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Polymer pendant crown thioethers: synthesis, characterization and Hg 21 extraction studies of polymer-supported thiacrowns ([14]aneS 4 and [17]aneS 5 )
Theodore F. Baumann*, John G. Reynolds, Glenn A. Fox
Lawrence Livermore National Laboratory, University of California, P.O. Box 808, Livermore, CA 94551, USA Received 4 April 1999; received in revised form 30 September 1999; accepted 4 October 1999

Abstract We are interested in designing polymer-bound extractants for Hg 21 remediation in mixed-waste streams. Towards this goal, we have synthesized novel polymer extractants where 2-aminomethylthiacrowns are immobilized on a polystyrene– divinylbenzene matrix through the pendant arm of the crowns. Reaction of 2,3-dimercapto-1-propanol with either 4,7-dithiadecane-1,10-di-p-toluenesulfonate or 4,7,10-trithiatridecane-1,13-di-p-toluenesulfonate generated the 2-hydroxymethylthiacrowns, 3 ([14]aneS 4 -OH) and 4 ([17]aneS 5 -OH). Treatment of the 2-hydroxymethylthiacrowns with thionyl chloride, followed by monomethylamine, produced the N-(methyl)-2-aminomethylthiacrowns, 5 ([14]aneS 4 -NR1 R2 ) and 6 ([17]aneS 5 -N R1 R2 ) (R1 5 Me, R2 5 H). The thiacrown polymers were prepared through the copolymerization of a 4-vinylbenzyl-substituted aminomethylthiacrown, 7 ([14]aneS 4 -N R1 R2 ) or 8 ([17]aneS 5 -N R1 R2 ) (R1 5 Me, R2 5 4vinylbenzyl), with divinylbenzene. Extraction of Hg 21 from aqueous media using the [17]aneS 5 thiacrown polymer 10 with under a variety of conditions ([Hg 21 ] 4–200 ppm, pH 1.5–6.2) shows that the resin effectively and selectively removes Hg 21 ions from acidic aqueous solutions with extraction efficiency | 95%. Mercury recovery and polymer regeneration was also demonstrated using chloroform solutions of diphenylthiocarbazone to strip the bound Hg 21 from the resin. © 2000 Elsevier Science B.V. All rights reserved.
Keywords: Polymer pendant ligand; Thiacrown; Toxic metal; Metal extraction

1. Introduction Owing to increased environmental concerns about waste remediation, major efforts are under way to design new materials that can effectively remove and recover toxic metal ions from aqueous solution. One approach to this problem has been to utilize organic ligands attached to

*Corresponding author.

solid supports [1,2]. Such a strategy presents several advantages. Specific binding properties of the ligands can be exploited to selectively remove a desired metal ion from a complex solution of cations. These materials can also be recycled and reused to make the treatment process cost-effective. In addition, this technique can potentially minimize the amount of secondary waste generated in the extraction process, a major challenge in waste treatment. The utility of polymer pendant ligands for the extraction of a variety of metal ions from

1381-5148 / 00 / $ – see front matter © 2000 Elsevier Science B.V. All rights reserved. PII: S1381-5148( 99 )00085-1

