aryl-containing quaternized nitrogen moiety; an alkyl-containing, alkenyl-containing, alkynyl-containing, or aryl-containing nitrogen moiety; an alkyl, alkenyl, alkynyl, or aryl chain containing at least one fluorine moiety substitution; ora hydroxyl inclusive or nitrogen and hydroxyl inclusive variation of any of these.

[0061] In another embodiment of the process of forming a hydrophobized IEX resin, the hydrophobizing reagent is an epoxide, an alkyl halide, an acid halide, a hydroxyl inclusive hydrophobizing reagent, a nitrogen inclusive hydrophobizing reagent, a nitrogen and hydroxyl inclusive hydrophobizing reagent, or an activated ester inclusive hydrophobizing reagent. In some embodiments, the epoxide is a glycidyl ester.FP0025-W001

[0062] Appropriate epoxides may be non-halogenated, partially halogenated, or fully halogenated and may include, but are not limited to, isobutylene oxide, styrene oxide, 2-(phenymethoxy)oxirane, glycidyltrimethylammonium, N,N,N-triethyl-2-oxiranemethanaminium, N,N,N-trimethyl-2-oxiranebutanaminium, N,N,N-trimethyl-2-oxiranepropanaminium, N,N,N-trimethyl-2-oxiraneethanaminium, ethylhexylglycidyl ether, propylene oxide, hexafluoropropene oxide, 1 ,2-epoxybutane, 2-propyloxirane, 2-butyloxirane, pentyloxirane, 2-hexyloxirane, 1 -nonene oxide, 1 ,2-epoxydecane, 2-octyloxirane, 2-nonyloxirane, 1 ,2-epoxydodecane, 2-undecyloxirane, 1,2-epoxytetradecane, 2-tridecyloxirane, 1 ,2-epoxyhexadecane, 2-pentadecyloxirane, 1 ,2-epoxyoctadecane, heptadecyloxirane, allyl glycidyl ether, methyl glycidyl ether, ethyl glycidyl ether, propyl glycidyl ether, butyl glycidyl ether, pentyl glycidyl ether, 2-[(hexyloxy)methyl]oxirane, 2-[(heptyloxy)methyl]oxirane, 2-[(octyloxy)methyl]oxirane, 2-[(nonyloxy)methyl]oxirane, 2-[decyloxymethyl]oxirane, 2-[(undecyloxyl)methyl]oxirane, 2-(trifluoromethyl)oxirane, 2,2-bis(trifluoromethyl)oxirane, dodecyl glycidyl ether, 1-[(tridecyloxy)methyl]oxirane, tetradecyl glycidyl ether, 1-[(pentadecyloxy)methyl]oxirane, hexadecyl glycidyl ether, 2-[(heptadecyloxy)methyl]oxirane, or stearyl glycidyl ether.

[0063] Appropriate alkyl halides may be non-halogenated, partially halogenated, or fully halogenated, may include aromatic groups and / or quaternary ammonium groups, and may include, but are not limited to, 1-chloro-2-methylhexane, 1-bromo-2-methylhexane, 1-iodo-2-methylhexane, 1-bromo-N,N,N-trimethylmethanaminium, 2-bromo-N,N,N-trimethylethanaminium, 3-bromo-N,N,N-trimethyl-1-propanaminium, 4-bromo-N,N,N-trimethyl-1-butanaminium, 5-bromo-N,N,N-trimethyl-1-pentanaminium, benzylchloride, benzylbromide, benzyliodide, chloromethane, bromomethane, iodomethane, iodopropane, 1 -bromopropane, 2-bromopropane, 1-iodopropane, 2-iodopropane, 1 -bromobutane, 1 -iodobutane, 2-bromobutane, 2-iodobutane, 1-bromopentane, 2-bromopentane, 3-bromopentane, 1 -iodopentane, 2-iodopentane, 3-iodopentane, 1 -bromohexane, 2-bromohexane, 1 -iodohexane, 2-iodohexane, 1 -bromoperfluorohexane, 1 -bromoheptane, 2-bromoheptane, 1-iodoheptane, 2-iodoheptane, 1 -bromooctane, 2-bromooctane, 1 -iodooctane, 2-iodooctane, 1 -bromononane, 2-bromononane, 1 -iodononane, 2-iodononane, 1-bromodecane, 1-iododecane, 1-bromoundecane, 2-bromoundecane, 1-iodoundecane, 2-iodoundecane, 1 -bromododecane, 1 -iodododecane, 1-FP0025-W001bromotridecane, 1 -iodotridecane, 1 -bromotetradecane, 1 -iodotetradecane, 1-bromopentadecane, 1 -iodopentadecane, 1 -bromohexadecane, 1 -iodohexadecane, dibromomethane, 1,6-dibromohexane, 1,10-dibromodecane, 1,4-bis(bromomethyl)benzene, 1 -bromohexadecane, 1 -iodohexadecane, or Compound 6, having the structure:

