High capacity perchlorate-selective resins from hyperbranched macromolecules

Abstract

A resin is provided for selectively binding to perchloride and related anions (e.g., TcO.sub.4.sup.−, ReO.sub.4.sup.− and I.sup.−) in aqueous solution. The resin may take the form of microparticles or beads. The beads are prepared by cross-linking macromolecules such as hyperbranched PEI, and quaternizing the amines with hydrocarbon substituents.

Claims

1. A perchlorate-selective microparticle prepared by a method comprising: (a) providing a water soluble branched molecule comprising polyethyleneimine (PEI) with a molecular weight in excess of 1500 Da, the molecule comprising a plurality of branches including a plurality of tertiary amine moieties, a plurality of primary amine moieties, and optionally one or more secondary amine moieties; (b) reacting the branched molecule with a cross-linking agent in an inverse suspension of toluene and water stabilized by a surfactant to produce a cross-linked resin matrix in the form of a spherical microparticle comprising a plurality of primary, secondary, and/or tertiary amine moieties; (c) quaternizing the plurality of primary, secondary, and/or tertiary amine moieties by reacting a haloalkane reactant with the amine moieties to provide quaternary substitution of the amine moieties with alkyl moieties; and (d) during and/or after step (b), removing water from the microparticle so that the water content of the microparticle is less than about 50% water by weight; wherein the perchlorate-selective microparticle is selective for perchlorate and comprises a plurality of branched macromolecular structures (A) and a plurality of cross-linking moieties, wherein the plurality of A is cross-linked through the plurality of cross-linking moieties, and wherein each A comprises a plurality of branches and a plurality of terminal functional groups; wherein each of the plurality of branches comprises an N,N,N-substituted (quaternary) n-aminoalkyl moiety comprising three substituent moieties, and wherein each of the plurality of branches optionally comprises one or more N,N-substituted (tertiary) n-aminoalkyl moieties comprising two substituent moieties; wherein each of the substituent moieties comprises one of the following: (a) another of said plurality of branches; (b) one of the plurality of terminal functional groups; or (c) one of the cross-linking moieties attached at a first cross-linking end, wherein the cross-linking moiety further comprises a second cross-linking end, by which the moiety is also one of the substituent moieties of one of the plurality of branches at a different location within the microparticle; wherein the cross-linking agent comprises a combination of epichlorohydrin (—CH.sub.2—CHOH—CH.sub.2—) and 1-bromo-3-chloropropane (—CH.sub.2—CH.sub.2—CH.sub.2—); and wherein the surfactant comprises sodium dodecyl benzyl sulfonate (SDBS).

2. The microparticle of claim 1, wherein each of the plurality of terminal functional groups are alkyl moieties having no less than two and no more than six carbon atoms.

3. The microparticle of claim 1, wherein the strong-base exchange capacity (SBEC) of the microparticle is greater than about 1.5 eq/L.

4. The microparticle of claim 3, wherein the strong-base exchange capacity (SBEC) of the microparticle is greater than about 2.0 eq/L.

5. The microparticle of claim 4, wherein the strong-base exchange capacity (SBEC) of the microparticle is greater than about 2.5 eq/L.

6. The microparticle of claim 1, wherein the water content of the microparticle is less than about 40% and greater than about 25% by weight.

7. The microparticle of claim 2, wherein the haloalkane reactant is derived from iodoethane, bromobutane, or 1-bromohexane.

8. The microparticle of claim 1, wherein the microparticle selectively binds ClO.sub.4.sup.− in an aqueous media.

9. The microparticle of claim 1, wherein the microparticle is used for water treatment.

10. A perchlorate-selective microparticle prepared by a method comprising: (a) providing a water soluble branched molecule comprising polyethyleneimine (PEI) with a molecular weight of 1800, 10000 or 25000 Da, the molecule comprising a plurality of branches including a plurality of tertiary amine moieties, a plurality of primary amine moieties, and optionally one or more secondary amine moieties; (b) reacting the branched molecule with a cross-linking agent comprising a combination of epichlorohydrin (—CH.sub.2—CHOH—CH.sub.2—) and 1-bromo-3-chloropropane (—CH.sub.2—CH.sub.2—CH.sub.2—) in an inverse suspension of toluene and water stabilized by a surfactant comprising sodium dodecyl benzyl sulfonate (SDBS) to produce a cross-linked resin matrix in the form of a spherical microparticle comprising a plurality of primary, secondary, and/or tertiary amine moieties; (c) quaternizing the plurality of primary, secondary, and/or tertiary amine moieties by reacting a haloalkane reactant with the amine moieties to provide quaternary substitution of the amine moieties with alkyl moieties; and (d) during and/or after step (b), removing water from the microparticle so that the water content of the microparticle is less than about 50% water by weight; wherein the perchlorate-selective microparticle comprises a plurality of branched macromolecular structures (A) and a plurality of cross-linking moieties, wherein the plurality of A is cross-linked through the plurality of cross-linking moieties, and wherein each A comprises a plurality of branches and a plurality of terminal functional groups; wherein each of the plurality of branches comprises an N,N,N-substituted (quaternary) n-aminoalkyl moiety comprising three substituent moieties, and wherein each of the plurality of branches optionally comprises one or more N,N-substituted (tertiary) n-aminoalkyl moieties comprising two substituent moieties; wherein each of the substituent moieties comprises one of the following: (a) another of said plurality of branches; (b) one of the plurality of terminal functional groups; or (c) one of the cross-linking moieties attached at a first cross-linking end, wherein the cross-linking moiety further comprises a second cross-linking end, by which the moiety is also one of the substituent moieties of one of the plurality of branches at a different location within the microparticle.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) The accompanying drawings, which are incorporated into and constitute a part of this specification, illustrate one or more exemplary embodiments of the inventions disclosed herein and, together with the detailed description, serve to explain the principles and exemplary implementations of these inventions. One of skill in the art will understand that the drawings are illustrative only, and that what is depicted therein may be adapted based on the text of the specification or the common knowledge within this field.

(2) In the drawings:

(3) FIG. 1 is a diagram showing two equivalent chemical formulas illustrating an example of hyperbranched poly(ethyleneimine) polymers, which may in one embodiment be used as building blocks for the synthesis of perchlorate-selective media.

(4) FIG. 2 is a diagram and chemical equation illustrating the preparation of base PEI beads by inverse suspension polymerization.

(5) FIG. 3 is a chemical equation illustrating a reaction scheme for alkylation reactions of base PEI resins. The reactions may, for example, be carried out in ethanol or isopropanol (IPA) using diisopropylethylamine (DIPEA) as scavenger.

(6) FIG. 4 is a diagram and chemical equation illustrating a reaction scheme for the production of an alkylated resin. In another embodiment, R may be hydrogen rather than an alkyl group.

(7) FIG. 5 is a diagram and chemical equation illustrating a reaction scheme for the production of a high performance resin using mixed crosslinking.

(8) FIG. 6 is a diagram and chemical equation illustrating a reaction scheme for a method of producing a high performance resin.

(9) FIG. 7A is a graph illustrating the effect of resin mass on the final ClO.sub.4.sup.− concentration from the Redlands makeup groundwater solution. FIG. 7B is a graph illustrating the percentage of ClO.sub.4.sup.− removed.