10-di-p-toluenesulfonate were prepared according to literature procedures [20]. Fe 31 . 2. 31 31 21 21 such as Al . these mixed-waste streams are not only very acidic. 0. v / v) mixtures. 1 H-NMR spectra ¨ were obtained on a 300 MHz Bruker MSL-300 NMR spectrometer.15]. 4. This report includes Hg 21 extraction studies for thiacrown polymer 10 which show that the resin is both highly effective and selective for the removal of the Hg 21 ion from acidic aqueous media. Materials and methods 4. Experimental 2. Plasma standards of 1000 and 10 000 ppm (guaranteed 63 ppm) metal ion solutions (Al 31 . To address this difficult and expensive problem.13 -diol (1) Sodium metal (3. As pendant ligands on solid supports. In this paper. Typically. pH measurements were made on an Orion model 420A pH meter using an Orion model 91-57 Triode electrode (automatic temperature calibration). Removal of Hg 21 thus requires a robust and selective sequestering agent. Fe . but also contain a wide variety of other metal ions. USA). Synthesis of precursors and polymers 2. 2. Baumann et al.1 g. Melting points were determined using a MelTemp hot-stage microscope and are uncorrected. we have synthesized polymer–pendant crown thioethers for the selective 21 removal of Hg from acidic aqueous media [8.5:0. We are interested in designing polymer bound extractants for Hg 21 remediation in mixedwaste streams generated at US Department of Energy (DOE) facilities. The resulting solution was brought to reflux and 3-chloro-1propanol (12.9].7. Hg 21 and Pb 21 . All optical spectra were recorded on an HP8453 general purpose UV– vis spectrometer and solutions were measured in 1-cm pathlength SpectroChem R-2010-T cells. IN.1. A comparison of Hg 21 extraction efficiency between polymer 10 and previously reported polymer-based Hg 21 extractants is also discussed. 2mercaptoethyl sulfide (10 g. Positive ion electrospray mass spectra were performed using a Finnigan TSQ700 instrument and ESI source on MeOH–H 2 O–acetic acid (50:49.11] are well-suited for this task due to the high affinity that sulfur crowns have for the Hg 21 ion [12–14] as well as their resistance to degradation under acidic conditions [11.5. When all of the sodium had undergone reaction.065 mol) was added under nitrogen with stirring.7-Dithiadecane1. and the white precipitate . obtained from Aldrich and were used as received. Pb 21 . such as Ag 1 . 0. cooled. The reaction was kept at reflux for an additional 2 h. / Reactive & Functional Polymers 44 (2000) 111 – 120 aqueous media has been previously demonstrated [3–7]. Elemental analyses were performed by Midwest Microlab (Indianapolis.136 mol) was slowly added in small pieces to EtOH (150 ml). Chemical ionization mass spectra were performed on a Finnigan GCQ mass spectrometer.2. All other reagents and solvents were of reagent grade quality. Cd and Pb .10-diol and 4.F. Crown thioethers [10. Cd 21 ) in 2–5% nitric acid were purchased from Spex. directly from aqueous solutions [16–19]. Infrared spectra were recorded on a Nicolet Impact 400D spectrometer. thiacrowns have been shown to remove soft metal ions. we describe the synthesis of novel pendant-arm thiacrowns and the details for the incorporation of the thiacrowns into a polystyrene–divinylbenzene co-polymer matrix.1.85 g.10 -Trithiatridecane-1.112 T. 0.136 mol) was added dropwise.7-dithiadecane-1.2.