[0064] Appropriate acid halides may be non-halogenated, partially halogenated, or fully halogenated and may include, but are not limited to, pivaloyl chloride, benzoyl chloride, benzoyl bromide, acetyl chloride, acetyl bromide, propanoyl chloride, propanoyl bromide, butanoyl chloride, butanoyl bromide, pentanoyl chloride, pentanoyl bromide, hexanoyl chloride, hexanoyl bromide, heptanoyl chloride, heptanoyl bromide, 2,2,3,3,4,4,5,5,6,6,7,7-dodecafluoroheptanoyl chloride, octanoyl chloride, octanoyl bromide, nonanoyl chloride, nonanoyl bromide, decanoyl chloride, decanoyl bromide, undecanoyl chloride, undecanoyl bromide, dodecanoyl chloride, dodecanoyl bromide, tridecanoyl chloride, tridecanoyl bromide, tetradecanoyl chloride, tetradecanoyl bromide, pentadecanoyl chloride, pentadecanoyl bromide, hexadecanoyl chloride, hexadecanoyl bromide, heptadecanoyl chloride, heptadecanoyl bromide, octadecanoyl chloride, octadecanoyl bromide, nonadecanoyl chloride, 2-chloro-N,N,N-trimethyl-2-oxoethanaminium, or nonadecanoyl bromide.

[0065] Appropriate nitrogen inclusive hydrophobizing reagents may include, but are not limited to, 1-(dimethylamino)-2-propanol, 1-(dimethylamino)-2-methyl-2-propanol, 2-(dimethylamino)-1 -propanol, 2-(dimethylamino)-2-methyl-1 -propanol, N, / V-dimethylaniline, 2-(dimethylamino)pyridine, 2-(dimethylamino)3-pyridinol, A / , / V-dimethyl-3-pyridinamide, 4-(dimethylamino)pyridine, A / , / V-dimethyl-2-pyridinemethanamine, / V, / V-dimethyl-3-pyridinemethanamine, A / ,A / -dimethyl-4-pyridinemethanamine, / V-methyl-2-pyridinemethanamine, A / -methyl-3-pyridinemethanamine, / V-methyl-4-pyridinemethanamine, 2-[(methylamino)methyl]-3-pyridinol, 2-[(methylamino)methyl]-4-pyridinol, 2-[(dimethylamino)methyl]-3-pyridinol, 2-(dimethylamino)phenol, 2-(methylamino)phenol, 4-(dimethylamino)phenol, N-FP0025-W001methyl-p-aminophenol, 2-(dimethylamino)phenol, 3-(dimethylamino)phenol, 3-(methylamino)phenol, N, / V, / V / V-tetramethylenediamine, A / , / V, / -trimethylethylenediamine, 2,4,6-tris[(dimethylamino)methyl]phenol, tetramethylhydrazine, trimethylhydrazine, A / -methyl-4-(trifluoromethyl)benzenamine, A / , / V-dimethyl-4-(trifluoromethyl)benzenamine, A / , / V-dimethyl-4-(trifluoromethyl)benzenemethanamine, and / V-methyl-4-(trifluoromethyl)benzenemethanamine and Compound 7:(7).

[0066] In some embodiments, Compound 7 is synthesized as described in Inorg. Chem., Vol. 59, pp. 7167-7180, (2020), supplementary information, which is incorporated by reference in its entirety herein.

[0067] In some embodiments, the hydrophobizing reagent includes an activated ester. In some embodiments, the activated ester is a cyclic sulfonate ester. In some embodiments, the hydrophobizing reagent including an activated ester is 1,3-propanesultone.

[0068] In some embodiments, the process includes contacting the first I EX resin and the hydrophobizing reagent under conditions to react the reactive group of the first IEX resin with the hydrophobizing reagent to form the hydrophobized IEX resin.

[0069] In some embodiments, the process includes contacting a first IEX resin, such as a Merrifield resin with a nitrogen inclusive, hydroxyl inclusive, or nitrogen and hydroxyl inclusive hydrophobizing reagent to form the hydrophobized IEX resin [see, for example, Vaino etal., Journal of Combinatorial Chemistry, Vol. 2, pp. 579-596, (2000)].

