Studies of selective adsorption resin. XXIV. Preparation and properties of macroreticular chelating resins containing both polyethylenepolyamine side chains and mercapto groups

The macroreticular chelating resins containing both polyethylenepolyamine side chains and mercapto groups were prepared by the reaction of 2,3-epithiopropyl methacrylate-divinylbenzene macroreticular copolymer beads with polyethylene-polyamine. The adsorption behavior of metal ions on the obtained resins was then investigated. The amination of the macroreticular copolymer beads could effectively be carried out by treatment of the polymer beads with polyethylenepolyamine in organic solvent (benzene, terahydrofuran) or in the absence of organic solvent at 80°C or 100°C for 60 min. It was found that the adsorption capacity of the resins for metal ions is not only affected by the ion exchange capacity of the resins but also by the porosity of the resins. Hg²⁺, Ag⁺, and Cu²⁺ were effectively adsorbed on the resins even at a pH below 3, whereas Co²⁺, Ni²⁺, and Cd²⁺ were adsorbed at a pH above 3, Mn²⁺ at a pH above 7, and Ca²⁺ at a pH above 8. These metal ions adsorbed on the resins could easily be eluted with dilute mineral acid solution or dilute mineral acid solution containing thiourea.     

Studies on selective adsorption resins. XXI. Preparation and properties of macroreticular chelating ion exchange resins containing phosphoric acid groups

Macroreticular cation exchange resins containing phosphoric acid groups (RGP) were prepared by the reaction of glycidyl methacrylate–divinylbenzene copolymer [or poly(glycidyl methacrylate)]beads (RG) with phosphoric acid or phosphorous oxychloride, and the adsorption behavior of metal ions on the RGP was investigated. The phosphorylation of the polymer beads could be effectively carried out by treatment of the polymer beads with 85% phosphoric acid at 80°C for 3 h. The RGP obtained from glycidyl methacrylate–divinylbenzene (2 mol %) copolymer beads showed high cation exchange capacity, salt splitting capacity, and adsorption capacity for Cu²⁺, Zn²⁺, Cd²⁺, Ca²⁺, and Ag⁺. On the other hand, the RGP obtained from poly(glycidyl methacrylate)beads had high adsorption capacity for Al³⁺, Fe³⁺, and UO₂²⁺. The RGP prepared by treating the RG with phosphoric acid had a higher selective adsorption for Li⁺ than for Na⁺.     

Preparation and uranyl ion adsorptivity of macroreticular chelating resins containing phosphono groups

Macroreticular copolymer beads were prepared by suspension polymerization of styrene, bis(2-chloroethyl) vinyl phosphonate (CEVP) and divinylbenzene (DVB) in the presence of toluene as diluent. The bis(2-chloroethyl) phosphonate groups on the bead surface were converted into phosphono groups by hydrolysis with dilute nitric acid. For the additional enrichment of phosphono groups, the copolymers were phosphorylated at the phenyl rings with phosphorus trichloride in the presence of aluminum chloride and hydrolyzed and oxidized with dilute nitrics acid. The investigations on metal ion chelation characteristics of the bead-type copolymers revealed that they have very high adsorptivity toward uranyl ions and good chemical resistance under acidic and alkaline media. It was also found that the phosphono group-containing copolymer beads are effective adsorbents for other heavy metal ions such as Pb²⁺, Hg²⁺, Cd²⁺, and Cu²⁺.     

Studies of selective adsorption resins. XXV. Preparation of macroreticular chelating resins containing aminomethylphosphonic acid groups from methyl methacrylate/divinylbenzene copolymer beads and their adsorption capacity

Macroreticular chelating resins containing aminomethylphosphonic acid groups were prepared by reaction of methyl methacrylate/divinylbenzene copolymer beads with triethylenetetramine, followed by the reaction of the products with phosphorous acid and formaline. The adsorption capacities of this resin for Cu²⁺, Pb²⁺, Zn²⁺, Ni²⁺, Co²⁺, Ca²⁺, and Mg²⁺ were determined at various pH values. The order of chelate stability for the resin was Cu²⁺ > Pb²⁺ > Zn²⁺ > Ni²⁺ > Co²⁺ > Ca²⁺ > Mg²⁺. Copper, nickel, zinc, calcium, and magnesium ions can be eluted with 1 mol dm^?3 hydrochloric acid. The proposed resin appears to be useful for the removal of Ca²⁺ and Mg²⁺ from salt solution.     

