Phosphonic Acid Resin Research Articles

Development of Recyclable Polystyrene-Supported Phosphonic Acid Resins for Carbohydrate Immobilization and Glycosylation.

This article describes the development of a recyclable polystyrene-based phosphonic acid resin and its use for the synthesis of immobilized glycosyl phosphonate donors and subsequent glycosylation reaction. This solid support was generated on a decagram scale from the commercially available Merrifield resin and subsequently functionalized via two different methods into eight different glycosylphosphonates. The resultant glycosylphosphonate-containing resins were obtained in 59-96% yields and were found to be bench-stable at room temperature. These donors could be activated using trifluoroborane etherate at 80 °C to react with various alcohol- and thiol-based acceptors to provide 17 different glycosides in good-to-excellent yields (53-98%). In addition, it was demonstrated that glycosylated resin could be recovered and recycled multiple times to regenerate immobilized glycosylphosphonate donors and could be subjected to on-resin glycan elongation.

Membrane-free electrodeionization using phosphonic acid resin for nickel containing wastewater purification

Membrane-free elctrodeionization (MFEDI) is a technology in which ion exchange resins can be electrically regenerated in situ. It allows the purification of nickel containing wastewater, as well as the production of concentrated nickel solution, which could be recycled. However, proper choice of packed ion exchange resins is crucial to MFEDI. In this study, emphasis was placed on improving the performance of MFEDI by the introduction of phosphonic acid resin. Much of this information was obtained by analyzing the characteristic of phosphonic acid resin, the stack configuration of packed ion exchange resin and the mechanism of electrical regeneration. The layered hybrid resin bed filled with both phosphonic acid resin and weak acid resin was found to be the most effective stack configuration for the adjustment of concentrate pH. The purification study demonstrated that, pure water with conductivity below 0.3 μS/cm was produced. The electrical regeneration study showed that, the average concentrate nickel concentration was over 95 mg/L, the concentrate pH was around 7.4, thus precipitation of nickel hydroxide was prevented. Moreover, in comparison to previous study, in which MFEDI was packed with hybrid strong acid and weak base resin and hybrid weak acid and strong base resin, the water recovery ratio was increased from 88.0% to 89.5%, the energy consumption was decreased from 5.6 to 4.1 kWh/m3 wastewater. The regeneration mechanism study revealed that, more than 72% of resin regeneration was attributed to the water splitting, and less than 28% of resin regeneration was contributed by the water electrolysis.

Phosphonic acid and alkyl phosphate-derivatized resins for the simultaneous concentration and detection of uranium in environmental waters

The objective of this study was to synthesize extractive scintillating resins for the direct, real-time analysis of uranium in neutral pH environmental waters. In the first synthetic approach, a methyl phosphonic acid-derivatized resin was prepared by suspension polymerization to create a matrix containing a covalently bound fluorophore and 4-vinylbenzyl chloride, followed by phosphorylation and hydrolysis to add phosphonic acid functionality. In the second approach, methyl phosphate-derivatized resin was synthesized in a one-step suspension polymerization, resulting in matrix containing a covalently bound fluorophore and ethylene glycol methacrylate phosphate ligand. Uranium binding capacity and detection efficiency of the resins were evaluated in pH 4, 6 and 8 simulated ground water and compared. The ability of both resins to detect uranium from neutral pH simulated ground water was evaluated through a Shewart-3σ control statistic applied to real-time data collected in a flow-cell detector. Resins exhibited similar binding capacities (0.18 mmol g−1) and detection efficiencies; however, the methyl phosphate resin concentrated uranium more rapidly from simulated ground water than the phosphonic acid resin. The pH dependence on the volume to detection was interpreted through changes in uranium speciation and binding mechanism supported by computational simulations.