(10) FIG. 8 is a graph illustrating the extent of ClO.sub.4.sup.− desorption for selected QPEI and commercial resins in 5.8 wt % (1.0 M) NaCl as a function of equilibration time.

(11) FIG. 9 is a graph illustrating perchlorate breakthrough curves of QPEI CJ-4 and PUROLITE A530E resins.

(12) FIG. 10 is a diagram illustrating the structure of a G5-NH.sub.2 poly(propyleneimine) dendrimer.

(13) FIG. 11 is a diagram illustrating the structure of a G4-NH.sub.2 poly(amidoamine) dendrimer.

(14) FIG. 12 is a chemical equation illustrating an example of the production of a hyperbranched lysine macromolecule.

(15) FIG. 13 is a chemical equation illustrating the synthesis of a dendrigraft macromolecule synthesized via grafting of poly(2-ethyl-2-oxazoline) (PEOX) onto linear poly(ethyleneimine).

(16) FIG. 14 is a histogram showing a size distribution of PEI-1.

(17) FIG. 15 is a chemical equation illustrating a functionalization of PEI-1 to create Resin 2.

(18) FIG. 16 is a chemical equation illustrating a functionalization of PEI-1 to create Resin 3.

(19) FIG. 17 is a chemical equation illustrating a functionalization of PEI-1 to create Resin 5.

(20) FIG. 18A is a graph comparing the volume and mass strong-base exchange capacity at various water contents for resin beads in which there was complete crosslinking and removal of water. FIG. 18B shows corresponding resin beads with high exchange capacity.

(21) FIG. 19A is a graph comparing the volume and mass strong-base exchange capacity at various water contents for resin beads in which there was incomplete crosslinking and no step of dehydration. FIG. 19B shows corresponding resin beads with lower exchange capacity.

(22) FIG. 20A is an FT-IR spectrograph of PEI resin beads prepared using the scheme of FIG. 2 (to create beads designated as HPR-2). FIG. 20B shows the similar spectrograph for PEI resin beads with methyl quaternary ammonium groups (HPR-2M), as per the scheme of FIG. 4.

(23) FIG. 21 is a graph showing .sup.13C NMR spectrographic lines for PEI resin beads prepared using the scheme of FIG. 2 (to create beads designated as HPR-2), and for PEI resin beads with methyl quaternary ammonium groups (HPR-2M), as per the scheme of FIG. 4.

(24) FIG. 22 is a graph showing thermogravimetric analysis (TGA) lines for PEI resin beads prepared using the scheme of FIG. 2 (to create beads designated as HPR-2), and for PEI resin beads with methyl quaternary ammonium groups (HPR-2M), as per the scheme of FIG. 4.

(25) FIG. 23A is a graph of particle diameter versus the weight percent of surfactant in the mixture for various PEI resin beads. FIG. 23B shows a similar plot in which both particle size and strong-base exchange capacity are plotted on the same graph, versus weight percent of surfactant in a limited, small range.

(26) FIG. 24 is a graph of perchlorate breakthrough curves of the bifunctional PEI and Styrene-DVB resins in Redlands Makeup Groundwater.

DETAILED DESCRIPTION

(27) In this disclosure there are presented various embodiments of inventions relating to high capacity media that can selectively extract perchlorate from aqueous solutions. As described herein, extraction can in various embodiments be obtained from solutions of varying ionic strength and in the presence of competing anions (e.g. chloride, sulfate, bicarbonate and nitrate) including groundwater, surface water and industrial/municipal wastewater. Media may be created that have higher exchange capacity and selectivity than commercial resins such as the PUROLITE A-530E resin. Hyberbranched PEI macromolecules (FIG. 1) can be used as building blocks to synthesize a new generation of perchlorate-selective anion exchange resins with high capacity. Batch and column studies of perchlorate removal from a simulated groundwater indicate that our these new resins outperform commercial resins in both exchange capacity and selectivity.

(28) Those of ordinary skill in the art will understand that the following detailed description is illustrative only and is not intended to be in any way limiting. Other embodiments of the present inventions will readily suggest themselves to such skilled persons having the benefit of this disclosure, in light of what is known in the relevant arts. Reference will now be made in detail to exemplary implementations of the present inventions as illustrated in the accompanying drawings.

(29) In the interest of clarity, not all of the routine features of the exemplary implementations described herein are shown and described. In the development of any such actual implementation, numerous implementation-specific decisions must be made in order to achieve the specific goals of the developer, such as compliance with application and business-related constraints, and that these specific goals will vary from one implementation to another and from one developer to another. Moreover, such a developmental effort might be complex and time-consuming, but would nevertheless be a routine undertaking of engineering for those of ordinary skill in the art having the benefit of this disclosure.

(30) Throughout the present disclosure, relevant terms are to be understood consistently with their typical meanings established in the relevant art. However, without limiting the scope of the present disclosure, further clarifications and descriptions are provided for relevant terms and concepts as set forth below:

(31) The term degree of branching (DB) has a meaning known in the field, and use herein is consistent with that meaning. A definition is provided, for example, in C. J. Hawker, R. Lee, and J. M. J. Fréchet, The One-Step Synthesis of Hyperbranched Dendritic Polyesters, J. Am. Chem. Soc., 1991, 113: 4583. The degree of branching may be defined by the formula:

(32) $\mathrm{DB}=\frac{.Math.D+.Math.T}{.Math.D+.Math.T+.Math.L}$

(33) where ΣD is the sum of dendritic units, ΣT is the sum of terminal units, and ΣL is the sum of linear units. The terms dendritic units, terminal units, and linear units have their normal meaning as understood by those of skilled in the field. The degree of branching may be determined in several different ways, including directly through analysis of the structure, and indirectly through characterization of .sup.13C-NMR spectra or other indirect means known in the art.

(34) The terms hyperbranched polymer and hyperbranched as used herein refer to their definitions as known to those of skill in the art. A hyperbranched polymer comprises polydisperse dendritic macromolecules which are generally prepared in a single synthetic polymerization step that forms imperfect branches, generally in a non-deterministic way. However, there are many synthetic strategies known in the art to prepare hyperbranched polymers with lower polydispersity. They are typically characterized by their degree of branching (DB). An amine-based hyperbranched polymer may comprise tertiary, secondary, and primary amines, unless it has been modified, in which case the primary amines might as an example be converted to secondary and/or tertiary amines and secondary amines might, for example, be converted to tertiary amines, leading the same imperfect branched structure.

(35) The terms hyperbranched polyethyleneimine (PEI) polymer, or simply polyethyleneimine, or PEI, refers to a class of hyperbranched polymers known in the art. Generally, PEI polymers typically have a degree of branching (DB) of approximately 65-70%, consisting of primary, secondary, and tertiary amines, the amines being linking by C.sub.2 alkyl chains. PEI with various molecular weights (MW) ranging from about 1,000 to several million Daltons are commercially available. Among many ways known in the art for preparing hyperbranched PEI, one is through ring opening polymerization of aziridine. A diagram showing two equivalent chemical formulas illustrating an example of hyperbranched poly(ethyleneimine) polymers, which may in one embodiment be used as building blocks for the synthesis of perchlorate-selective media is illustrated in FIG. 1.

(36) The term moiety as used herein refers to any part of an organic molecule, and may include, without limitation, a functional group, an alkyl chain, a branch of a branched molecule, or a continuation of a branched structure.