Preparation of macroreticular chelating resins containing dihydroxyphosphino and/or phosphono groups and their adsorption ability for uranium

The macroreticular chelating resins (RSP, RSPO, RCSP, and RCSPO) containing dihydroxy-phosphino and/or phosphono groups were prepared and their adsorption capacity for UO₂²⁺ and the recovery of uranium from sea water were investigated. RSP and RCSP were prepared by phosphorylation of macroreticular styrene–divinylbenzene copolymer beads and the chloromethylated copolymer beads, respectively. RSPO and RCSPO were prepared by oxidation of RSP and RCSP, respectively. The order of recovery of uranium from sea water with these four resins is as follows: RCSPO ? RCSP > RSPO > RSP. The adsorption of uranium in sea water was not only affected by the chemical structure, but also by physical structure of the resins. Uranium absorbed on the resins was eluted with 0.25 ～ 1 mol·dm^?3 Na₂CO₃ or NaHCO₃ solution by batch and column methods. The average recovery ratios of uranium from sea water with Na-form and H-form RCSP on 10 recycles were 84.9% and 90.5%, respectively, when 20 dm³ of sea water was passed through the column (resin 4 cm³, 10 mm ? × 50 mm) at the space velocity of 60 h^?1. RCSP has a high physical stability and resistance against acid and alkali solution.     

Studies on selective adsorption resins. XXXIII. Behavior of macroreticular chelating resins containing phosphinic and/or phosphonic acid groups in the adsorption of trivalent lanthanides

The effect of the crosslinking and the porosity of the chelating resins containing phosphinic and/or phosphonic acid groups (RSP and RCSP) on uptake of trivalent lanthanides was studied; RSP and RCSP were prepared by hydrolysis of condensation products of phosphorus trichloride with styrene–divinylbenzene copolymer beads (RS) and with chloromethylated RS, respectively. From a series of RSs synthesized by systematically changing the amount of the crosslinker (divinylbenzene) or the porogen (2,2,4-trimethylpentane), RSPs and RCSPs with different degrees of crosslinking and with different porosities were derived. Measurements of their uptake of La(III), Gd(III), or Yb(III) have clarified that RSP and RCSP with moderately crosslinked highly porous structures exhibit high capacities toward the lanthanides. Using these optimized RSP and RCSP and their respective oxidized derivatives RSPO and RCSPO, the distribution of all lanthanides (III) except for Pm(III) from aqueous hydrochloric acid solutions (0.1–1M) was examined. The distribution of each lanthanide(III) at a given concentration of the acid increases in the order RCSPO ≈ RCSP < RSPO < RSP. Their lanthanide selectivity patterns resemble one another; the selectivity increases with increasing the atomic number of the lanthanides except for the elements from Sm to Ho. In order to illustrate usefulness of these resins in the separation of lanthanides, the chromatographic separation of La(III), Nd(III), and Sm(III) was conducted using columns packed with RCSP. The three lanthanides were successfully separated by the elution with 0.5M hydrochloric acid solution without use of any organic complexing reagents, such as EDTA. © 1994 John Wiley & Sons, Inc.     

Recovery of uranium from seawater V. Preparation and properties of the macroreticular chelating resins containing amidoxime and other functional groups

We have synthesized macroreticular chelating resins containing amidoxime groups from acrylonitrile (AN)-divinylbenzene (DVB)-alkyl acrylate, alkyl methacrylate, or vinylpyridine (VPy) copolymer beads. It was found that the chelating resin (RNMH)-containing amidoxime groups prepared from AN-DVB-methyl acrylate (MA) indicated the highest adsorption ability for uranium in seawater. Hydroxamic acid and carboxylic groups in addition to amidoxime groups were formed during the reaction of the copolymer beads with a methanol solution of hydroxylamine. The adsorption ability for uranium was greatly influenced by the physical pore structure (macropore) and the pore structure formed by the swelling(micropore). RNMH (RNMH10-10) prepared with 10 mol% of DVB and 10 mol% of MA had the highest adsorption ability and physical stability for uranium. On the other hand, improved adsorption ability for uranium was not observed in the case of the macroporous resins (RNPyH) prepared by the copolymerization of VPy as the basic component. After seawater was passed through the column packed with RNMH10-10 at a space velocity (SV) of 180 h^?1 (up-flow) for 10 days, the amount of uranium adsorbed on the resin was about 100 mg/dm³-R and 260 mg/kg-R.     