Solid-liquid extraction of Gd(III) and separation possibilities of rare earths from phosphoric acid solutions using Tulsion CH-93 and Tulsion CH-90 resins

Solid-liquid extraction of gadolinium was investigated from phosphoric acid medium using commercial amino phosphonic acid resin, Tulsion CH-93. The experimental conditions studied included equilibration time, acid concentration, mass of the resin, metal concentration, loading and elution. The percent extraction of Gd(III) was studied as a function of phosphoric acid (0.05-3 mol/L) using Tulsion CH-93 resin. The corresponding lgD vs. equilibrium pH plot gave straight line with a slope of 1.8. The percent extraction decreased with acid concentration increasing, conforming ion exchange mechanism. Under observed experimental conditions the loading capacity of Tulsion CH-93 for gadolinium was 10.6 mg/g. Among several eluants screened, the quantitative elution of Gd(III) from loaded Tulsion CH-93 was obtained with ammonium oxalate (0.15 mol/L). The extraction behavior of commonly associated metals with gadolinium was studied as a function of phosphoric acid concentration. Tulsion CH-93 resin showed selective extraction towards heavy rare earths (Lu and Yb) which could be separated from other rare earths at 3 mol/L H3PO4, similar to wet phosphoric acid (3–5 mol/L). On the other hand Gd(III) and other rare earths were studied with chelating resin Tulsion CH-90. Light rare earths were highly extracted and these could be separated from heavy rare earths and Gd.

Synthesis of Amino Methylene Phosphonic Acid Resin-Supported Hydrated Cerium Oxide Hybrid Sorbent and its Application in Drinking Water

The hydrated cerium oxide (CeH) was synthesized and it was loaded on amino methylene phosphonic acid resin (APAR) to form the hybrid adsorbent CeH-APAR. The structure and thermal properties of CeH-APAR were tested by FTIR and TGA. And then, it was investigated that pH values and temperatures affected the adsorption property of CeH and CeH-APAR for fluoride ion. The results showed that CeH-APAR hybrid sorbent formed by Ce4+ and APAR with coordination bond is relatively stable below 270°C. Its adsorption property is similar to that of CeH, i.e. it is less affected by pH value, so it can be used in a wide pH range. Besides, under a stable pH, adsorption capacity of CeH-APAR also increases along with increasing temperature. As a result, it is a temperature-controlled sorbent and belongs to chemical adsorption.

Adsorption behavior and mechanism of amino methylene phosphonic acid resin for Ag(I)

The sorption properties of amino methylene phosphonic resin(APAR) for Ag(I) were studied. The amino methylene phosphonic acid resin(APAR) has a good adsorption ability for Ag(I) at pH=6.0 in the HAc-NaAc medium. The statically saturated adsorption capacity is 272 mg/g resin, Ag(I) adsorbed on APAR can be eluted by 5% (NH 2) 2CS-0.5 mol/L hydrochloric acid quantitatively. The adsorption rate constants determined under various temperatures are k 15°C=3.89 × 10 −5S −1, k 25°C=5.93 × 10 −5S −1, k 35°C=7.59 × 10 −5S −1, k 45°C=9.45 × 10 −5S −1, respectively. The apparent activation energy of adsorption, E a is 22.8 kJ/mol, the enthalpy change (Δ H) of sorption is 17.4 kJ/mol. The adsorption mechanism shows that the functional group of APAR coordinates with Ag(I) to form coordination bond, the coordination molar ratio of the functional group of APAR to Ag(I) is 1:1.

Adsorption of macroporous phosphonic acid resin for nickel

The adsorption behavior and mechanism of a novel chelate resin, macroporous phosphonic acid resin (PAR) for Ni(II) were investigated. The statically saturated adsorption capacity is 64.3 mg·g−1 resin at 298 K in HAc-NaAc medium. The Ni(II) adsorbed on PAR can be eluted by 0.5 mol·L−1 HCl and the elution percentage reaches 96.6%. The resin can be regenerated and reused without obvious decrease in adsorption capacity. The apparent adsorption rate constant is k298=2.6×10−5 s−1. The adsorption behavior of PAR for Ni (II) obeys the Freundlich isotherm. The thermodynamic adsorption, parameters, enthalpy change ΔH, free energy change ΔG and entropy change ΔS of PAR for Ni(II) are 3.36 kJ·mol−1, −5.47 kJ·mol−1 and 29.6J·mol−1·K−1, respectively. The apparent activation energy is Ea=12.2kJ·mol−1. The molar coordination ratio of the functional group of PAR to Ni(II) is about 4∶1. The adsorption mechanism of PAR for Ni(II) was examined by a chemical method and IR spectrometry.