[0070] In some embodiments, appropriate conditions to react include a solvent, such as, for example, diglyme, acetonitrile, / V, / V-dimethylformamide, N,N-dimethylacetamide, methanol, ethanol, or water, and optionally a salt, such as, for example, potassium carbonate, under nitrogen, optionally with increased pressure, such as, for example, to at least 20 psig, alternatively to at least 30 psig, alternatively to at least 40 psig, and increased temperature, such as, for example, to at least 50FP0025-W001°C, alternatively at least 75 °C, alternatively at least 100 °C, for at least 8 hours, alternatively at least 12 hours, alternatively at least 16 hours, alternatively at least 48 hours, or any value, range, or sub-range therebetween.

[0071] In some embodiments, a resulting iodide form is first converted to a bromide form by exposure to aqueous potassium bromide followed by conversion to a chloride form by exposure to aqueous sodium chloride.

[0072] In some embodiments, a resulting bromide form is converted to a chloride form by exposure to aqueous sodium chloride.

[0073] In some embodiment, the hydrophobized I EX resin is more effective at removing FOC from a system than the first I EX resin.

[0074] In some embodiments, the system is a fluoropolymer dispersion containing one or more FOC. In some embodiments, the fluoropolymer dispersion contains total concentrations of fluorinated residuals, by weight, of about 1 part-per-trillion (ppt) to about 20,000 parts-per-million (ppm), alternatively about 1 ppt to about 10,000 ppm, alternatively about 1 part-per-billion (ppb) to about 5000 ppm, alternatively about 10 ppb to about 5000 ppm, alternatively about 20 ppb to about 10 ppm, alternatively about 4000 ppm to about 6000 ppm, alternatively about 10,000 ppm or less, alternatively about 5000 ppm or less, alternatively about 2000 ppm or less, alternatively about 1000 ppm or less, alternatively about 500 ppm or less, alternatively about 100 ppm or greater, alternatively about 500 ppm or greater, alternatively about 1000 ppm or greater, alternatively about 5000 ppm or greater, or any value, range, or sub-range therebetween, prior to the exposing.

[0075] Any of a variety of techniques that bring the fluoropolymer dispersion in contact with the hydrophobized IEX resin and then separate the fluoropolymer dispersion from the hydrophobized IEX resin can be used for carrying out the FOC reduction process. For example, the process can be carried out by addition of the hydrophobized IEX resin to the fluoropolymer dispersion in a stirred tank, in which a slurry of the fluoropolymer dispersion and hydrophobized IEX resin is formed, followed by separation of the fluoropolymer dispersion from the hydrophobized IEX resin beads by filtration. Another suitable method is to pass the fluoropolymer dispersion through a fixed bed of hydrophobized IEX resin instead of using a stirred tank. Flow can be upward or downward through the bed and no separate separationFP0025-W001step is needed beyond the flowing since the hydrophobized I EX resin remains in the fixed bed.

[0076] In some embodiments, the contacting reduces the FOC concentration in the system by at least 90%, by weight, alternatively at least 95%, alternatively at least 98%, alternatively at least 99%, alternatively at least 99.9%, or any value, range, or sub-range therebetween.

[0077] In some embodiments, the contacting reduces the FOC concentration in the system to about 100 parts-per-million or less, alternatively about 5 parts-per-mi II ion or less, alternatively about 500 parts-per-bill ion or less, alternatively about 100 parts-per-billion or less, alternatively about 500 parts-per-trillion or less, or any value, range, or sub-range therebetween.

[0078] In some embodiments, a process includes concentrating an aqueous fluoropolymer dispersion having a reduced FOC content to a predetermined solids percent.

[0079] In some embodiments, the concentrating is by a method taught in U.S. Patent No. 3,037,953, which is incorporated by reference herein. In some embodiments, the concentrating includes adding a nonionic surfactant to the as polymerized dispersion, heating to above the cloud point, and removing the clear upper supernatant layer forming above the concentrated dispersion. In some embodiments, the heating is to about 60 to about 70 °C for about 2 to about 4 hours.

[0080] In some embodiments, the system is waste water containing one or more FOC. In some embodiments, the waste water contains total concentrations of FOC, by weight, of about 1 part-per-trillion (ppt) to about 20,000 parts-per-million (ppm), alternatively about 1 ppt to about 10,000 ppm, alternatively about 1 part-per-billion (ppb) to about 5000 ppm, alternatively about 10 ppb to about 5000 ppm, alternatively about 20 ppb to about 10 ppm, alternatively about 4000 ppm to about 6000 ppm, alternatively about 10,000 ppm or less, alternatively about 5000 ppm or less, alternatively about 2000 ppm or less, alternatively about 1000 ppm or less, alternatively about 500 ppm or less, alternatively about 100 ppm or greater, alternatively about 500 ppm or greater, alternatively about 1000 ppm or greater, alternatively about 5000 ppm or greater, or any value, range, or sub-range therebetween, prior to the exposing.FP0025-W001

[0081] Any of a variety of techniques that bring the waste water in contact with the hydrophobized I EX resin and then separate the waste water from the hydrophobized I EX resin can be used for carrying out the FOC reduction process.

