Russian Journal of Applied Chemistry, Vol. 75, No. 3, 2002, pp. 385!388.

Translated from Zhurnal Prikladnoi Khimii, Vol. 75, No. 3, 2002, pp. 398! 400. Original Russian Text Copyright + 2002 by Ergozhin, Bektenov, Akimbaeva.

SORPTION AND ION-EXCHANGE PROCESSES

Polyfunctional Anion Exchanger as Sorbent of Copper(II) and Vanadium(V) Ions

E. E. Ergozhin, N. A. Bektenov, and A. M. Akimbaeva
Bekturov Institute of Chemical Sciences, Almaty, Kasakhstan
Received February 12, 2001

Abstract Sorption of copper and vanadium ions from aqueous solutions by cross-linked anion exchanger based on a copolymer of glycidyl methacrylate with styrene and polyethylenimine was studied. The effect of the solution pH on the completeness of sorption is considered.

The continuous and impetuous expansion of the application fields of synthetic polyelectrolytes is stimulating the growing interest in synthesis of ionexchange polymers. Particular attention is attracted by sorption recovery of metals from aqueous solutions and metal separation, widely used in hydrometallurgy, chemical technology, environmental protection, and analytical chemistry [1, 2]. To enable these applications, a wide variety of ion-exchange resins, membranes, and fibers based on polymer ion exchangers of cation- and anion-exchange type are being manufactured at present. Of much interest for obtaining various ion-exchange polymers are copolymers of glycidyl methacrylate, exhibiting a high reactivity and a number of valuable physicochemical properties. The known methods for preparing ion exchangers of the styrene type are multistage and involve the use of toxic and sometimes difficultly available monomers. Therefore, a promising direction in the field of synthesis of ion exchangers is the use of a copolymer of glycidyl methacrylate and styrene, which allows synthesis of polyelectrolytes with high chemical and thermal stability and mechanical strength and makes it possible to perform reactions under mild conditions with the possibility of controlling the composition and properties of the obtained products [3, 4]. In radical homo- and copolymerization of glycidyl esters, the double bond is cleaved and the epoxy group, whose presence in a macromolecule allows synthesis of infusible and insoluble cross-linked products, is preserved. In this work, we tested for sorption of metal ions an anion exchanger prepared by modifying with polyethylenimine a copolymer of glycidyl methacrylate and styrene (GMA3ST3PEI) [3].

EXPERIMENTAL The polyfunctional anion exchanger GMA3ST3PEI was synthesized by the procedure reported in [3]. The IR spectra of the initial and metal-containing anion exchangers were measured in KBr pellets on a UR-20 spectrophotometer. Polymer samples were dried in a vacuum drying box to constant weight prior to each set of experiments. The static exchange capacity (SEC) was determined using the technique described in [5]. A weighed portion (1 g in terms of dried substance) of anion-exchange resin in the OH form was placed in 200 ml of 0.1 N HCl solution. The mixture was kept for 24 h with intermittent stirring. After that the ion exchanger was filtered off, and 25 ml of the filtrate was taken with a pipette and titrated with 0.1 N NaOH solution in the presence of phenolphthalein. The SEC of the anion exchanger (mg-equiv g31) was calculated by the formula
[200F ! (200/25)VF1]  0.00365  1000 SEC = 36.5g 200F ! 8VF1 = , 10g

where F is the correction factor for 0.1 N HCl solution, V is the volume of 0.1 N NaOH solution (ml), F1 is the correction factor for 0.1 N NaOH solution, 0.00365 is the titer of 0.1 N HCl solution, 36.5 is the molecular weight of HCl, and g is the weighed portion of anion exchanger (g). The sorption of copper and vanadium ions was done under static conditions from copper sulfate solution (initial concentration of CuSO4 . 5H2O 6.24 g l31)

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ERGOZHIN et al.

and sodium vanadate (initial concentration of Na3VO4. 2H2O 6 g l31 in terms of V2O5) [6]. To determine the sorption capacity (SC) of the anion exchanger for ions in relation to the solution pH, weighed portions of the polymer (SEC 8.09 mg-equiv g31, grain size 0.253 0.50 mm, weight 0.10 3 0.12 g) were placed in six vessels and brought in contact for 6 37 days [6] with a solution containing 20 ml of a solution of a salt of the corresponding metal, sulfuric acid (for maintaining constant the solution pH) in amount of 0 to 12 ml, and water to make the total volume of solution

in each vessel equal to 40 ml. The solution pH was measured with an EV-74 pH-meter with the accuracy D = 0.02. The content of vanadium ions was found by titration with Mohrs salt in the presence of phenylanthranilic acid. The concentration of copper cations was determined by atomic-absorption spectroscopy. Chemical modification of the starting polymer GMA3ST, containing active epoxy groups, with aliphatic polyamine PEI was carried out in toluene by the scheme
N CH2 CH 2 NH CH2 CH 2 CH2 OH CH CH2 O O C ( CH2 C )m ( CH2 CH )n ( CH2 C6 H5 CH 3 ... GMA!ST!PEI N ... CH2 CH OH CH2 O C O C )m CH 3