3. 2 -Hydroxymethyl-1.028 mol) and triethylamine (6. Baumann et al. m. Electrospray-MS m /z (C 11 H 22 OS 4 . 2. after which the solvent was removed in vacuo.29). 2.2 g. HOCH2 CH–). 0.7 g. The product was purified by column chromatography on silica gel (eluent: 2% MeOH in CHCl 3 ) and was isolated as a white crystalline solid (1. 71–738C. 23%).62 (1H.061 mol) was added dropwise over 0.6 g. After stirring for 6 h.79 (43.36 (44. for C 11 H 22 OS 4 ): C.2. 7. –CH2 SCH2 –). 2. s. 44.85 (4H. R 5 H) (5) To a solution of SOCl 2 (0.85 (4H.17 (2H.8 g. filtered. dried (Na 2 SO 4 ). –CH2 SCH2 –).4. 0. dd.5 g. The product was isolated as a white crystalline solid after recrystallization from hot MeOH (12. 4. 2.8 g.29 (44. m. S. OH ). 42. and filtered.032 mol) was suspended in DMF (200 ml) under a nitrogen atmosphere and the reaction was heated to 908C.10-di-p-toluenesulfonate (10.0 (4H. overlapping triplets. 0. The organic phase was collected. 2. 3.76 (4H.32 (1H. 2 -Hydroxymethyl-1.6–2.7. HOCH2 CH–). 29%).93 (42.85 (18 H. / Reactive & Functional Polymers 44 (2000) 111 – 120 113 was collected by filtration.73 (1H. OH ). dd. ArCH3 ).3-Dimercapto-1-propanol (2. The product was purified by column chromatography on silica gel (eluent: 2% MeOH in CHCl 3 ) and was isolated as a waxy.11.021 mol) was allowed to react with compound 2 (12. d.T. [14] aneS4 1 2 1 2 NR R ( R 5 Me. 0. –CH 2 CH2 CH 2 –). CI-MS m /e (C 10 H 22 O 2 S 3 .8. Anal.8.2.5–2.1 (4H. 3. off-white solid (1. t. 7.45 (6H. 85%). m.4. 298): 297 (M2H 1 ).57).50– 2. for C 11 H 22 OS 4 ): C. –CH2 SCH2 –). 7.8 g.91). CI-MS m /e (C 24 H 34 O 6 S 5 . 270): 271 (M1H 1 ). HCl (100 ml) and stirred for 30 min.2. 2. 2. Electrospray-MS m /z (C 13 H 26 OS 5 . m. [28] aneS4 -OH (3) Finely powdered anhydrous cesium carbonate (10.70 (12H.8–2. br s.78 (12H. 0. qnt. 44. 5. –CH2 OH). t.5. br s. HOCH2 CH–). After addition was complete.75 (4H.6 g.8–2.p.95 (1H.F. H.11 tetrathiacyclotetradecane. –CH 2 CHS–). 2. The reaction was stirred at 08C for an additional 6 h and then placed in the freezer overnight.3dimercapto-1-propanol (2. 358): 357 (M2H 1 ). 75%). OH ). The precipitate was then dissolved in hot acetone (300 ml) and the suspension was filtered to remove NaCl.2.86 (1H. qnt. H.p.2 g.13 -di-ptoluenesulfonate (2) A solution of 1 (7.33 (7.60–2. aromatic). –CH 2 CH2 CH 2 –). dd. 1 H NMR (CDCl 3 ) d 1.09 (4H. 37–398C.021 mol) under conditions identical to those described above for crown 3.2. d.11 tetrathiacyclotetradecane. HOCH2 CH–). 578): 579 (M1H 1 ).44). 43. To the vigorously stirred suspension was added a solution of 2. qnt.021 mol) in DMF (75 ml) from a dropping funnel over a 12-h period. m. [17] aneS5 -OH (4) 2.p.4 mmol) in CH 2 Cl 2 (10 ml) was added dropwise a solution of crown 3 (0. Anal.3 g. S. 0.7 mmol) in CH 2 Cl 2 (10 ml). The reaction was then poured over crushed ice in conc. –CH 2 CH2 CH 2 –). 1 H NMR (CDCl 3 ) d 1. –CH 2 CH2 CH 2 –).6 g. 3. The filtrate was washed with water (33100 ml). dd. –CH2 SCH2 –). found (calcd.061 mol) in CH 2 Cl 2 was cooled to 08C with stirring and p-toluenesulfonyl chloride (11.4.4. m. m.31 (4H.p.021 mol) and 4. 3.32). Slow cooling of the acetone solution afforded white needles that were collected by filtration (15 g. 2. dried (MgSO 4 ).2 g.5 h. –CH 2 CHS–). 1 H NMR (CDCl 3 ) d 1.10 -Trithiatridecane-1.9 (14 H.9 (1H. 2. 1 H NMR (CDCl 3 ) d 1. 0. 30–328C.3. 4. overlapping triplets. the reaction was stirred for an additional 12 h. 2. –CH2 OH). and the chloroform was removed to leave a gold oil.3 (1H.14 pentathiacycloheptadecane. The reaction residue was taken up in CHCl 3 (200 ml) and filtered.45 (7. the reaction was . 7. The chloroform was removed by rotary evaporation to yield a light yellow oil. m. 2. 2 -( N-Methyl)aminomethyl-1. 57–598C.77 (1H. 2. qnt.8. 7-dithiadecane-1.65). 2.64 g. aromatic). 0. 2. found (calcd.