[0082] In some embodiments, the system is drinking water containing one or more FOC. In some embodiments, the drinking water contains total concentrations of FOC, by weight, of about 1 part-per-trillion (ppt) to about 20,000 parts-per-million (ppm), alternatively about 1 ppt to about 10,000 ppm, alternatively about 1 part-per-billion (ppb) to about 5000 ppm, alternatively about 10 ppb to about 5000 ppm, alternatively about 20 ppb to about 10 ppm, alternatively about 4000 ppm to about 6000 ppm, alternatively about 10,000 ppm or less, alternatively about 5000 ppm or less, alternatively about 2000 ppm or less, alternatively about 1000 ppm or less, alternatively about 500 ppm or less, alternatively about 100 ppm or greater, alternatively about 500 ppm or greater, alternatively about 1000 ppm or greater, alternatively about 5000 ppm or greater, or any value, range, or sub-range therebetween, prior to the exposing.

[0083] Any of a variety of techniques that bring the drinking water in contact with the hydrophobized I EX resin and then separate the drinking water from the hydrophobized I EX resin can be used for carrying out the FOC reduction process.

[0084] Research efforts aimed at developing next generation resins and adsorbents with enhanced FOC removal capability are ongoing in both the industrial and academic arena. Resin modification could potentially include altering crosslinking and attributes such as porosity and surface area. Additional areas of pursuit could include optimization of the I EX resin functional group and / or polymeric scaffold through manipulation of hydrophobicity, which optionally includes fluorinated moieties.TEST METHODSThermodynamic Shaker Test Procedure

[0085] A predetermined amount of IEX resin was measured by volume (2 ml_ unless otherwise noted) in a fully wetted setting to allow the material to settle fully. Before addition to a 125-mL Erlenmeyer flask, the IEX resin was dewatered by drying on an absorbent surface. Once the IEX resin was charged to the ErlenmeyerFP0025-W001flask, 50 mL of a test sample containing a predetermined amount of fluorinated residual was added to the Erlenmeyer flask. In the case of hexafluoropropylene oxide dimer acid (HFPO-DA) as the fluorinated residual, the test sample was a stabilized fluoropolymer dispersion, such as disclosed in U.S. Patent No. 7,705,074, which is incorporated by reference herein. In the case of a short chain as the fluorinated residual, the test sample was a waste water sample. The flask was capped, placed on a shaker table, and allowed to shake at 150 rpm for at least 48 hours. After the system was allowed to equilibrate, the Erlenmeyer flask was removed from the shaker table and the IEX resin / adsorbent material was removed by filtration from the system. The filtrate was then analyzed for HFPO-DA or USC fluorinated residual concentration.HFPO-DA Measurements

[0086] The relative amount of HFPO-DA was measured using fluorine nuclear magnetic resonance (19F NMR).Short Chain Measurements

[0087] Short chains fluorinated residuals, including trifluoroacetic acid (TFA), difluoroacetic acid (DFA), perfluoropropionic acid (PFPrA), and tetrafluoropropanoic acid (TFPrA), were measured liquid chromatography tandem mass spectrometry with triple quadruple detection (LC / QqQ).EXAMPLESSynthesis of Hydrophobizinq Reagent

[0088] Methyl tert-butyl ether (650.00 g) was added to a round bottom flask equipped with a thermocouple, a reflux condenser, an addition funnel, and an overhead stirrer under a blanket of nitrogen. Dichloro-p-xylene (48.00 g) was then added, and the mixture was stirred at room temperature. Separately, N,N-dimethylbenzylamine (52.00 g) was dissolved in methyl tert-butyl ether (50.00 g) and the resultant solution was added to the addition funnel. The contents of the addition funnel was then added to the round bottom flask over 90 minutes. The contents of the round bottom flask were heated to 50°C during adding and the resultant mixture was stirred for 20 hours at 50°C. The contents of the reactor were then cooled toFP0025-W001room temperature and then concentrated by rotary evaporation. Acetonitrile (500.00 g) was added to the residue and swirled in the flask for five minutes. The mixture was filtered through a Buchner funnel fitted with a Whatman 1 filter to remove dimer. The filtrate was concentrated by rotary evaporation. The resultant residue was placed under high vacuum for twenty minutes to remove any residual acetonitrile. Deionized water (300.00 g) was added to the residue. The mixture was filtered through a Buchner funnel fitted with a Whatman 1 filter to remove residual dichloro-p-xylene. The aqueous filtrate was lyophilized. The lyophilized solid was dissolved in acetonitrile (500.00 g), dried over sodium sulfate, and concentrated by rotary evaporation to give Compound 6 (39.69 g).Synthesis of Hydrophobized Ion Exchange Resins: Inventive Examples Inventive Example 1: Indion® 850 resin hydrophobized with 2,2-bis(trifluoromethyl)oxirane