Enhanced metal ion affinities by supported ligand synergistic interaction in bifunctional polymer-supported aminomethylphosphonates

The Mannich reaction is applied to the phosphorylation of amine resins with monoamine, ethylenediamine, diethylenetriamine, and tetraethylenepentamine ligands to give a series of bifunctional aminomethylphosphonic acid resins. The microenvironment around each ligand was varied by preparing fully functionalized resins, a second set of resins with 82 mol% phenyl groups in the polymer, and a third set with 82 mol% carbomethoxy groups. The affinity of the resins for Cu(II), Cd(II), Pb(II), and Eu(III) was evaluated from solutions buffered at pH 5. Synergism is observed under certain conditions where both groups operating together complex more metal ions than either one alone. Ion exchange by the phosphonate portion of the ligand and coordination by the amine portion cooperate as a dual mechanism for metal ion complexation. Synergistic complexation of Cd(II) by all bifunctional aminomethylphosphonate resins (regardless of microenvironment) and of all metal ions by all bifunctional resins within the carbomethoxy microenvironment is quantified. For example, 26% Cd(II) is complexed by the ethylenediamine resin (distribution coefficient of 26), and 49% Cd(II) is complexed by the phosphonic acid resin (distribution coefficient of 48), but the bifunctional aminomethylphosphonic acid resin complexes 98% Cd(II) (distribution coefficient of 2300), which far exceeds the combined distribution coefficients of the monofunctional resins.

Sorption behavior and mechanism of indium(III) onto amino methylene phosphonic acid resin

The sorption behavior of amino methylene phosphonic acid resin (APAR) for In(III) was investigated. Experimental results show that In(III) adsorbed on APAR can be eluted with 2mol·L−1 HCl. The apparent rate constant is k298=1.50×10−5s−1. The sorption behavior of APAR for In(III) obeys the Freundlich isotherm. The thermodynamic parameters of sorption, enthalpy change ΔH, free energy change ΔG and entropy change ΔS of sorption (APAR) for In(III) are 24.1kJ·mol−1, −35.1kJ·mol−1 and 200J·mol−1·K−1, respectively. The coordination molar ratio of the functional group of APAR to In(III) is 2∶1. The sorption mechanism of APAR for In(III) was examined by IR spectrometry.

METAL ION SELECTIVITY OF MACRORETICULAR CHELATING CATION EXCHANGE RESINS WITH PHOSPHONIC ACID GROUPS ATTACHED TO PHENYL GROUPS OF A STYRENE-DIVINYLBENZENE COPOLYMER MATRIX