(37) In one embodiment, a class of roughly spherical base PEI beads may be prepared in a first step. This class of beads may be created as shown in FIG. 2. This figure is a chemical equation illustrating a hyperbranched polyethyleneimine (PEI) macromolecule (in one embodiment M.sub.w is roughly 25000 Dalton). This macromolecule may be crosslinked with epichlorohydrin (ECH) to afford nearly spherical beads in inverse suspensions of toluene and water stabilized by a surfactant (for example, sodium dodecyl benzyl sulfonate (SDBS), although other surfactants are appropriate). The surfactant may in one embodiment be generated in-situ by reacting dodecyl benzyl sulfonic acid with sodium hydroxide (NaOH). Other cross-linkers may be used with equal effect. Cross-linkers may be expected to have a carbon or other organic chain, with at least two functional groups capable of binding to the primary and secondary amines of the PEI. After cross-linking, what results is a cross-linked hyperbranched class of macromolecules, referred to here as High Performance Resin (HPR).

(38) In addition to hyperbranched PEI macromolecules (FIG. 1), the resin synthesis methodologies described in this disclosure can be applied to any water-soluble branched macromolecules with functional nitrogen (N) groups, including Gx-NH.sub.2 PPI dendrimers (FIG. 10) (see Diallo, M. S. et al. (2007), “Dendritic anion hosts: perchlorate binding to G5-NH.sub.2 poly(propyleneimine) dendrimer in aqueous solutions,” Environmental Science and Technology 41: 6521-6527), Gx-NH.sub.2 PAMAM dendrimers (FIG. 11) (id.), hyperbranched lysine macromolecules (FIG. 12) (Scholl, M. et al (2007), “Controlling polymer architecture in the thermal hyperbranched polymerization of 1-lysine,” Macromolecules 40: 5726-5734), Hybrane hyperbranched polymers and scheme for dendrigraft macromolecules (FIG. 13) synthesized through the grafting of poly(2-ethyl-2-oxazoline) (PEOX) onto linear poly(ethyleneimine) (PEI) (Kee, R. A., Guathier. M. & Tomalia, D. A. (2001), “Semi-controlled dendritic structure synthesis,” in Dendrimers and Other Dendritic Polymers, Frechet, J. M. J. & Tomalia, D. A. eds., John Wiley & Sons, Ltd., pp 209-236).

(39) The synthesis described in FIG. 2 may in one embodiment proceed as follows: A Morton-type flask (one liter) may be used, equipped with an overhead mechanical stirrer, a thermometer, a reflux condenser, an additional funnel, and an inert gas port. To the flask may be added 63 g of water-free PEI. While the flask is cooled in a water bath, a solution of 36 g of concentrated HCl in 42 g of DI-water may be added with an occasional shaking. To this warm PEI solution may be added a mixture of 1 g of sulfonic 100 (acid form of a branched surfactant) in 4 mL of 1.1 N sodium hydroxide solution. After shaking well, 450 mL of toluene may be added and the mixture may be stirred at an oil bath with temperature set at about 70° C. or 80° C. under nitrogen. After about 30 min, a solution of 40 g of ECH (epichlorohydrin) in 70 mL of toluene may be added through an additional funnel within 45 min. The mixture may be stirred for another 30 min after completion of ECH solution and then temperature may be adjusted to 110° C. and a dehydration process using a Dean-Stark apparatus or other equivalent dehydration process may be initialed until about 30 mL of water is collected. After cooling to room temperature, top solvents may be decanted, 400 mL of methanol may be added and the resulting beads may be filtered off and washed twice with methanol. The resulting beads may be transferred into 600 mL of 3 N NaOH solution. The beads may be filtered off, washed three times with DI-water and stored at room temperature. Size and size distributions of these beads may be measured using standard equipment and procedures. The PEI beads may be directly used for the next step reaction. This procedure is for illustrative purposes, and the specifics of this procedure may be modified according to principles of chemical synthesis known in the art.

(40) Reagent grade chemicals may be used to synthesize all the base PEI beads and perchlorate-selective PEI resins described herein. Precursor polyethylenimine macromolecules (PEI) (e.g., SP-018 (molecular weight M.sub.n=1800) and SP-200 (M.sub.n=10,000)) may be purchased from several commercial sources, for example, from Nippon Shokubai Co., Ltd. of Japan. Although commercial-grade PEI is used in this example, other hyperbranched molecules based on amine linkages may also be used, and the hyperbranched macromolecule can be expected to have a wide variety of possible degrees of branching. The degree of branching is expected to affect the size and efficiency of the ultimate bead.

(41) In a second step, the base PEI resins (HPR) may in one embodiment be alkylated via the scheme of FIG. 3 to afford the synthesis of quartemized PEI (QPEI) resins with different alkyl chains. This second step may in one embodiment involve a high temperature refluxing of the reaction mixture at 110° C. using a Dean-Stark apparatus. Because ECH contains two functional groups with different reactivity, it is expected that its more reactive epoxy groups undergo ring opening at the lower temperature of 70° C. to react with amino groups of the PEI. This may be followed by nucleophilic displacement of the chloro groups by the remaining amino groups of the PEI at the higher temperature of 110° C. In all cases, the complete dehydration of the reaction mixtures at 110° C. may be interpreted as an indicator of the completeness of crosslinking reactions.

(42) Table 1 shows that perchlorate has a larger ionic radius and hydration free energy than most anions present in groundwater and surface water. Thus, it would be expected that QPEI resins with hydrophobic cavities will selectively bind perchlorate over more hydrophilic anions such as Cl.sup.−, NO.sub.3.sup.−, HCO.sub.3.sup.− and SO.sub.4.sup.2− based on studies of perchlorate binding to a generation 5 (G5-NH.sub.2) poly(propyleneimine) [PPI] dendrimer and a generation 4 (G4-NH.sub.2) poly(amidoamine) [PAMAM] dendrimer in water and model electrolyte solutions (Diallo et al. 2007).

(43) TABLE-US-00001 TABLE 1 Selected Properties of Perchlorate and Related Anions. .sup.aIonic .sup.bCharge-to- .sup.aHydration Free Anion Radius (nm) Size Ratio Energy (kJ/mol) .sup.cShape ClO.sub.4.sup.− 0.24 −4.2 −259 Tetrahedral TcO.sub.4.sup.− 0.25 −4 −245 Tetrahedral ReO.sub.4.sup.− 0.26 −3.8 −240 Tetrahedral IO.sub.4.sup.− 0.25 −4 −250 Tetrahedral I.sup.− 0.21 −4.8 −282 Spherical Cl.sup.− 0.172 −5.81 −340 Spherical NO.sub.3.sup.− 0.196 −5.10 −300 Trigonal Planar HCO.sub.3.sup.− 0.156 −6.41 −335 Trigonal Planar SO.sub.4.sup.2− 0.230 −8.69 −1295 Tetrahedral .sup.aData compiled by Moyer, B. A. and Bonnese, P. V. (1997), “Physical factors in anion separations,” in Supramolecular Chemistry of Anions. Bianchi, A.; Bowman-James, K. & Garcia-Espana, E., eds., Wiley-VCH, New York, pp 1-44. .sup.bEqual to the ratio of the charge of the anion to its ionic radius. .sup.cGeometrical arrangements of anions taken from Gloe, K.; Stephan, H. and Grotjahn, M. (2003), “Where is the anion extraction going?” Chem. Eng. Technol. 26: 1107-1117.