[0089] Indion® 850 resin is a weak base polystyrene-divinylbenzene anion exchange microporous resin containing tertiary and quaternary ammonium groups. Wet Indion® 850 resin beads (25.00 g) were washed with diglyme (3 x 100 g). The washed wet beads were placed into a Hastelloy pressure reactor (400 mL). Diglyme (100 g) followed by 2,2-bis(trifluoromethyl)oxirane (43.60 g) were added to the reactor. The reactor was pressurized with 41 psig nitrogen and heated to 110 °C. The contents of the reactor were heated for 16 hours. The maximum pressure reached during the reaction was 73 psig. The maximum temperature reached was 110.9 °C. The reactor was cooled to room temperature and vented. The beads were subsequently filtered using Whatman 1 filter paper and washed with acetone (2 x 250 g) and deionized (DI) water (2 x 250 g) to give wet beads (35.05 g, 56.00% solids) as Inventive Example 1 (IE1).Inventive Example 2: Indion® 850 resin hydrophobized with 1 -bromooctane

[0090] Wet Indion® 850 resin beads (80.00 g) were washed with acetonitrile (3 x 100 g). The washed wet beads were placed into a 1-L round-bottom flask equipped with an agitator, a condenser, a nitrogen inlet, and a thermocouple. Potassium carbonate (32.91 g) and 1-bromooctane (229.89 g) were added to the flask.Acetonitrile (200.00 g) was added to dilute the mixture further. The mixture was stirred at 75 °C for 24 hours under nitrogen. The contents of the reactor wereFP0025-W001allowed to cool to room temperature. The beads were subsequently filtered using Whatman 1 filter paper and washed with acetone (3 x 200 g) and DI water (3 x 200 g) to give wet beads (124.79 g, 52.9% solids).

[0091] The beads were converted from the bromide to the chloride form by the following procedure. 10.00 grams of dry resin was added to a 1 L Griffin beaker, and the beaker was filled to 1 L total volume with a 1 N NaCI solution (NaCI in DI water). The contents were stirred with an overhead stirrer for 30 minutes. The beads were then allowed to settle and the top liquid was decanted off. The remaining liquid was removed by filtration. The beads were then placed back in the same 1L Griffin beaker and the process was repeated two more times to give the resulting chloride form as Inventive Example 2 (IE2).Inventive Example 3: DIAION™ WA21 J resin hydrophobized with iodoethane

[0092] DIAION™ WA21 J resin is a weak base polystyrene-divinylbenzene polyamine anion exchange porous resin. Wet DIAION™ WA21 J beads (68.09 g) were washed with acetonitrile (3 x 100 g). The washed wet beads were placed into a 1-L round-bottom flask equipped with an agitator, a condenser, a nitrogen inlet, and a thermocouple. Acetonitrile (100.00 g), potassium carbonate (42.42 g), and iodoethane (300.00 g) were added to the flask. The mixture was stirred at 65 °C for 24 hours under nitrogen. The contents of the reactor were allowed to cool to room temperature. The beads were subsequently filtered using Whatman 1 filter paper and washed with ethanol (3 x 200 g) and DI water (3 x 200 g) to give wet beads (103.18 g wet beads, 57.87% solids).

[0093] The beads were converted from the iodide to the chloride form by the following procedure. 10.00 grams of dry resin was added to a 1-L Griffin beaker, and the beaker was filled to 1 L total volume with a 1 N KBr solution (KBr in DI water). The contents were stirred with an overhead stirrer for 30 minutes. The beads were then allowed to settle and the top liquid was decanted off. The remaining liquid was removed by filtration. The beads were then placed back in the same 1-L Griffin beaker and the process was repeated three more times, but with a 1 N NaCI solution instead of the 1 N KBr solution, to give the resulting chloride form as Inventive Example 3 (IE3).FP0025-W001Inventive Example 4: DIAION™ WA21 J resin hydrophobized with 1-bromobutane

[0094] Wet DIAION™ WA21 J resin beads (68.09 g) were washed with acetonitrile (3 x 100 g). The washed wet beads were placed into a 1-L round-bottom flask equipped with an agitator, a condenser, a nitrogen inlet, and a thermocouple.Acetonitrile (100.00 g), potassium carbonate (42.42 g), and 1-bromobutane (264.00 g) were added to the flask. The mixture was stirred at 65 °C for 24 hours under nitrogen. The contents of the reactor were allowed to cool to room temperature. The beads were subsequently filtered using Whatman 1 filter paper and washed with ethanol (3 x 200 g) and DI water (3 x 200 g) to give wet beads (85.24 g wet beads, 59.76% solids). The beads were converted to the chloride form as Inventive Example 4 (IE4) using the same procedure as for Inventive Example 2.Inventive Example 5: Indion® 850 resin hydrophobized with Compound 6