–CH 2 CH2 CH 2 –). vinyl). 1.75 (1H.83 (56. m. aromatic).28) S.71 g. NCH3 ).25 (2H. aromatic). R 2 54 -VB) (7) Crown 5 (0.35 (2H. q. AIBN (6 mg.1 (4H. m.1 g.05 (22 H. 4 mmol). s. d. 2.6.05 (4H.11tetrathiacyclotetradecane as a yellow oil. [17] aneS5 NR 1 R 2 ( R 1 5 Me.25 (3H. 2.7 mmol).1 mmol) was converted to the desired product and purified using the procedure described above for compound 5 and isolated as a light yellow oil. 66%). –CH 2 CH2 CH 2 –).5 g.8. 3. d. The reaction was then filtered and the solvent was removed by rotary evaporation. –CH2 SCH2 –. 29. The product 2. s. q.87) S. 76%). s.4. –NCH2 Ar–). NCH2 CH–. 1 H NMR (CDCl 3 ) d 1. 2. 7.2.26 mmol) were added to freshly distilled MeOH (4 ml) in a 20-ml vial. The oil was then dissolved in CH 3 CN (15 ml) and was added to CH 3 CN (50 ml) that had been saturated with CH 3 NH 2 at 08C and charged with Na 2 CO 3 (0.8. dd. The solid was dried under vacuum.2. 1 H NMR (CDCl 3 ) d 1. 0. NCH3 ). found (calcd for C 23 H 37 NS 5 ): C. N-(4 -Vinylbenzyl)-N-methyl-2 aminomethyl-1. d. Anal. The reaction solution was degassed for 10 min by bubbling nitrogen through the solution. This material was not characterized.5–3.40 (2H. 5. 6.85–2.2 (1H. N-(4 -Vinylbenzyl)-N-methyl-2 aminomethyl-1. 3.6–3. 62%). 1.5 g. NCH3 ). The product was purified by column chromatography on silica gel (eluent: CHCl 3 ) and was isolated as a light yellow oil (0. 1.85–2. the vial was capped tightly and the reaction was heated to 788C for 12 h. 5. 7. 1.84.14 pentathiacycloheptadecane.2 (1H. –CH2 SCH2 –.91 (32. d. found (calcd.1 (21 H. 6. R 2 54 -VB) (8) Crown 6 (0. vinyl). vinyl). 0. vinyl). 3.45 g. 31. 5. CI-MS m /z (C 14 H 29 NS 5 . R 2 5 H) (6) Crown 4 (1. 7. 2. 4-Vinylbenzyl chloride (0. CI-MS m /z 1 (C 23 H 37 NS 5 .5–3.11. . 1 H NMR (CDCl 3 ) d 1. –CH 2 CHS–. CI-MS m /z (C 21 H 33 NS 4 .7. 55.0 (4H.40 (7.18 g.66).11 tetrathiacyclotetradecane. / Reactive & Functional Polymers 44 (2000) 111 – 120 treated with MeOH (2 ml) to quench excess SOCl 2 .94). s. The white solid that formed during the reaction was collected by filtration and washed thoroughly with hot MeOH.0 (17 H.5 (2H. d. m. –CH2 SCH2 –.75 (1H. N. 2.00).24 g. d. but its yield was assumed to be quantitative: TLC (CH 2 Cl 2 .53 (2H.F. –NCH2 Ar–).72 (2.4. 2. The solvent was removed by rotary evaporation to yield a yellow oil. 5.89 (59. m. –CH 2 CHS–). Anal. m. [14] aneS4 -N R 1 R 2 ( R 1 5 Me. –CH 2 CHS–.21 (3. 427): 428 (M1H 1 ). aromatic). 487): 488 (M1H ). 