(44) Various embodiments of the above QPEI resins may include, for example, Resins 1-3 which may be synthesized by reacting a base PEI resin with iodomethane, 1-bromobutane, and 1-bromohexane, respectively. Resin 3 may be further reacted with iodoethane to increase its extent of quaternization (Resin 4). Conversely, Resin 5 may be prepared by reacting a base PEI resin with a branched haloalkane (i.e., 1-bromo-2-methylpropane) and subsequently with 1-iodopropane. In this example, the second alkylation reactions for Resins 4 and 5 would be for the purpose of increasing the conversion of amines to quaternary ammonium groups.

(45) In other embodiments the resins described herein may be used with anions that are related to perchlorate, including TcO.sub.4.sup.−, ReO.sub.4.sup.− and I.sup.−. While significant research efforts have been devoted to the development of selective chelating agents for cation separations, anion separations have comparatively received limited attention. See Moyer, B. A. & Bonnese, P. V. (1997), “Physical factors in anion separations,” in Supramolecular Chemistry of Anions, Bianchi, A.; Bowman-James, K. & Garcia-Espana, E., eds., Wiley-VCH, New York, pp 1-44; Gloe, K., Stephan, H. & Grotjahn, M. (2003), “Where is the anion extraction going?” Chem. Eng. Technol. 26: 1107-1117.

(46) Unlike cations, anions have filled orbitals and thus do not covalently bind to ligands in most cases. Anions have a variety of geometries (e.g., spherical for Cl.sup.− and tetrahedral for ClO.sub.4.sup.−) (Table 1). The charge-to-radius ratios of anions are also lower than those of cations. Because of this, anion binding to ligands through electrostatic interactions tends to be weaker. In addition to electrostatic interactions, anion binding capacity and selectivity also depend on (i) anion hydrophobicity, (ii) solution pH and (iii) solvent polarity (19-20). Table 1 shows that the physicochemical properties (e.g. size, charge, shape and hydration free energy) of anions such as TcO.sub.4.sup.−, ReO.sub.4.sup.−, and I.sup.− are similar to those of ClO.sub.4.sup.−. This strongly suggests that perchlorate selective QPEI resins may also be used to extract TcO.sub.4.sup.−, ReO.sub.4.sup.−, and I.sup.− from aqueous solutions and mixtures. TcO.sub.4.sup.− and I.sup.− are, respectively, the dominant species of .sup.99Tc and .sup.129I. See Icenhower, J. P. et al. (2010), “The biogeochemistry of technetium: a review of the behavior of an artificial element in the natural environment,” American Journal of Science 310: 721-752; Hou X et al. (2009), “A review on speciation of iodine-129 in the environmental and biological samples,” Anal. Chim. Acta. 632: 181-196. These two radionuclides are among the most problematic radionuclides in the environment due to their high inventory, long half-life, and high mobility. Similarly, ReO.sub.4.sup.− is one the major species of Re, a valuable and expensive metal used in the manufacturing of jet engines and catalysts.

EXPERIMENTAL PROCEDURES

(47) Several examples are described. Unless otherwise stated, the experimental details for the Examples are as follows:

(48) All chemicals were reagent grade or better and were used as received. Unless otherwise stated, all salts used were anhydrous potassium salts and were obtained from Alfa Aeasar. Anhydrous sodium perchlorate (NaClO.sub.4) were obtained from Alfa Aesar (ACS, >98%). Polyethyleneimine (PEI) (SP-200, M.sub.n 10,000) was donated by Nippon Shokubai Co., Ltd. Sulfonic 100 (branched dodecyl benzene sulfonic acid, 97%) was obtained from Stepan Company. Commercial ion exchange resins were generously supplied by the respective manufacturer as follows: PUROLITE A-850 and A-530E from The PUROLITE Company, Bala Cynwyd, Pa.; and DOWEX 1 from Dow Chemical Company, Dow Center Midland, Mich. PUROLITE A-850 is a type 1 gel-type acrylic resin and A-530E is a bifunctional macroporous styrene resin. DOWEX 1 is a type 1 marcoporous styrene based resin. All laboratory-prepared resins were synthesized from and converted to the chloride form at AquaNano, LLC, Monrovia, Calif. Each resin was characterized by exchange capacity and moisture content. Deionized water was obtained from an Academic Milli-Q filtration unit (minimum resistivity 18MEΩ).

(49) For uniformity, all resins were initially in the chloride form prior to equilibration with matrix solutions. Unless otherwise stated, all resins were treated by washing successively with 1.0 N HCl (1 L/110 g of resin), deionized water until the pH of the eluate was neutral, 5 wt % NaCl (1 L/10 g resin), and again with deionized water (1 L/10 g resin). Resins 4 and 5 were treated by stirring resins in a pressure vessel containing 5 wt % NaCl (1:5 EtOH solution). The vessel was heated to 60° C. for 1 h, and then the supernatant was dumped. Treatment in pressure was repeated twice for resins 4 and 5 before undergoing the successive treatment washes as described above done on all other resins. After wash treatment, resins were then partially dried to a slightly moist consistency by filtration through a Büchner funnel. Water content of Büchner dried resins was performed by drying 1 g of resin for 8 h at ambient temperature under reduced pressure and reweighed the dried resin. The strong-base exchange capacity (SBEC) for all resins was determine by performing a Mohr titration in accordance to ASTM 2187 sections 59-66. Each resin was packed in a column where the chloride counter-ions were displaced using sodium nitrate. The effluent was collected and the concentration of chloride was measured by titrating with a known concentration of silver nitrate. The chloride concentration corresponds to the available quaternary exchange sites. The SBEC and the water content are listed in Table 2; SBEC is listed on both volume and mass basis.

(50) TABLE-US-00002 TABLE 2 Strong-base exchange capacity and percent moisture of resins. SBEC SBEC Water (mequiv/ (mequiv/ content Functional/alkyl Resin mL) g) (%) group 1 2.7 5.34 41.8 methyl 2 1.8 4.48 43.8 butyl 3 0.7 1.38 23.8 hexyl 4 1.4 2.08 25.0 hexyl, ethyl 5 1.23 2.33 37.9 isobutyl, propyl PUROLITE 1.25 3.90 47.7 Trimethylammonium A-850 DOWEX 1 1.4 4.43 45.5 Trimethylammonium PUROLITE 0.6 3.44 53.5 Triethyl- and trihexyl- A-530E ammonium

(51) Ion chromatography (IC) analyses were performed with a Dionex ICS-2000 equipped with an electrolytic suppressor (CSRS-300 4 mm), dual piston pump, potassium hydroxide eluent generator cartridge (EGCIII), heated conductivity cell, an AS40 autosampler, 4×250 mm AS20 analytical column, and 4×50 mm AG20 guard column. External water mode was employed as described in EPA method 314.0. The analytical detection limit was about 1.5 μg/L.

(52) Scanning electron microscopy (SEM, JEOL JEM-2100F HR) was used to image microcapsules mounted on carbon-tape covered stages. SEM images were acquired after sputter-coating the samples with platinum.

(53) Determination of distribution coefficients (K.sub.d) for ClO.sub.4.sup.− sorption on resins was determined by bringing 50 mg (dry weight equivalent) of resin in contact with a solution containing ClO.sub.4.sup.− (50 mL of test solution). An aliquot of sample was taken after 24 h of continuous shaking on a rotisserie shaker and filtered with a PTFE syringe filter (0.45 μm). The samples were then analyzed for ClO.sub.4.sup.− concentration by IC as described above.