[0095] Wet Indion® 850 resin beads (20.20 g) were weighed into a beaker.Acetonitrile (500.00 g) was added and the resin beads were soaked for one hour. The resin beads were filtered through a Buchner funnel fitted with Whatman 1 filter paper. A round bottom flask was assembled with an overhead stirrer, an addition funnel, a reflux condenser, a thermocouple, and a nitrogen inlet. The filtered Indion® 850 resin beads were added. Compound 6 (23.43 g) in acetonitrile (200.00 g) was added. The flask was heated to 60 °C and stirred for approximately 40 hours under a blanket of nitrogen. The contents of the flask were then cooled. The resin beads were filtered using a Buchner funnel fitted with Whatman 1 filter paper. The resin beads were washed with acetonitrile (2 x 300 g), ethanol (2 x 300 g), and deionized water (2 x 300 g) to give wet beads (27.76 g, 48.26% solids) as Inventive Example 5.Inventive Example 6: Lewatit™ MP 62 resin hydrophobized with Compound 6

[0096] Lewatit™ MP 62 is a weak base polystyrene-divinylbenzene anion exchange macroporous resin. Wet Lewatit™ MP 62 resin beads (17.06 g) were washed with deionized water (2 x 300 g) using a Buchner funnel fitted with Whatman 1 filter paper. Compound 6 (19.55 g) was placed in deionized water (70.00 g). The washed resin beads were added to the solution of Compound 6 in deionized water. The mixture was transferred to a pressure reactor. The reactor was pressurized with 51.7 psig nitrogen and heated to 110 °C and maintained for 16 hours. The maximum pressure reached during the reaction was 94.3 psi. The maximum temperature wasFP0025-W001110 °C. The contents of the reactor were then cooled and vented. The resin beads were filtered using a Buchner funnel fitted with a milk filter. The resin beads were washed with acetonitrile (3 x 200 g) then washed with deionized water (3 x 200 g) to give wet resin beads (30.45 g, 49.52% solids) as Inventive Example 6.Inventive Example 7: lndion®850 resin hydrophobized with 1 ,2-propanesultone

[0097] Wet Indion® 850 resin beads (40.00 g) were soaked in ethanol (200 g) for one hour. The beads were filtered through a Whatman 1 filter and washed with ethanol (200 g). The beads were placed in a 500-mL round-bottom flask equipped with an agitator, a condenser, a nitrogen inlet, and a thermocouple. Ethanol (33.5 g) was added, followed by 1 ,3-propanesultone (49.87 g). The mixture was stirred at room temperature for 72 hours under nitrogen. Additional ethanol (10.0 g) was added to the reactor, and the mixture was heated to 70 °C and stirred for 72 hours. The contents of the reactor were then allowed to cool to room temperature. The beads were subsequently filtered using Whatman 1 filter paper and washed with ethanol (1 x 500 g), DI water (1 x 500 g), ethanol (1 x 500 g), and DI water (2 x 500 g) to give wet beads (72.34 g, 52.55% solids). The beads were subsequently soaked in 1M sodium hydroxide (500 g) for five minutes and filtered using a Pall filter. The beads were again soaked in 1 M sodium hydroxide (500 g) for one minute and filtered using a Pall filter. The resin beads were washed with DI water (500 g) to give wet beads as Inventive Example 7.Removal of HFPO-DA by Ion Exchange Resin

[0098] Inventive Examples 1 , 2, 3, 4, 5, and 6 were evaluated for their ability to remove hexafluoropropylene oxide dimer acid (HFPO-DA) as a fluorinated residual from a stabilized fluoropolymer dispersion, such as disclosed in U.S. Patent No. 7,705,074, following the test procedures described above. Unhydrophobized commercial Indion® 850 resin beads were evaluated as Comparative Example 1. Unhydrophobized commercial DIAION™ WA21J resin beads were evaluated as Comparative Example 2. Unhydrophobized commercial Lewatit™ MP 62 resin beads were evaluated as Comparative Example 3. Table 1 shows the remaining percent concentrations of the HFPO-DA following exposure to the IEX resin relative to the amount in the original sample.FP0025-W001Table 1

[0099] As shown in Table 1, the hydrophobized I EX resins of the Inventive Examples were more efficient at removing the HFPO-DA than the Comparative Examples, achieving up to 97% removal.