( CH2

? ?????? ? ? C C?C C C ?? ???? ?? ? CA C C ?E ???? ???? C ?? ? C?C ?? C?C ?

CH 3 C )n ( CH2 CH )m C6 H5 C O O CH2 CH CH2 O GMA!ST
776

PEI

( CH2 CH )n C6 H5

The practical use of ion exchangers involves their prolonged contact with water and aqueous solutions, occurring at elevated temperatures. In the process, physicochemical and technical properties of ion exchangers undergo irreversible changes associated with degradation of the polymer matrix or functional groups. Therefore, the thermal stability is an important factor for these materials. The recent success in studies of the mechanism and kinetics of thermal degradation of ion exchangers allows, in some cases, proper choice of ion exchanger and prediction of the service life and direction of changes in physicochemical properties of ion exchangers [7]. It has been established that two mechanisms of thermal degradation of anion exchangers are possible: deamination
R!CH2!N+(CH3)3OH!
H2O % %$ ,

complete loss of capacity with the formation of nonionic alcohol groups. The second way assumes conversion of functional groups with higher basicity into low-basic groups, with possible insignificant change in the ion exchanger capacity. The thermal stability of anion exchangers depends not only to the structure of amino groups, but also on the structure of the ion exchanger skeleton. Of three constituents of a swollen ion exchanger (polymer matrix, functional groups, and water), the functional groups are the least stable [7]. Therefore, decomposition of ion exchangers commonly starts with functional groups and primarily affects the exchange capacity (after tests of ion exchangers), which is the quantitative criterion of thermal stability. According to some studies [7, 8], the ion exchanger is more stable in the salt form, compared with the basic form. The anion exchanger in the salt form is characterized by reactions described for an anion exchanger in the hydroxide form, with the exception of dealkylation to give methanol [Eq. (2)]. Therefore, experiments were carried out with samples in the OH form, boiled in water for 48 h. On heating the synthesized anion exchanger in water, its exchange capacity changes somewhat (6.02% loss of capacity). A different behavior is observed for EDE-10P and AV-18 commercial anion exchangers. Their loss of capacity on heating in water
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RCH2OH + N+H(CH3)3OH! (1)

and dealkylation
R!CH2!N+(CH3)3OH!
H2O % %$ ,

RCH2!N+H(CH3)2OH! (2)

+ CH3OH.

Degradation by the first scheme is accompanied by

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387

to 100oC for 48 h is 23%, which is nearly 4 times that for the anion exchanger under study. Presumably, the matrix degrades, with decrease in the cross-linking density and elimination of the functional groups of the ion exchanger. Polyfunctional cross-linked and linear ion exchangers with primary, secondary, and tertiary amino groups exhibit donor properties and, when brought in contact with substances whose molecules have acceptor groups or ions, form coordination compounds via unshared electron pairs at ionogenic groups [9]. It is known that the higher the content of protonated amino groups in the polymer phase, the smaller the number of active centers coordinated with metal. Protonated ligands of coordinated compounds form no coordination compounds with metal ions. In weakly acidic, neutral, or alkaline medium, the unprotonated form of the ion exchanger is in the undissociated state; under these conditions, the interaction of the polymer with metals occurs via coordination bonding. On the whole, it was noted [8] that the sorption capacity of ion exchangers for transition metal ions grows with decreasing acidity of the medium. However, in alkaline solutions metal hydroxides can precipitate, and, therefore, copper ions were recovered with a polyelectrolyte based on GMA3ST3PEI at pH 235 (see table). At pH 4.94, the capacity of the polymer for copper ions is 380 mg g31. It can be seen from the table that the sorption capacity of the polymer grows with increasing solution pH. The change in the solution color suggests occurrence of complexation. It is known [6, 8, 10] that many polyfunctional anion exchangers well recover vanadium(V) ions from solutions of its salts. The figure shows the sorption capacity of the anion exchanger under study as a function of the solution pH. For comparison, the figure presents the curve describing the sorption of vanadium ions by a commercial polyfunctional anion exchanger of the EDE-10P brand. The strong influence of the solution pH on the sorbent capacity is due to the influence of the ionic state of vanadium in solution [11]:
Ionic state of V VO3! 4 HVO2! 4 V3O3! 9 V10O6! 28 HV10O5! 28 H2V10O4! 28 VO+ 2 pH >13 8!3 8.0!6.6 6.5!6.0 6.0!3.5 3.2!2.0 <2
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Change in sorption capacity of anion exchanger based on GMA!ST!PEI for copper(II) ions in relation to solution pH