Preparation and adsorption properties of the chelating resins containing carboxylic,sulfonic, and imidazole groups

The crosslinked poly(1‐vinylimidazole‐co‐acrylic acid), P(VIm‐co‐AA), and poly(1‐vinylimidazole‐co‐2‐acrylamido‐2‐methyl‐1‐propane sulfonic acid) P(VIm‐co‐APSA) were synthesized by radical polymerization and tested as adsorbents under competitive and noncompetitive conditions for Cu(II), Cd(II), Hg(II), Zn(II), Pb(II), and Cr(III) by batch equilibrium procedure. The resin–metal ion equilibrium was achieved before 1 h. The resin P(VIm‐co‐AA) showed a maximum retention capacity (MRC) value for Pb(II) at pH 3 and Hg(II) at pH 1 of 1.1 and 1.2 mEq/g, respectively, and the resin P(VIm‐co‐AA) showed at pH 3 the following MRC values: Hg(II) (1.5 mEq/g), Cd(II) (1.9 mEq/g), Zn(II) (2.7 mEq/g), and Cr(III) (2.8 mEq/g). The recovery of the resin was investigated at 25°C with 1 M and 4 M HNO₃ and 1 M and 4 M HClO₄. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 2852–2856, 2003     

Preparation and adsorption properties of the chelating fibers containing amino groups

Four kinds of amino-group-containing chelating fibers were prepared by reacting diethylenetriamine, diethanolamine, diethylamine, and aminopyridine, respectively, with a grafted fiber PVA-g-GMA containing epoxy groups. The γ-ray preirradiation initiated graft copolymerization of GMA onto PVA fiber, the functionalization of the grafted fiber PVA-g-GMA with amino compounds, and the adsorption properties of the obtained chelating fibers were systematically investigated. It is concluded that with increasing monomer concentration, reaction time, and temperature, the grafting percentage increases significantly. In the functionalization of the grafted fiber, reaction time, temperature, solvent, and amount of amine used greatly influence the reaction. 1,4-Dioxane is a reasonable solvent for the reaction. The chelating fibers present great adsorption amounts and high adsorption rates for Cu²⁺ ion and Au³⁺ ion. Among the chelating fibers, the fiber with diethylenetriamine group is the most reasonable chelating fiber for the adsorption of Cu²⁺ and Au³⁺. The chelating fibers present good selectivities for Cu²⁺ in the solution with Cu²⁺, Mn²⁺, Ni²⁺, Co²⁺, and Zn²⁺, while presenting quite high selectivities for Au³⁺ ion in the solution with Cu²⁺, Au³⁺, Zn²⁺, and Cr³⁺ ions. The chelating fiber with diethanolamine or diethylamine can reduce the adsorbed Au³⁺ into metallic gold. © 1994 John Wiley & Sons, Inc.     

Studies of selective adsorption resins. XVIII. The influence of porosity of macroreticular chelating resin on adsorption of heavy metal ions in an aqueous solution

In order to choose the most practical macroreticular chelating resins for the removal and recovery of heavy metal ion from industrial waste solution, the influence of the porosity of macroreticular chelating resins on the adsorption for metal ion was studied. The four macroreticular chelating resins (RST) containing triethylenetetramine side chain with different porosity were used. It was found that the adsorption of zinc ion at its low concentration solution was affected by the porosity of the RST. Among the four resins with average pore radius of 21.0, 24.5, 28.0, and 66.5 nm, a resin with that of 66.5 nm gave the highest initial adsorption rate and the largest breakthrough capacity for zinc ion at a space velocity of 15 h^?1.     

Studies of selective adsorption resins. XXVI. Removal of calcium and magnesium ions in a salt solution with chelating resin containing aminomethylphosphonic acid groups

Removal of calcium and magnesium ions in a salt solution with the macroreticular chelating resin containing aminomethylphosphonic acid groups was investigated. The resin (RMT-P) exhibited high affinity for calcium and magnesium ions in a salt solution containing 200 g/dm³ of sodium chloride. In the column method, calcium and magnesium ions in a salt solution were preferentially absorbed on the RMT-P, when the salt solution containing 100 mg/dm³ of calcium or magnesium ion was passed through the RMT-P column at a space velocity of 15 h^?1. The calcium and magnesium ions adsorbed were eluted by allowing 1 mol/dm³ hydrochloric acid to pass through the column. The recycle of adsorption and elution was found to be satisfactory.     

含氦聚醚型螯合树脂的合成及吸附性能

通过接枝反应制备了一系列以粜环氧氯丙烷为主链,侧链末端含吡略配位基的HPnCP(n=6,4,2)螯整合树脂,各步产物的化学结构经IR和1H NMR检洲得以确认,静态吸附实验及等温吸附实验结果表明:该类树脂对Cu(Ⅱ)和Hg(Ⅱ)有着较好的吸附性能(大于1.0mmol/g),对Co(Ⅱ)和Cd(Ⅱ)达到饱和吸附时的平衡浓度约为(0.06～0.07)mol/L; HP4CP对Co(Ⅱ)和Cd(Ⅱ)以及HP2CP对co(Ⅱ)的等温吸附既可用Langmuir方程描述也可用Freundlich方程描述;但HP2CP对Cd(Ⅱ)的等温吸附不符合Langmuir方程.只可用Freundlich方程描述.     