[0100] Table 2 shows the percentage removal of HFPO-DA for the hydrophobized I EX resin relative to the unhydrophobized I EX resin.Table 2

[0101] As shown in Table 2, the HFPO-DA was removed much more efficiently by the Inventive Examples than the Comparative Examples. The measured remainingFP0025-W001concentrations of the HFPO-DA for the hydrophobized IEX resins were 47.5 to 80.5% lower than with the unhydrophobized IEX resins.Removal of Short Chains by Ion Exchange Resin

[0102] Inventive Example 1 (IE1) and Inventive Example 7 (IE7) were evaluated for their ability to remove trifluoroacetic acid (TEA), difluoroacetic acid (DFA), perfluoropropionic acid (PFPrA), and tetrafluoropropanoic acid (TFPrA) as test short chains from a test aqueous sample following the test methods described above. Commercial Lewatit™ TP108 resin beads were evaluated as Comparative Example 4 (CE4). Table 3 shows the remaining percent concentrations of the short chain following exposure to the IEX resin relative to the amount in the original sample.Table 3N / D = not determinedFP0025-W001

[0103] As shown in Table 3, IE1 and IE7 performed significantly better than CE4 for each tested USC. For IE1 , remaining concentrations were from 72 to over 99% lower than the remaining concentrations for CE4. For IE7, remaining concentrations were from 52 to over 99% lower than the remaining concentrations for CE4.

[0104] All above-mentioned references are hereby incorporated by reference herein.

[0105] While the invention has been described with reference to a preferred embodiment, it will be understood by those skilled in the art that various changes may be made, and equivalents may be substituted for elements thereof, without departing from the scope of the invention. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from the essential scope thereof. Therefore, it is intended that the invention not be limited to the particular embodiment disclosed as the best mode contemplated for carrying out this invention, but that the invention will include all embodiments falling within the scope of the appended claims.

Claims

FP0025-W001CLAIMSWhat is claimed is:

1. An ion exchange resin of Formula 1 :wherein Y is a polystyrenic scaffold or polyacrylic scaffold; wherein Y1is -H or the same or a different polystyrenic scaffold or polyacrylic scaffold as Y;wherein R1, R2, and R3are independently a substituted or unsubstituted compound having a functionality of alkyl, alkylene, alkyne, alkenyl, alkynyl, aryl, alkylaryl, arylalkylene, arylalkyne, arylalkenyl, arylalkynyl, cyclic, cycloaliphatic, or polycyclic moieties, which may optionally independently contain at least one heteroatom, at least one active hydrogen containing component, at least one quaternized nitrogen moiety, at least one fluorine moiety, or at least one carbonyl-containing component;wherein R4is -H, a substituted or unsubstituted compound having a functionality of alkyl, alkylene, alkyne, alkenyl, alkynyl, aryl, alkylaryl, arylalkylene, arylalkyne, arylalkenyl, arylalkynyl, cyclic, cycloaliphatic, or polycyclic moieties, which may optionally independently contain at least one heteroatom, at least one active hydrogen containing component, at least one quaternized nitrogen moiety, at least one fluorine moiety, or at least one carbonyl-containing component; wherein X is a chloride, bromide, iodide, fluoride, sulfate, nitrate, acetate, hydroxide, or formate counterion; andwherein n is a positive integer.

2. The ion exchange resin of claim 1 , wherein the scaffold is polystyrenic.

3. The ion exchange resin of claim 1 , wherein the scaffold is polyacrylic.FP0025-W0014. The ion exchange resin of any of claims 1-3, wherein R3has the structure:

5. The ion exchange resin of any of claims 1-3, wherein R3has a structure selected from -CH2-C(OH)(CF3)2 and -CH2-C(O-)(CF3)2.

6. The ion exchange resin of any of claims 1-5, wherein the ion exchange resin is a weak base.

7. A process of forming a hydrophobized ion exchange resin, the process comprising:contacting a first ion exchange resin and a hydrophobizing reagent under conditions to react the at least one reactive group of the first ion exchange resin with the hydrophobizing reagent to form the hydrophobized ion exchange resin;wherein the first ion exchange resin has a scaffold selected from polystyrenic and polyacrylic.

8. The process of claim 7, wherein the conditions comprise a solvent selected from the group consisting of diglyme, acetonitrile, N,N- dimethylformamide, / V, / V-dimethylacetamide, methanol, ethanol, and water.

9. The process of claim 7 or 8, wherein the conditions comprise a nitrogen atmosphere of at least 20 psig.

10. The process of any of claims 7-9, wherein the conditions comprise a temperature of least 50 °C and a time of at least 8 hours.