(54) The effectiveness of ClO.sub.4.sup.− desorption by NaCl (1 N, ˜5.8 wt %) was determined by contacting 0.1 g of resin (dry weight equivalent) with a 50-mL test solution containing 200 mg/L ClO.sub.4.sup.−. Samples were shaken overnight, and the supernatant was then decanted and analyzed for ClO.sub.4.sup.− via IC as described above. The amount of ClO.sub.4.sup.− adsorbed by the resin was calculated as the difference between the initial amount of ClO.sub.4.sup.− added and the amount found at equilibrium. Desorption was then induced by rinsing twice with 50 mL of deionized water to remove residual ClO.sub.4.sup.− in the resin after sorption; it was subsequently equilibrated in 50 mL of 1 N NaCl. At different time intervals (0.5, 1, 2, 4, 12, and 24 h), an aliquot (0.1 mL) of supernatant solution was sampled, and after proper dilution with deionized water and filtration through DIONEX OnGuardII Ag cartridge (to precipitate excess chloride), the supernatant was analyzed using the IC parameters shown above.

(55) The particle size distribution was analyzed using a particle-sizer (BECKMAN COULTER RapidVue). Particle size was for the PEI-1 is 597.4±148.01 μm. See FIG. 14 for the corresponding histogram.

Example 1: Synthesis of Example Resins

(56) The following abbreviations are used herein: “ECH” refers to epichlorohydrin. “BCP” refers to 1-bromo-3-chloropropane. “HCl” refers to hydrochloric acid. “DMF” refers to dimethylformamide. “MeOH” refers to methanol. “EtOH” refers to ethanol. “IPA” refers to isopropanol. “NaOH” refers to sodium hydroxide. “MeI” refers to methyliodide. “DIPEA” refers to diisopropylethylamine. “RT” refers to room temperature, or approximately 25° C.

(57) Synthesis of Base PEI Resin (HPR).

(58) In general accordance with the scheme of FIG. 2, a solution of 86 g of 36-38% HCl in 138 g of DI water was added to the reaction flask containing 100 g of PEI over a course of 10 min at ambient temperature under nitrogen. Then a solution of 4 mg of surfactant Sulfonic 100 in 1.1 M NaOH (30 wt %) was then added to the vessel, followed by addition of 450 mL of toluene. The heating bath temperature was then brought to 80° C. In a separate vessel, 50 g ECH and 100 g BCP toluene solution (40 wt %) was prepared. Using an addition funnel, the ECH solution was added over a 60 min period and then the reaction was continued for an additional 2 h before beginning a dehydration using a dean stark apparatus (bath temperature about 110° C.). The reaction end point was reached when all the water from the system had been removed. After temperature cooled to ambient temperature the resins were collected by filtration over a Büchner funnel and were purified by washing with methanol and washing with a 20 wt % solution of NaOH (to remove the surfactant). The beads were then washed twice with deionized water to remove excess NaOH. Büchner dried beads were then stored in 50 mL polypropylene centrifugal tubes at RT.

(59) Synthesis of Resin 1.

(60) In general accordance with the scheme of FIG. 4, 50 mL EtOH (methanol may be used instead, in another embodiment) was added into a 250 mL pressure vessel containing 25 g of Büchner dried base PEI resin (HPR). Then 80 g MeI and 20 mL of DIPEA (proton scavenger) was added to the mixture. Reaction was stirred and heated to 60° C. in a heating bath for 6 h. After temperature cooled to RT, resins were collected by filtration over a Büchner funnel. Resins were washed successively with MeOH (1 L/110 g of resin) to remove organic reagents and byproducts, and then with deionized water (1 L/10 g of resin). Resin was then converted to chloride form as described in the treatment procedure above.

(61) Synthesis of Resin 2.

(62) In general accordance with the scheme of FIG. 15, 50 mL EtOH was added into a 250 mL pressure vessel containing 25 g of Büchner dried HPR for Resin 2.100 g 1-bromobutane and 20 mL of was added to the mixture. Reaction was stirred and heated to 80° C. in a heating bath for 6 h. After temperature cooled to RT, resins were collected by filtration over a Büchner funnel. Resins were washed successively with MeOH (1 L/110 g of resin), and then with deionized water (1 L/10 g of resin). Resin was then converted to chloride form as described in the treatment procedure above.

(63) Synthesis of Resin 3.

(64) In general accordance with the scheme of FIG. 16, 75 mL IPA was added into a 250 mL pressure vessel containing 40 g of Büchner dried HPR. 100 g 1-bromohexane and 20 mL of was added to the mixture. Reaction was stirred and heated to 80° C. in a heating bath overnight. After temperature cooled to RT, resins were collected by filtration over a Büchner funnel. Resins were washed successively with MeOH (1 L/110 g of resin) and then with deionized water (1 L/10 g of resin). Resin was then converted to chloride form as described in the treatment procedure above.

(65) Synthesis of Resin 4.

(66) 40 mL EtOH was added into a 250 mL pressure vessel containing 25 g of Büchner dried Resin 3. Then 50 g 1-iodoethane and 20 mL of DIPEA was added to the mixture. Reaction was stirred and heated to 0° C. in a heating bath for 6 h. After temperature cooled to RT, resins were collected by filtration over a Büchner funnel. Resins were washed successively with MeOH (1 L/10 g of resin) and then with deionized water (1 L/10 g of resin). Resin was then converted to chloride form as described in the modified treatment procedure above.

(67) Synthesis of Resin 5.

(68) In general accordance with the scheme of FIG. 17, 75 mL IPA was added into a 250 mL pressure vessel containing 40 g of Büchner dried PEI-1.100 g 1-bromohexane and 20 mL of was added to the mixture. Reaction was stirred and heated to 80° C. in a heating bath overnight to afford A5. Supernatant was then decanted and 75 mL EtOH was added to A5. Then 50 g 1-iodoethane and 20 mL of DIPEA was added to the mixture. Reaction was stirred and heated to 80° C. in a heating bath for 6 h. After temperature cooled to RT, resins were collected by filtration over a Büchner funnel. Resins were washed successively with MeOH (1 L/10 g of resin) and then with deionized water (1 L/10 g of resin). Resin was then converted to chloride form as described in the modified treatment procedure above.

Example 2: Comparison of QPEI Resin Sorption Against Sorption of Commercial Resins

(69) Batch sorption studies are described which evaluate the performance of the QPEI resins against representative commercial resins. Perchlorate sorption onto the resins was measured by mixing varying amounts of media (25, 50, 100, 150, 200, and 250 mg in dry weight) with 50 mL of a test solution containing 625 ppb (g/L) of perchlorate. The test solution was representative of a contaminated groundwater from Redlands (California) that was employed in a previous study of perchlorate-selective resins conducted by Oak Ridge National Laboratory. See Gu, B. H. et al. (1999), “Selective anion exchange resins for the removal of perchlorate (ClO.sub.4.sup.−) from groundwater,” Oak Ridge National Laboratory Report ORNL/TM-13753. The makeup Redlands groundwater was prepared by dissolving 3 mM NaHCO.sub.3, 1 mM CaCl.sub.2, 0.5 mM MgCl.sub.2, 0.5 mM Na.sub.2SO.sub.4, and 0.5 mM KNO.sub.3 in deionized water. Table 3 lists the concentration of perchlorate and competing anions in the simulated Redlands groundwater matrix.