含氮聚醚型螯合树脂的合成及吸附性能

通过接枝反应制备了一系列以聚环氧氟丙烷为主链,侧链末端含吡咯配位基的HPnCP（n=6．4,2）螯合树脂。各步产物的化学结构经IR和^1H NMR检测得以确认。静态吸附实验及等温吸附实验结果表明：该类树脂对Cu（Ⅱ）和Hg（Ⅱ）有着较好的吸附性能（大于1．0mmol／g）;对Co（Ⅱ）和Cd（Ⅱ）达到饱和吸附时的平衡浓度约为（0．06～0．07）mol／L;HP4CP对Co（Ⅱ）和Cd（Ⅱ）以及HP2CP对Co（Ⅱ）的等温吸附既可用Langmuir方程描述也可用Freundlich方程描述;但HP2CP时Cd（Ⅱ）的等温吸附不符合Langmuir方程,只可用Freundlich方程描述。     

Synthesis and heavy metal ion adsorptivity of macroreticular chelating resins containing phosphono and carboxylic acid groups

Macroreticular copolymer beads were prepared by suspension polymerization of 4-vinylbenzyl chloride (VBC), divinylbenzene (DVB) and monomers with carboxylic ester groups like dibutyl maleate (DBM), dibutyl fumarate (DBF) and dibutyl itaconate (DBI) in the presence of toluene as diluent. The copolymer beads were phosphorylated at the chloromethylated phenyl rings with triethyl phosphite and hydrolyzed by an aqueous sodium hydroxide solution; the hydrolysis on the bead surface converted carboxylic ester/phosphonate groups into carboxylic acid/phosphono groups, respectively. The investigations on the metal ion chelation characteristics of the H-form copolymer beads revealed that they have good adsorptivity toward heavy metal ions like Pb²⁺, Cd²⁺ and Cu²⁺, and poor adsorptivity toward ions like Hg²⁺ and UO₂²⁺. The adsorptivity caused by the three carboxylic ester monomer derivatives was in the order DBM > DBI > DBF. Especially, the Na-form copolymer beads neutralized by alkali treatment were very available for the adsorption of all the metal ions under investigation.     

Recovery of uranium from sea water. IV. Influence of crosslinking reagent of the uranium adsorption of macroreticular chelating resin containing amidoxime groups

Macroreticular chelating resins (RNH) containing amidoxime groups with various degrees of crosslinking were synthesized by using various amounts of ethyleneglycol dimethacrylate (1G), dimethyleneglycol dimethacrylate (2G), triethyleneglycol dimethacrylate (3G), tetraethyleneglycol dimethacrylate (4G), and nanoethyleneglycol dimethacrylate (9G) as crosslinking reagent. The effect of crosslinking reagents on the pore structure, ion exchange capacity, swelling ratio, and adsorption ability for uranium of RNH was investigated. RNH (RNH–1G) prepared by using 1G were showed to have macroreticular structures by the measure of specific surface area. RNH–1G had the high adsorption ability and physical stability. Though RNH (RNH–4G) obtained by using 4G have little macroreticular structure (macropore), these resins showed the high adsorption ability for uranium by the treatment with 0.1 mol dm^?3 NaOH at 30°C for 15 h (alkali treatment). These results suggest that the formation of not only the favorable macropore but also the micropore is important for the effective recovery of uranium in sea water, whereas RNH–4G was defined to be low physical and chemical stability. For the preparation of RNH which have effective pore structure for the recovery of uranium, chemical, and physical stability, the simultaneous use of divinylbenzene (DVB) and 1G or 4G as crosslinking reagent was examined (abbreviated as RNH–DVB–1G and RNH–DVB–4G). The specific surface area of RNH–DVB–1G increased with an increase of 1G used. These RNH–DVB–1G have been shown the high adsorption ability for uranium. On the other hand, the specific surface area and adsorption ability for uranium of RNH–DVB–4G decreased with an increase of 4G used. Repeated use did not cause the deterioration of both RNH–DVB–1G and RNH–DVB–4G. This result suggests that the simultaneous use of DVB and 1G or 4G contributed the improvement of chemical and physical stability. In particular, RNH–DVB–1G has the effective macropore and micropore for the recovery of uranium.     