To clarify the metal ion selectivity sequence of the phosphonic acid resin named RSPO, in which the functional groups were introduced into phenyl groups of a macroreticular poly(styrene-co-divinylbenzene) matrix, the distribution of 20 kinds of metal ions from 0.0001 mol/L solution of each metal ion onto RSPO was studied in nitric, hydrochloric, sulfuric, and phosphoric acid media. Distribution ratios of divalent metal ions Ba(II), Ca(II), Cd(II), Co(II), Cu(II), Mg(II), Mn(II), Ni(II), Pb(II), Sr(II), and Zn(II) normally decreased with solutions of increased acidity and were not significantly affected by acid species. The clear effect of acid species was observed in the distribution of Fe(III), Mo(VI), and U(VI); although their distributions from hydrochloric and sulfuric acid media normally decreased with increasing acidity of solutions, the minimum was observed in their distribution from nitric acid media, indicating that they were distributed onto the resin from approximately 6 mol/L nitric acid through the mechanism similar to solvation extraction of their nitrate complexes with organophosphorous compounds. Phosphoric acid markedly depressed the distribution of Fe(III), Mo(VI), and U(VI) but not the distribution of Al(III), Bi(III), Cr(III), Gd(III), La(III), and Lu(III). The overall metal ion selectivity sequence of RSPO is the order of Mo(VI) ≅ Fe(III) ≅ U(VI) > Bi(III) ≅ Lu(III) > Al(III) ≅ Gd(III) > La(III) > Cr(III) > Pb(II) > Mn(II) ≅ Cd(II) ≅ Cu(II) > Ca(II) ≅ Co(II) ≅ Zn(II) ≅ Ba(II) ≅ Sr(II) > Ni(II) ≅ Mg(II). The metal ion selectivity sequence was also illustrated on the basis of uptake of U(VI), Pb(II), Ca(II), Ba(II), Ni(II) from 0.01 mol/L solutions of each metal ion.

Phosphonate-based resins for the selective enrichment of uranium(VI)

Phosphonate-derivatized polystyrene–divinylbenzene-based (PS–DVB) resins have been prepared from chloromethylpolystyrene–divinylbenzene (Cl–CH 2–PS–DVB) by the Arbuzov-reaction using lithium or sodium alkyl chlorophosphites. Base-promoted hydrolysis of the diethyl phosphite-derivatized resin in refluxing 1,4-dioxane resulted in phosphonic acid-derivatized PS–DVB resins with an average capacity of 0.8–2.2 mmol phosphonate, depending on the alkyl chlorophosphate used. Both the free phosphonic acid as well as the diethyl, dibutyl- and bis(2-ethylhexyl)-phosphonate-derivatized sorbents were investigated in terms of their extraction characteristics for U(VI), Th(VI) as well as for other transition metal ions such as Fe(III), Zn(II), Co(II), Cd(II), Ni(II) and Cu(II) from acidic aqueous solutions. In contrast to phosphonate resins, the phosphonic acid-derivatized resins exhibited a high sorption capacity and selectivity for U(VI). Breakthrough experiments were conducted for both U(VI) and Th(IV) within a pH-range of 0–4. U(VI)-uptake was measured as a function of the concentration of nitric and hydrochloric acids, respectively. The sorbent was found to possess a high selectivity for U(VI) with an optimum extraction pH of 4. Recoveries for U(VI) determined prior to breakthrough were found to be quantitative (97–99%) on the free phosphonic acid resin within the investigated pH-range. Finally, masking and synergetic effects on the extraction efficiency of the phosphonic acid-derivatized resin for U(VI) have been investigated using 5-sulfosalicylic acid as a masking reagent and dipyridyl amine as an auxiliary ligand.

A MECHANISM FOR ENHANCING IONIC ACCESSIBILITY INTO SELECTIVE ION EXCHANGE RESINS

ABSTRACT A bifunctional monophosphonic/sulfonic acid ion exchange resin with high capacity has been synthesized. Metal ion studies have been carried out with europium, americium, and ferric nitrate in solutions of varying acidity, with and without sodium nitrate added. The bifunctional resin complexes far higher levels of Eu(III) from 0.5 and 1 N nitric acid than the monofunctional phosphonic acid resin. It is postulated that the sulfonic acid ligand provides an access mechanism for the metal ions into the polymer matrix by hydrating the matrix and preventing its collapse in high ionic strength solutions thus allowing for rapid ionic complexation by the selective phosphonic acid ligands. The bifunctional monophosphonic/sulfonic acid resin has both ligands bound to a polystyrene support. It complexes higher levels of metal ions than a comparable resin differing only by having the monophosphonic acid ligand directly bound to the C-C backbone. Results are compared to a diphosphonic / sulfonic acid resin.