(70) TABLE-US-00003 TABLE 3 Concentration of perchlorate and competing anions in a Redlands makeup ground water..sup.a Anion Concentration Unit ClO.sub.4.sup.− 625 μg/L Cl.sup.− 106 mg/L NO.sub.3.sup.− 31 mg/L HCO.sub.3.sup.− 183 mg/L SO.sub.4.sup.2− 49 mg/L .sup.aThe test solution was a simulation of a typical contaminated groundwater found in Redlands California. The makeup ground water was prepared by dissolving 3 mM of NaHCO.sub.3, 1 mM of CaCl.sub.2, 0.5 mM MgCl.sub.2, and 0.5 mM Na.sub.2SO.sub.4, and 0.5 mM KNO.sub.3 in deonized water.

(71) Following Gu & Brown (2006), the resin-water distribution coefficient K.sub.d (mL/g) of perchlorate was expressed as:

(72) $\begin{array}{cc}{K}_d=\frac{\left(C_i-C_f\right)/M}{C_f}& \mathrm{Eq}.1\end{array}$

(73) where C.sub.i and C.sub.f are, respectively, the initial and final concentrations of ClO.sub.4.sup.− (mg/L) in solution and M is the mass of resin per unit volume of solution (mg/L). K.sub.d was subsequently used to calculate the normalized resin-water distribution coefficient K.sup.Eq (mL/meq) as given below:

(74) $\begin{array}{cc}{K}_d^{\mathrm{Eq}}=\frac{K_d}{\mathrm{SBEC}}& \mathrm{Eq}.2\end{array}$

(75) where SBEC (meq/g) is the strong-base exchange capacity (SBEC) of each resin as measured by Mohr titration. See Bonnesen, P. V. et al. (2000), “Development of bifunctional anion-exchange resins with improved selectivity and sorptive kinetics for pertechnetate: batch-equilibrium experiments,” Environ. Sci. Technol. 34: 3761-3766. The final K.sub.d and K.sub.d.sup.Eq values reported in Table 4 are the average of 6 measurements after 24 hours of equilibration time.

(76) TABLE-US-00004 TABLE 4 ClO.sub.4.sup.− Distribution Coefficients for Selected QPEI Beads and Commercial Resins. Water .sup.aSBEC .sup.aSBEC Content .sup.bK.sub.d .sup.cK.sub.d.sup.Eq Resin Quaternary Resin (eq/L) (meq/g) (%) (mL/g) (mL/meq) Backbone Amine Alkyl Group CJ-1 2.70 5.34 41.8 7359 1379 PEI Methyl CJ-2 1.80 4.48 43.8 48906 10917 PEI Butyl CJ-3 0.70 1.38 23.8 233318 169071 PEI Hexyl CJ-4 1.40 2.08 25.0 295490 142062 PEI Hexyl and Ethyl CJ-5 1.23 2.33 37.9 123098 52832 PEI Isobutyl and Propyl PUROLITE 1.25 3.90 47.7 3617 927 Acrylic- Trimethyl A-850 DVB DOWEX 1.40 4.43 45.5 97398 21980 Styrene- Trimethyl 1 DVB PUROLITE 0.60 3.44 53.5 195422 56795 Styrene- Triethyl and Trihexyl A-530E DVB .sup.aThe strong-base exchange capacity (SBEC) of each resin was measured by Mohr titration. $\begin{array}{c}{}^b\mathrm{The}\mathrm{resin}\text{-}\mathrm{water}\mathrm{distribution}\mathrm{coefficient}{K}_d\left(\mathrm{mL}\text{/}g\right)\mathrm{of}\mathrm{perchlorate}\mathrm{was}\mathrm{expressed}\mathrm{as}\text{:}\\ K_d=\frac{\left(C_i-C_f\right)/M}{C_f};\mathrm{where}{C}_i\mathrm{and}{C}_f\mathrm{are},\mathrm{respectively},\mathrm{the}\mathrm{initial}\mathrm{and}\mathrm{final}\mathrm{concentrations}\mathrm{of}\\ \mathrm{perchlorate}\left(\mathrm{mg}\text{/}L\right)\mathrm{in}\mathrm{solution}\mathrm{and}M\mathrm{is}\mathrm{the}\mathrm{mass}\mathrm{of}\mathrm{resin}\mathrm{per}\mathrm{unit}\mathrm{volume}\mathrm{of}\mathrm{solution}\left(\mathrm{mg}\text{/}L\right).\\ \mathrm{The}\mathrm{final}{K}_d\mathrm{values}\mathrm{reported}\mathrm{in}\mathrm{Table}3\mathrm{are}\mathrm{the}\mathrm{average}\mathrm{of}6\mathrm{measurements}\mathrm{after}24\mathrm{hours}\\ \mathrm{of}\mathrm{equilibration}\mathrm{time}.\end{array}\hspace{1em}$.sup.cThe K.sub.d was subsequently used to calculate the normalized resin-water distribution coefficient K.sup.Eq (mL/meq) as given below: $\begin{array}{c}{K}_d^{\mathrm{Eq}}=\frac{K_d}{\mathrm{SBEC}};\mathrm{where}\mathrm{SBEC}\left(\mathrm{meq}\text{/}q\right)\mathrm{is}\mathrm{the}\mathrm{strong}\text{-}\mathrm{base}\mathrm{exchange}\mathrm{capacity}\left(\mathrm{SBEC}\right)\mathrm{of}\mathrm{each}\mathrm{resin}\\ \mathrm{as}\mathrm{measured}\mathrm{by}\mathrm{Mohr}\mathrm{titration}.\end{array}\hspace{1em}$

(77) Table 4 lists the measured K.sub.d and K.sub.d.sup.Eq values for the QPEI beads and commercial resins. The distribution coefficient K.sub.d is often employed as a measure of the sorption capacity of trace anions by ion exchange resins in aqueous solutions per unit mass of media (Gu & Brown, 2006; Gu et al. 1999). Conversely, the normalized distribution coefficient K.sub.d.sup.Eq can be used as a measure of the anion sorption affinity/selectivity of the resins per exchange site of media (Bonnesen et al. 2000). The magnitudes of the K.sub.d and K.sub.d.sup.Eq values of the QPEI 1-3 resins clearly indicate their selectivity for perchlorate increases with resin hydrophobicity (Table 1). This is consistent with previous measurements showing that in aqueous solutions and model electrolyte solutions a G5-NH.sub.2 PPI dendrimer provides a more favorable environment for the partitioning of perchlorate anions than the more hydrophilic G4-NH.sub.2 PAMAM dendrimer (Diallo et al. 2007). This observation is also consistent with the preferential sorption of perchlorate onto the styrene-DVB DOWEX-1 resin over the more hydrophilic acrylic-DVB PUROLITE A-850E resin. Table 4 also shows that the QPEI 3 resin with hexyl quaternary ammonium groups has a higher ClO.sub.4.sup.− selectivity (i.e. K.sub.d.sup.Eq value) than the PUROLITE A-530E resin with trihexyl and triethyl quaternary ammonium groups even though both resins have volumetric SBEC (0.6-0.7 eq/L). Note that the bifunctional QPEI 4 resin with hexyl and ethyl quaternary ammonium groups has larger exchange capacity (1.4 eq/L) and higher perchlorate K.sub.d and K.sub.d.sup.Eq values than the A-530E resin. FIGS. 7A and B show the selective QPEI resin CJ-3 can remove perchlorate from the Redlands makeup groundwater solution to below detection limit (˜2 ppb). Conversely, the non-selective resins (QPEI CJ-1 and PUROLITE A-850) are not able to remove perchlorate below detection limit even at higher resin loads.