Preparation and adsorption properties of chelating resins from thiosemicarbazide and formaldehyde

A novel chelating resin was synthesized in just one step under mild synthetic conditions. The synthesis was carried out through the copolymerization of thiosemicarbazide and formaldehyde in an aqueous solution. The adsorption properties for some noble metal ions were investigated. The results showed that the resin had high adsorption selectivity for Au(III) and Ag(I). The adsorption capacities for the two metal ions reached up to 7.3 and 11.8 mmol/g, respectively. The adsorption rate for the two metal ions in a dilute solution was 99.9%. The adsorption fit first‐order kinetics, and an isothermal adsorption study indicated that it corresponded to Langmuir monomolecular layer adsorption. The change in the bonding energy during the chelating process was investigated with X‐ray photoelectron spectroscopy. The study revealed that nitrogen and sulfur atoms of the resins were electron donors and metal ions were electron acceptors in the process. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Preparation and metal ion adsorption properties of the resin containing sulfonic acid groups

In this study, we explored a new ion exchange material synthesized by radical polymerization of styrene and 2‐acrylamido‐2‐methyl‐1‐propane sulfonic acid by using 2,2′‐azo‐isobutyronitrile (1 mol %) and divinylbenzene (0.5 mol %) as initiator and crosslinking reagents, respectively. The resin was obtained from a large excess (90%) of styrene in the feed. The yield was 72.3%. The resin was completely insoluble in water and characterized by elemental analysis, FTIR spectroscopy, scanning electron microscopy, and thermal analysis. The metal ion retention capability was investigated for Ag(I), Hg(II), Cd(II), Zn(II), Pb(II), and Cr(III). The effect of pH, time, and resin/metal ion mol ratio on the metal ion retention was studied. Selectivity of the resins from a mixture of metal ions and the maximum retention capacity at optimum pH were also determined. The recovery of the resin by using 1 and 4 M HClO₄ and HNO₃ demonstrated that it is possible to recover the resin above 80%. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 1230–1235, 2003     

Preparation and thermal properties of liquid crystalline ionomers having mesogenic ester side chains containing three phenyl groups

A series of liquid crystalline (LC) copolymers having both the repeat units of mesogenic ester side chains containing three phenyl groups and the repeat units possessing an acid group were prepared. The acid groups of the LC copolymers were neutralized with sodium acetate to give a varying degree of neutralization. It was found that the LC properties of the ionomers depended strongly on both the relative amount of the units having the mesogenic side chains and the amount of ionic units. It was also observed that the formation of the nematic phase of the LC ionomers was suppressed by the increase in ion contents. After the analysis of the thermal data of the phase transitions, it was suggested that the transition temperatures of the LC phases of the copolymers and their ionomer forms, and the temperature ranges for the LC phases were affected by the relative amounts of both mesogenic and acidic units and by the degree of neutralization, simultaneously.     

Acid-basic and sorption properties of modified polyvinyl alcohol fibre containing polyethylenepolyamine groups

The function of formation of copper(II) ion complexes was determined, and the distribution and separation coefficients of heavy metal ions were calculated in sorption from complex salt solutions. The selectivity of polyamine-containing PVA fibre with respect to copper(II) and lead(II) ions was determined in sorption from complex salt solutions. It was found that the fibre exhibits sorption activity for platinum group metals. Translated from Khimicheskie Volokna, No. 1, pp. 32–36, January–February, 1998.     

Synthesis and adsorption properties of magnetic resin microbeads with amine and mercaptan as chelating groups

Three magnetic chelating resins containing amino and mercapto groups were prepared by the suspended condensation polymerization of 2‐chloroethoxymethyl thiirane with diamines. The magnetic resins were microbeads whose diameter was in the range of 10 to 45 μm. The structure of the resins was characterized by XPS, IR, and elemental analysis. Their adsorption properties for Hg(II), Au(III), Pd(II), Pt(IV), Ag(I), Cu(II), Zn(II), and Pb(II) were investigated. The experimental results show the magnetic resins have high affinity for Hg(II) and noble metal ions. In the competitive adsorption, the resins predominantly adsorbed Hg(II) or Pd(II) in the coexistence of Cu(II), Zn(II), and Mg(II). Desorption of Pd(II) loaded on the resins was studied by using 2M hydrochloric acid solution containing 1% thiourea as desorbent. A high desorption ratio (up to 96.5%) was observed, and repeated adsorption/desorption operations showed the probability of repeated use of the magnetic resins. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 1587–1592, 2001