pH !1 Color of solution pHin eq SC, mg g after sorption 4.94 5.93 380 Dark blue 2.49 4.42 118 Blue 2.04 3.12 82 

As a result, the sorption capacity of the anion exchanger grows dramatically in the acid range and decreases with the solution pH growing further. The sorption capacity is as high as 1674 mg g31 (pH 3.30) for the GMA3ST3PEI sorbent and 520 mg g31 for EDE-10P. The formation of metal ion complexes with anion exchangers was studied by IR spectroscopy. An analysis of the IR spectra of a polymer containing bound copper revealed broadening of bands associated with stretching vibrations of the N3H bond (3000 3 3400 cm31) and appearance of absorption in the range 200 3360 cm31, attributable to a coordination bond between metal ions and amino groups. In the spectrum of the anion exchanger saturated with vanadium ions, an absorption band related to decavanadate ion appears at about 960 cm31. CONCLUSION An anion exchanger based on a copolymer of glycidyl methacrylate with styrene and on polyethylenimine can be effectively used for sorption of copper(II) and vanadium(V) ions from weakly acidic solutions.
SC, mg g!1

Sorption capacity SC of GMA3ST-based anion exchanger for V2O5 vs. solution pH. Sorbent: (1) EDE310P and (2) GMA3ST3PEI. No. 3 2002

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REFERENCES
1. Senyavin, M.M., Ionnyi obmen v tekhnologii i analize neorganicheskikh veshchestv (Ion Exchange in Technology and Analysis of Inorganic Substances), Moscow: Khimiya, 1980. 2. Juo, A., Matsufune, S., Ono, H., and Egawa, H., J. Appl. Polym. Sci., 1997, vol. 63, no. 10, pp. 1327! 1333. 3. Akimbaeva, A.M., Bektenov, N.A., and Ergozhin, E.E., Izv. Minist. Nauki Vyssh. Obraz. Nats. Akad. Nauk Resp. Kazakhstan, Ser. Khim., 1999, no. 3, pp. 68!73. 4. Akimbaeva, A.M., Bektenov, N.A., and Ergozhin, E.E., Izv. Minist. Obraz. Nauki, Ser. Khim., 2000, no. 1, pp. 67!71. 5. Toroptseva, A.M., Belogorodskaya, K.V., and Bondarenko, V.M., Laboratornyi praktikum po khimii i tekhnologii vysokomolekulyarnykh soedinenii (Laboratory Manual of Chemistry and Technology of Macromolecular Compounds), Leningrad: Khimiya, 1972.

6. Bektenov, N.A., Ergozhin, E.E., and Menligaziev, E.Zh., Izuchenie sorbtsionnoi sposobnosti glitsidilmetakrilatnykh ionoobmennikov po otnosheniyu k ionam nekotorykh metallov (Investigation of Sorption Capacity of Glycidyl Methacrylate Ion Exchangers for Ions of Some Metals), pp. 45! 60. 7. Tulupov, P.E., Stoikost ionoobmennykh materialov (Stability of Ion-Exchange Materials), Moscow: Khimiya, 1984. 8. Ergozhin, E.E. and Menligaziev, E.Zh., Polifunktsionalnye ionoobmenniki (Polyfunctional Ion Exchangers), Alma-Ata, 1989. 9. Saldadze, K.M. and Kopylova-Valova, V.D., Kompleksoobrazuyushchie ionity (Complexing Ion Exchangers), Moscow: Khimiya, 1980. 10. Ptitsyn, A.N., Zolotavin, V.L., and Maletina, L.E., in Khimiya i tekhnologiya vanadievykh soedinenii (Chemistry and Technology of Vanadium Compounds), Perm, 1974, pp. 167!171. 11. Ivakin, A.A., Tr. Inst. Khim. Akad. Nauk SSSR, Ural. Fil., 1968, issue 18, pp. 3!11.

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