11. The process of any of claims 7-10, wherein the hydrophobized ion exchange resin has the structure of Formula 1 :FP0025-W001wherein Y is a polystyrenic scaffold or polyacrylic scaffold; wherein Y1is -H or the same or a different polystyrenic scaffold or polyacrylic scaffold as Y;wherein R1, R2, and R3are independently a substituted or unsubstituted compound having a functionality of alkyl, alkylene, alkyne, alkenyl, alkynyl, aryl, alkylaryl, arylalkylene, arylalkyne, arylalkenyl, arylalkynyl, cyclic, cycloaliphatic, or polycyclic moieties, which may optionally independently contain at least one heteroatom, at least one active hydrogen containing component, at least one quaternized nitrogen moiety, at least one fluorine moiety, or at least one carbonyl-containing component;wherein R4is -H, a substituted or unsubstituted compound having a functionality of alkyl, alkylene, alkyne, alkenyl, alkynyl, aryl, alkylaryl, arylalkylene, arylalkyne, arylalkenyl, arylalkynyl, cyclic, cycloaliphatic, or polycyclic moieties, which may optionally independently contain at least one heteroatom, at least one active hydrogen containing component, at least one quaternized nitrogen moiety, at least one fluorine moiety, or at least one carbonyl-containing component; wherein X is a chloride, bromide, iodide, fluoride, sulfate, nitrate, acetate, hydroxide, or formate counterion; andwherein n is a positive integer.

12. The process of any of claims 7-11 , wherein the scaffold is polystyrenic.

13. The process of any of claims 7-11 , wherein the scaffold is polyacrylic.

14. The process of any of claims 7-13, wherein the hydrophobizing reagent is selected from the group consisting of epoxides, alkyl halides, acid halides, hydroxyl inclusive hydrophobizing reagents, nitrogen inclusive hydrophobizingFP0025-W001reagents, nitrogen and hydroxyl inclusive hydrophobizing reagents, and activated ester inclusive hydrophobizing reagents.

15. The process of any of claims 7-13, wherein the hydrophobizing reagent is selected from the group consisting of 2-(trifluoromethyl)oxirane, 2,2- bis(trifluoromethyl)oxirane, hexafluoropropene oxide, 1 -bromooctane, 1- bromoperfluorohexane, and the following compound:

16. A process of reducing an amount of fluorinated organic constituents (FOC) in an aqueous system, the process comprising:contacting the aqueous system having a first cumulative concentration of FOC with a hydrophobized ion exchange resin of Formula 1:wherein Y is a polystyrenic scaffold or polyacrylic scaffold; wherein Y1is -H or the same or a different polystyrenic scaffold or polyacrylic scaffold as Y;wherein R1, R2, and R3are independently a substituted or unsubstituted compound having a functionality of alkyl, alkylene, alkyne, alkenyl, alkynyl, aryl, alkylaryl, arylalkylene, arylalkyne, arylalkenyl, ary lalky ny I, cyclic, cycloaliphatic, or polycyclic moieties, which may optionally independently contain at least one heteroatom, at least one active hydrogen containing component, at least one quaternized nitrogen moiety, at least one fluorine moiety, or at least one carbonyl-containing component;FP0025-W001wherein R4is -H, a substituted or unsubstituted compound having a functionality of alkyl, alkylene, alkyne, alkenyl, alkynyl, aryl, alkylaryl, arylalkylene, arylalkyne, arylalkenyl, arylalkynyl, cyclic, cycloaliphatic, or polycyclic moieties, which may optionally independently contain at least one heteroatom, at least one active hydrogen containing component, at least one quaternized nitrogen moiety, at least one fluorine moiety, or at least one carbonyl-containing component; wherein X is a chloride, bromide, iodide, fluoride, sulfate, nitrate, acetate, hydroxide, or formate counterion; andwherein n is a positive integer; andwherein the contacting removes at least 95%, by weight, of the FOC from the aqueous system.

17. The process of claim 16, wherein the contacting removes at least 98%, by weight, of the FOC from the aqueous system.

18. The process of claim 16, wherein the contacting removes at least 99%, by weight, of the FOC from the aqueous system.

19. The process of any of claims 16-18, wherein the aqueous system is a fluoropolymer dispersion.

20. The process of any of claims 16-18, wherein the aqueous system is waste water.

21. The process of any of claims 16-18, wherein the aqueous system is drinking water.

22. A fluoropolymer dispersion comprising particles of fluoropolymer dispersed in an aqueous liquid, the fluoropolymer dispersion having a solids content of at least 20 wt% and a total concentration of FOC of about 500 parts-per-billion or less.

23. The fluoropolymer dispersion of claim 22, wherein the total concentration of FOC is about 100 parts-per-billion or less.

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