7. The reaction was stirred in a sealed flask for 12 h and then filtered. The product was purified by column chromatography on silica gel (eluent: 10% MeOH in CHCl 3 ) and isolated as a light yellow oil.54 g. br m. 3.8.6 mmol) was dissolved in freshly distilled CH 3 CN (20 ml) containing Na 2 CO 3 (0. (0.70 (1H.70 (1H.8. 311): 312 (M1H 1 ). 2. 2.4. d. vinyl).8. The solvent was removed by rotary evaporation to yield 2-chloromethyl-1. d.82).55 (1H.4.9. –CH 2 CH2 CH 2 –). –CH 2 CH2 CH 2 –). for C 21 H 33 NS 4 ): C.42 g. 3. 65%).25 (3H. –NHCH3 . H. 7. [17] aneS5 -N R 1 R 2 ( R 1 5 Me.114 T.11.81 (29. aromatic). –NCH2 CH–).5 g. 2.79).2. –NH ). silica gel).8–2. NCH2 CH–). dd. m.2 (18 H.75–2. Synthesis of thiacrown polymers Thiacrown monomer and DVB (80% divinylbenzene) (45 mg. 2 -( N-methyl)aminomethyl-1.5 (3H.45 (1H.14 pentathiacycloheptadecane. (0. was purified by column chromatography on silica gel (eluent: CHCl 3 ) and was isolated as a colorless oil (0. 58.2. H. –NCH2 CH–). vinyl). m.05 (4H. NCH2 CH–).60 (7. 7. 1 H NMR (CDCl 3 ) d 1. 3.036 mmol) was added to the reaction.65). –CH 2 CHS–. –CH2 SCH2 –. s.30 (2H. 371): 372 (M1H 1 ).8 mmol) was then added and the reaction was heated to reflux for 12 h. 2. CI-MS m /z (C 12 H 25 NS 4 .5–3.34 mmol) was converted to the desired product using the procedure described above for compound 7. 2. N. Rf 0. Baumann et al.

11. 0. 1122 w. 0. the amount of Hg 21 in each aqueous solution was calculated from the concentration of the Hg(dtz) 2 complex in the organic phase following treatment with dtz in CHCl 3 .3.3. 1248 m. 2841 w.022 mmol) in CHCl 3 (100 ml). 1445 m. Mercuric dithizone. 1437 m. 1384 m.10.3. as well as at various dtz to Hg 21 ratios. found: C. The accuracy of this method was determined to be 61 ppm.016 g.3. 0. 2. [14] aneS4 Polymer (9) Thiacrown 7 (145 mg. Reagent solutions Aqueous Hg 21 reagent solutions were prepared by combining aliquots of the mercury solution. 0. 2920 s. and deionized H 2 O (15 ml) were combined and concentrated HCl was added to bring the pH to .T. 1506 w.51. IR (KBr. Stock solutions The Hg 21 stock solutions were prepared by dissolving Hg(NO 3 ) 2 monohydrate (0. 2920 s. 2. of a stock solution prepared by dissolving Hg(dtz) 2 (0.47 buffer (5 ml).42. cm 21 ): 3017 w. 710 m. 799 m.1285 g. 2. The presence of Hg 21 was immediately apparent due to a solution color change in the organic phase from blue to orange. 