Synthesis of α-, β-, and γ-Ketophosphonate Polymer-Supported Reagents: The Role of Intra-ligand Cooperation in the Complexation of Metal Ions

Bifunctional ligands, viz., α-, β-, and γ-ketophosphonic acids, wherein a carbonyl group is systematically separated from a phosphoryl group with methylene moieties, have been immobilized on cross-linked polystyrene beads via the Arbusov and Perkow reactions. Studies with Eu(III), Cu(II), Pb(II), Cd(II), Co(II), and Ag(I) in various acid solutions show that under conditions where coordination is the dominant mode of metal ion sorption, the α-ketophosphonate complexes greater levels of metal ions than the β-ketophosphonate and both complex far greater levels of ions than the γ-ketophosphonate. The latter performs in a manner comparable to the monofunctional phosphonic acid resin. The results are consistent with intra-ligand cooperation being an important factor in the design of polymer-supported reagents for the complexation of high levels of metal ions.

Effect of gamma irradiation on the metal sorption and separation of some divalent metals by some new polymeric bifunctional resins

The metal sorption and separation of some divalent metals from solutions of varying acidity by a new series of gamma-irradiated ionic polymer resins have been investigated. Three polymeric resins, viz., phosphonic acid, phosphonate monoethyl ester, and phosphonate diethyl/monoethyl ester, were used in this study. The results of metal sorption and separation were compared with those of the well-known cation exchange resin Dowex X8. The results were correlated in the usual manner of distribution coefficients (D) of three divalent metals Sr(II), Co(II), and Ni(II). The results of metal sorption by the ionic resins under investigation compared with that of sulfonic acid resin, showed that Ni showed the highest affinity for the unirradiated monoethyl ester/phosphonic acid resin, while Sr showed the highest affinity for phosphonic acid resin and Co showed the highest affinity for mono/diethyl ester phosphonic acid resin. Moreover, the three metals (Sr, Co, Ni) showed the lowest affinity toward sulfonic acid resin. The calculated separation factors for the different resins indicate that the unirradiated phosphonic acid resin has the highest capacity to separate Sr from Ni, whereas mono/diethyl ester/phosphonic acid resins have the highest capacity to separate Co from Sr and Ni. Furthermore, the affinity of the ionic polymers for the metal ions was not greatly changed after gamma irradiation. © 1997 John Wiley & Sons, Inc. J Appl Polm Sci 65:1091–1101, 1997

Dual mechanism bifunctional polymers: Phosphinic acid ion-exchange/redox resins and the kinetics of metal-ion complexation

The detailed study of bifunctional phosphinic acid resins has recently been introduced. It has been shown that they operate through the dual mechanism of ion exchange and metal-ion reduction. A key component in the synthesis is the Friedel-Crafts catalyst used for the reaction between PCl 3 and polystyrene. We now find that the order of catalyst activity is AlCl 3 > FeCl 3 > ZnCl 2 > SnCl 4 . Ferric chloride catalysis also operates by an additional redox mechanism which yields a phosphonic acid resin. The extent of loading onto phosphinic and sulfonic acid resins by zinc ions at equilibrium was studied as a function of the anion present both with and without the presence of an excess of sodium ions. Both sets of resins exchange at a comparable rate upon the introduction of macroporosity into the polystyrene support. The influence of the redox process as an additional variable in the phosphinic resin kinetics was studied with silver and mercury(II) nitrate solutions. All of the primary acid sites are oxidized after a 9-hour contact time with Ag(I) ions and a 2-hour contact time with Hg(II) ions. The mercury loading curves and the different behavior of silver, which shows more ion exchange than redox at short times while leaving a residual ion concentration on the resin irrespective of whether all of the primary acid sites have been oxidized or not, can be explained by the termolecular nature of the Ag(I) redox reaction in contrast to the bimolecular nature of the Hg(II) reaction. Studies with other ions show that the minimum metal-ion reduction potential below which no redox occurs with the phosphinic resins is probably between 0.0 and 0.3 V.