Example 3: Comparison of QPEI Resin Desorption Against Desorption of Commercial Resins

(78) Batch desorption studies are described which evaluate the desorption of perchlorate from selected QPEI and commercial resins. For each resin, 0.1 g of dry media was first equilibrated overnight with a 50 mL solution of Redlands makeup groundwater containing 200 mg/L of ClO.sub.4.sup.−. Following the determination of the amount of ClO.sub.4.sup.− sorbed by each media, the supernatant solutions were decanted. Each media was subsequently washed twice with a 50 mL aliquot of deionized water to remove residual and unbound ClO.sub.4.sup.−. Following this, each resin was equilibrated with an aqueous solution of 5.8 wt % NaCl to induce desorption through the exchange of Cl.sup.− ions with the sorbed ClO.sub.4.sup.− ions. FIG. 8 shows limited extent of ClO.sub.4.sup.− desorption (<50%) from the most selective resins (CJ-3 and PUROLITE A-530E). Conversely, the least selective resins (CJ-1 and PUROLITE A-850) exhibit a high extent of ClO.sub.4.sup.− desorption (>80%). The results are consistent with previous studies showing that perchlorate-selective resins have low regeneration efficiency in conventional brine (˜12 w % NaCl solution) (Gu & Brown 2006; Tripp & Clifford 2006; Lehman et al. 2008; Gu, Brown & Chiang 2007). The overall results of the sorption and desorption studies indicate the QPEI CJ-3 resin has a higher ClO.sub.4.sup.− selectivity than the PUROLITE A-530E. To our knowledge, the bifunctional A-530E resin has the highest ClO.sub.4.sup.− selectivity among all commercial styrene-DVB resins (Gu, Brown & Chiang 2007).

Example 4: Comparison of Operational Capacity of QPEI CJ-4 Resin with Bifunctional A-530E Resin

(79) Column studies are described which compare the operational capacity of the bifunctional QPEI CJ-4 resin against the bifunctional A-530E resin. Both resins have high selectivity for ClO.sub.4.sup.− and contain hexyl/ethyl quaternary ammonium exchange sites. Two different batches of QPEI CJ-4 resin were synthesized. The first batch (CJ-4-a) yielded a QPEI resin with a SBEC of 1.40 eq/L. The second batch (CJ-4-b) produced a SBEC of 1.9 eq/L. To compare the operational capacity of the resins while reducing the length of the column experiments, accelerated breakthrough experiments were carried out using Redlands makeup groundwater containing an initial ClO.sub.4.sup.− concentration of 10 mg/L. The ion exchange mini-column consisted of 3-3.4 mL of resins (Cl form) that were packed in a 0.7-cm-inner-diameter glass chromatography column, resulting in a bed depth of 8 cm. Test solutions were pumped through the mini-columns with a flow rate of 3.0 mL/min through a peristaltic pump, Model EP-1 ECONO PUMP (Bio-Rad Laboratories). The system had an empty bed contact time of 1 min and a superficial linear velocity of 8 cm/min (1,440 BV/d). FIG. 9 shows the ClO.sub.4.sup.− breakthrough curves of the media.

(80) Table 5 summarizes the results of the breakthrough experiments. Using the volume of water treated (Gallons) per volume of media (cubic foot) at 30% breakthrough as measure of operational capacity, we find that the operational capacity (OC) of both the QPEI CJ-4a and CJ-4-b resins are ≥2.20× than that of the PUROLITE A-530E (Table 5). The overall results of the sorption and column studies indicate the QPEI CJ-3 resin has a higher ClO.sub.4.sup.− selectivity and operational capacity (by more 2.2×) than the PUROLITE A-530E. It appears that the bifunctional A-530E resin may have the highest ClO.sub.4.sup.− selectivity and operational capacity among all commercial styrene-DVB resins (Gu, Brown & Chiang 2007).

(81) TABLE-US-00005 TABLE 5 Comparison of Operational Capacity for Perchlorate- Selective QPEI and Commercial Resins. Media .sup.aThroughput SBEC SBEC Bed Volume (Gallons/Cubic Performance Media (eq/L) Ratio [C/Co].sub.perc Volume (mL) Feet of Resin) Ratio CJ-4a 1.4 2.33 0.30 7558 3.4 56544 2.36 CJ4-b 1.9 3.17 0.30 7465 3.4 53662 2.24 A-530E 0.6 1.0 0.31 3200 3.0 23938 1.0 .sup.aThe volume of water treated per volume of media at 30% breakthrough (i.e. [C/Co].sub.perc = 0.3 was used as measure of the operational capacity of the perchlorate-selective resins.

Example 5: Characterization of Quaternized PEI Resin Beads

(82) In this example, quaternization of the base PEI resin beads with iodomethane leads to ion exchange resin beads with methyl quaternary ammonium exchange sites (FIGS. 18A and B) and SBEC of 2.8-3.0 eq/L. In contrast, branched PEI resins prepared without a prior complete dehydration of the reaction mixtures at 110° C. generally displayed a more granular structure (FIG. 19B) with high water content (>50%) and SBEC only reaching 1.16-1.68 eq/L (FIG. 19A). FIG. 20A, FIG. 20B, and FIG. 21 show the FT-IR and 13C solid-state NMR spectra of a base PEI resin (designated as HPR-2) and the same resin after quaternization with iodomethane (HPR-2M). Both resins were synthesized using a precursor PEI macromolecule with Mn=1800 Dalton. The .sup.13C NMR spectrum of the bare PEI resin (HPR-2) displays a broad C—N peak with three unresolved shoulders at ˜54.18 ppm corresponding to the primary, secondary and tertiary amine moieties of the resin. In contrast, a single, narrow and well-resolved C—N peak at ˜54.18 ppm is seen in the spectrum of the PEI resin with methyl quaternary ammonium groups (HPR-2M). In addition, the quaternized PEI resin displays a carbon-nitrogen stretch at 919 cm.sup.−1 in its IR spectrum, which is characteristic of quaternary ammonium groups (FIG. 20B) and is consistent with the .sup.13C NMR spectra. FIG. 22 shows the TGA curves of the base PEI resin and its fully quaternized counterpart. The base PEI resin (HPR-2) exhibits a three-step weight loss curve, which is consistent with literature data. The first weight loss, leveling off at ˜77° C., is attributed to loss of water from the resin; this is followed by another dehydration process involving the hydroxyl group of the resin seen as a step leveling off at ˜178° C. Finally, thermal decomposition of the base resin starts at 240° C. FIG. 22 shows a more complex weight loss pattern for the quaternized PEI resin (HPR-2M) with a first step leveling off at ˜180° C. corresponding to the combined loss of water, OH groups and quaternary ammonium groups followed by thermal degradation of the resin.