834 m. Typical procedure was as follows: an aqueous Hg 21 solution was treated with CHCl 3 (5 ml) containing a known concentration of dtz in a separatory funnel. buffer solution. The extinction coefficient of Hg(dtz) 2 in CHCl 3 at 490 was determined by Beer’s Law to be e490 5 58 000 M 21 cm 21 . the UV–vis spectrum of dtz has maxima at 444 and 606 nm. The molecular weights and particle sizes of the resulting polymers were not measured. 798 m. 1119 w.1 mM solutions using CHCl 3 . 19.3. thus each solution was diluted with additional CHCl 3 to meet this requirement. Hg(dtz) 2 . Mercury extraction studies 2. In CHCl 3 .18 g of polymer. 1698 w.10. 1196 w. IR (KBr. 7. 0.19 g of polymer. calibration solutions were prepared by volumetric dilution 2.46. The diphenylthiocarbazone (dithizone or dtz) stock solutions were prepared by dissolving dtz (0. 2789 w.129 mol) in deionized H 2 O (10 ml) and adding concentrated HCl to adjust the solutions to the desired pH. 901 w. S. 711 m. 1605 w. 1300 m. indicating the formation of Hg(dtz) 2 . the 200 ppm Hg 21 solution (5 ml). / Reactive & Functional Polymers 44 (2000) 111 – 120 115 The polymer was then ground under liquid nitrogen with a mortar and pestle. deionized H 2 O and then titrating the solution with HCl to the desired pH. S. 2.47.30. The optimum detection range for this method is 1. 24. 1034 m. 21 2.06 mmol) in 2 M HNO 3 (100 ml). 1259 m. 1016 m. 555 w. 922 w.2.F. 1018 m.0 absorbance units. 7. found: C.2. cm ): 3012 w.34 mmol) was used in the procedure described above to yield 0. The fine polymer powder was then washed thoroughly with hot CHCl 3 and hot MeOH to remove any unreacted starting material. For example. 567 w. 1030 w.3444 g. 1203 w. N. The reliability of this method was checked at each pH and each Hg 21 concentration used in the extraction experiments. Baumann et al. 1699 w. followed by volumetric dilution to 200 and 20 ppm solutions using deionized H 2 O.5 mmol) in CHCl 3 (50 ml) and volumetrically diluting to 1 and 0. Buffers were prepared by dissolving ammonium acetate (10 g. N.1. 65. 62. to prepare a 40 ppm Hg 21 solution at pH 1.74. in agreement with previously reported values [22. 1509 w. Using Beer’s Law.23]. [17] aneS5 Polymer (10) Thiacrown 8 (170 mg. 1418 s. 1603 w.2. Anal. while the spectrum of Hg(dtz) 2 has maxima at 223 and 490 nm. Anal. 1380 m. The phases were shaken together for 2 min. 1296 m.34 mmol) was used in the procedure described above to yield 0. Mercury concentration determinations The concentration of Hg 21 was quantitated spectrophotometrically using a dtz extraction adapted from the methods of Charlot [21].17. 825 m. H. 2. 2848 w. H.49. 1. pH 2. 1421 s.

3. could be chemically modified to allow for the attachment of the thiacrown to a variety of supports.116 T. Mercury extraction The reagent solution (5 ml) was stirred vigorously with the thiacrown polymer (20 mg) in a small vial for the desired time.6. The approximate concentration of Hg 21 in the solution being extracted (20. The suspension was then filtered through a cotton plug in a disposable pipette and the vial and pipette were washed with deionized H 2 O. following the cyclization reaction.49. those methods were not practical for our purposes. 2. however. Minor interference from Cd 21 and Al 31 were observed in the 2.3-dimercapto-1-propanol [26] as the acyclic precursor with the expectation that the resulting 2-hydroxymethyl thiacrown could be readily converted to a 2-aminomethyl thiacrown.4. allowing . Mercury recovery Thiacrown polymer 10. which translates to a 2% removal of Hg 21 for a 20-mg sample of the polystyrene–divinylbenzene copolymer. 200 and 2000 ppm working solutions were used) was calculated from dilution. The solution color immediately turned from deep blue to orange. 2.54310 24 g of Hg 21 (|40 ppm) for 30 min. After filtration of the polymer. the filtrate contained 1. was washed with acetone (5 ml) to remove any residual H 2 O.3. / Reactive & Functional Polymers 44 (2000) 111 – 120 1. alternatively. UV–vis spectra of Hg(dtz) 2 . Baumann et al. Hence we needed an acyclic thiacrown precursor containing a pendant moiety that.F. Synthesis of thiacrown polymers Preparation of a thiacrown polymer begins with the synthesis of a sulfur crown containing a pendant arm incorporated into the carbon framework. Competition experiments were done under the conditions described above and the dtz extraction technique was used to determine only the amount of Hg 21 left in solution. The method. The amount of Hg 21 in the solution was then directly measured by the dtz method described above. that had been treated with a Hg 21 solution by the method described above. The polymer was then dried and reused for the Hg 21 extraction process. The reaction solution and the washings were combined and tested using the dtz method described above to calculate the amount of Hg 21 remaining in the reaction solution. A 1-mM solution of dtz in CHCl 3 (1 ml) and CHCl 3 (3 ml) were added to the dried polymer. could still be used reliably for the quantitation of Hg 21 . The remaining solution was used for reactions with the thiacrown polymer.5.46) containing 1. The solution was stirred and the polymer was filtered from the CHCl 3 solution. polystyrene–co-divinylbenzene (200 mg). While syntheses have been reported for C-substituted sulfur crowns [24.273 10 24 g of Hg 21 . Fe 31 . The pendant arm can then be used to anchor the thiacrown directly to a chemically modified support [17] or. To determine the role that the polystyrene matrix plays in the removal of Hg 21 from aqueous solution. Results and discussion 3.1. This process was repeated until no further color was washed from the resin. 3.25]. Cd 21 and Pb 21 were prepared by volumetric dilution of 1000 and 10 000 (63) ppm plasma standards. was treated with an aqueous solution (pH 1. Metal ion competition studies The solutions of Al 31 . The amount of Hg 21 bound to the polymer was determined by subtracting the amount of Hg 21 remaining in the aqueous solution from the starting Hg 21 concentration of the reagent solution. indicating formation of Hg(dtz) 2 . the arm can be functionalized to form a thiacrown monomer that can be polymerized to generate the resin [16]. This preparation procedure was performed for every reagent solution.3. We selected the commercially available 2. a cross-linked polystyrene resin without appended thiacrowns.

Copolymerization of a 4-vinylbenzyl-substituted thiacrown with DVB (80% divinylbenzene) in MeOH using AIBN as the radical initiator generated the highly cross-linked thiacrown polymers 9 and 10. Polymer 10 was selected as the primary focus of the Hg 21 extraction studies since S 5 crowns have a tendency to form 1:1 metal–ligand complexes with the Hg 21 ion [29].v-ditosylthiaalkanes in N.N-dimethylformamide (Scheme 1). The N-(methyl)aminomethylthiacrowns. The styrene-like monomers can then be easily polymerized using a radical initiator [28].16]. were synthesized in |25% yield through reaction of 2. for 10. 