(83) FIGS. 23A and B illustrate the versatility of the new resin synthesis strategy in this example. By varying the weight fractions of surfactant in the water-in-toluene suspensions and the molar mass of the precursor PEI macromolecules, a series of HPRs were prepared with methyl quaternary ammonium groups and size ranging from 20 μm to 600 μm (FIGS. 23A and B). Here again, optimization of the water content of the resins during crosslinking was required to achieve resins with SBEC of ca. 2.8 eq/L (FIG. 23B). FIG. 23A highlights the effect of surfactant concentration on the size of the PEI resin beads. It is known in the art that the size and stability of water droplets in water-in-oil (W/O) emulsions may determine the size distributions of particles produced by inverse emulsion polymerization. It has been shown that in W/O emulsions, the size and stability of water droplets may be controlled by surfactant adsorption and subsequent reduction of the interfacial tension between the water and oil phases. FIG. 23A shows that the sizes of the resins prepared using PEI with molecular weight M.sub.n=1800 Da decrease from an initial value of ˜140 m to about 20 μm as the concentration of surfactant increases from 0.014 wt % to 0.51 wt %. In order to increase the size of the PEI beads to about 600 μm, a precursor PEI macromolecule was needed, with molar mass of about M.sub.n=10,000 Da instead of the lower molar mass PEI with M.sub.n=1800 Da.

(84) Although the PEI resins with methyl quaternary ammonium groups possess a high exchange capacity and can be used to remove a broad variety of anions from solutions, the selective extraction of toxic or valuable anions including perrhenate, pertechnetate and perchlorate is required in many environmental and industrial separation processes. Therefore, the use of the example high performance crosslinked PEI resins was investigated, to prepare novel highly selective resins suitable for the extraction of large and poorly hydrated anions such perchlorate (ClO.sub.4.sup.−), pertechtenate (TcO.sub.4.sup.−) and perrhenate (ReO.sub.4.sup.−) from aqueous solutions. ClO.sub.4.sup.− is a persistent and widespread contaminant found in surface and groundwater in various locations including the United States. At high concentration, ClO.sub.4.sup.− can inhibit the uptake of iodide by the thyroid gland and may disrupt its ability to produce hormones critical to developing fetuses and infants. TcO.sub.4.sup.− is the dominant species of .sup.99Tc.sup.25. It is among the most problematic radionuclides in the environment due to its high inventory, long half-life (213,000 years) and high mobility in groundwater. ReO.sub.4.sup.− is one the major species of Re, an expensive metal used in the manufacturing of jet engines and catalysts. Table 1 shows that ClO.sub.4.sup.−, TcO.sub.4.sup.−, and ReO.sub.4.sup.− have comparable physicochemical properties including size, shape and hydration free energies, which are much less favorable than those of anions such Cl.sup.−, NO.sub.3.sup.−, HCO.sub.3.sup.− and SO.sub.4.sup.2−. Thus, based on our earlier studies of ClO.sub.4.sup.− binding to a generation (G5-NH.sub.2) poly(propyleneimine) [PPI] dendrimer and a G4-NH.sub.2 poly(amidoamine) [PAMAM] dendrimer, it is expected that branched PEI resins with hydrophobic cavities containing quaternary amine groups would exhibit binding selectivity for ClO.sub.4.sup.−, TcO.sub.4.sup.−, and ReO.sub.4.sup.− over competing anions in aqueous solutions. It is known that a bifunctional St-DVB resin with trihexyl and triethyl ammonium chloride groups can selectively remove trace amounts of ClO.sub.4.sup.− and TcO.sub.4.sup.− in contaminated groundwater in the presence of competing anions. Therefore, a two-step approach can be employed to synthesize branched PEI resins that can selectively remove ClO.sub.4.sup.− and closely related anions such TcO.sub.4.sup.− and ReO.sub.4.sup.−. First, a series of resins with tunable hydrophobicity may be prepared using mixtures of epichlorohydrin (ECH) and 1-bromo-3-chloropropane (BCP) (FIG. 5) to crosslink a precursor PEI with molar mass M.sub.n=10000 Da.

(85) Next, the base PEI beads (HPR*) may be quaternized through the sequential addition of 1-bromohexane followed by dimethyl sulfate, 1-bromoethane, or 1-bromopropane (FIG. 6). By optimizing the molar ratio of ECH to BCP in the water-in-toluene suspensions (FIG. 5) and the alkylation conditions (FIG. 6), three strong-base PEI resins may be synthesized, containing both (i) hexyl and methyl groups (HPR*-ME), (ii) hexyl and ethyl groups (HPR*-HM) and (iii) hexyl and propyl groups (HPR*-HP). To assess the performance of the bifunctional PEI resins, column studies of perchlorate extraction were carried out from a Redlands make-up groundwater sample. The composition of this water is found in Table 6. The test solution was a simulation of the typical contaminated groundwater found in Redlands Calif. The makeup ground water was prepared by dissolving 3 mM of NaHCO.sub.3, 1 mM of CaCl.sub.2, 0.5 mM MgCl.sub.2, and 0.5 mM Na.sub.2SO.sub.4, and 0.5 mM KNO.sub.3 in deonized water. Redlands makeup groundwater containing an initial ClO.sub.4.sup.− was used to reduce the concentration of 10 mg/L to reduce the duration of the experiments by accelerating the breakthrough of perchlorate through the columns.

(86) TABLE-US-00006 TABLE 6 Concentration of perchlorate and competing anions in the Redlands Makeup Groundwater. Anion Concentration Unit Cl.sup.− 106 mg/L NO.sub.3.sup.− 31 mg/L HCO.sub.3.sup.− 183 mg/L SO.sub.4.sup.2− 49 mg/L ClO.sub.4.sup.− 10 mg/L

(87) The performance of the PEI bifunctional resins was also benchmarked against that of the bifunctional St-DVB resin PUROLITE A532E31. It appears that among all commercial St-DVB resins, the A532E resin provides the highest known selectivity and operational capacity for extraction of ClO.sub.4.sup.− and TcO.sub.4.sup.− from contaminated groundwater. FIG. 24 shows the ClO.sub.4.sup.− breakthrough curves of the PEI resins. The volume of water treated (m.sup.3) per volume of resin (m.sup.3) at 10% breakthrough (i.e., [C/Co]=0.1) is used as a measure of the operational capacity (OC). FIG. 24 shows that the bifunctional PEI resins with hexyl+ethyl groups (HPR*-HE) and hexyl+propyl (HPR*-HE) outperform the commercial A532E resin by a factor of 1.7 and 1.4, respectively, in OC for perchlorate extraction from Redlands makeup groundwater. Not surprisingly, the OC advantages of these PEI resins (OC Ratio) over the A532E resin match the corresponding exchange capacity advantages (SBEC Ratio). In contrast, the bifunctional PEI resin with hexyl+methyl groups has a lower OC than the A532E resin despite of its high exchange capacity advantage (SBEC Ratio=2.3). These findings suggest that the exchange capacity and selectivity of our new PEI-based high performance resins can be tuned to improve the efficiency and economics of anion separations by ion exchange with multiple applications in environmental and industrial separations including water purification, metal extraction, nuclear fuel processing, and nuclear waste treatment.

(88) While embodiments and applications have been shown and described, it would be apparent to those skilled in the art having the benefit of this disclosure that many more modifications than mentioned above are possible without departing from the inventive concepts disclosed herein. The invention, therefore, and the scope of the appended claims, should not be limited to the embodiments described herein.