1. / Reactive & Functional Polymers 44 (2000) 111 – 120 117 for more flexibility in attaching the thiacrown to a substrate. Since both crowns are waxy solids.5 mmol of Hg 21 binding sites per gram resin. Both polymers were isolated as white powders that were insoluble in both organic and aqueous media. From this experiment. Synthesis of the 4-vinylbenzyl-substituted thiacrowns. mass spectroscopy and elemental analysis. Crowns 3 and 4 were purified using column chromatography and their structures were confirmed by 1 H NMR spectroscopy. Elemental analysis of the resulting polymeric materials revealed that each gram of polymer contains. using the cesium carbonate mediated cyclization method introduced by Buter and Kellogg [27].3-dimercapto-1-propanol with their respective a. we Scheme 1.F. Assuming that each Hg 21 ion complexes with a single S 5 crown. Hydroxymethyl crown thioethers. were unable to obtain single crystals suitable for X-ray analysis.49 mmol of [14]aneS 4 crown and. it was determined that polymer 10 has |0. Functionalization of ligands with the vinylbenzyl group has been demonstrated previously as a convenient way to incorporate ligands into a polystyrene matrix [3. The fact that the resins were insoluble in H 2 O is important because the resins can be easily separated from aqueous solution once the Hg 21 extraction is complete. followed by reaction with monomethylamine. that .53 mmol of [17]aneS 5 crown (based on% by weight of sulfur). Baumann et al. were prepared in |65% yield through treatment of the hydroxymethylthiacrowns with thionyl chloride to form the 2-chloromethylthiacrowns.T.5. for 9. 3 ([14]aneS 4 -OH) and 4 ([17]aneS 5 -OH). 5 ([17]aneS 5 -N R1 R2 ) and 6 ([17]aneS 5 -N R1 R2 ) 1 2 where R 5Me and R 5H. the resin was treated with a large excess of Hg 21 at pH 1. was readily accomplished by treatment of 5 or 6 with 4-vinylbenzyl chloride. To ascertain the percentage of the thiacrowns in polymer 10 available for Hg 21 binding. 1. 7 ([17]aneS 5 -N R1 R2 ) and 8 ([17]aneS 5 -N R1 R2 ) 1 2 where R 5Me and R 54-vinylbenzyl.

The results of the ESCA studies on the Hg 21 -loaded thiacrown polymers will be presented in a future publication. due to time constraints of the experiment.45 2.F. even for reaction times as short as 30 min. Reaction time (h) 18 3 1 0.7 4.3. the amine is protonated to form a trialkylamTable 1 Extraction of Hg 21 from aqueous solution by 10 as a function of time a Initial Hg 21 concentration (ppm) 4.49 2.46– 6. Polymer 10 is more efficient in extracting Hg 21 from aqueous solution than previously reported thiacrown polymers [16–19]. Under acidic conditions.12 1.5 32 34 34 32 170 400 a b number suggests that only |30% of the thiacrowns are involved in Hg 21 extraction. Those systems.6.3 4.12.59 3. in a competitive situation.1 4.12 1. Results for these experiments are summarized in Tables 1 and 2. Metal ion competition studies The ability to selectively remove a particular metal ion from aqueous solution. however. since there could be cooperative binding of the Hg 21 ions.3. meaning that sulfur donors from two or more crowns may be involved in binding a single Hg 21 ion. in each experiment. These polymers are less hydrophilic relative to 10 and therefore we believe the kinetics of their extraction are slowed.45 2. Mercury extraction studies Mercury extraction capabilities of the thiacrown polymer 10 were tested in aqueous solution at various Hg 21 concentrations. pH 1. Thiacrown polymer 10 contains a trialkylamine moiety that links the crown to the polymer backbone. Hg 21 solutions (4 and 40 ppm) were treated with the [14]aneS 4 polymer and. making the resin hydrophilic. 3.5 Percent extraction b 98 95 95 95 99 monium cation. The improved performance of 10 can be attributed in part to the nature of the polymer matrix.118 T. the extraction of Hg 21 was 971%. we are currently examining the Hg 21 -loaded polymer using ESCA. pH values and reaction times.3 4. At pH 2.60 6. Previously reported thiacrown polymers contain an ether linkage between the polymer and the crown.2.60 6. which contain polymer pendant dithiocarbamate [4] or dithizone [7] ligands.3 4. These results differ from those reported for other polymer-based Hg 21 extractants.3 3. Extraction of Hg 21 by polymer 10 is 951% for each experiment. we have not been able to verify this claim. show decreased efficiency in binding Hg 21 below pH 3. The data in Table 2 show that the uptake of Hg 21 by resin 10 is independent of pH and is essentially quantitative over the pH range 1.5 0.3 34 a b Each extraction was stirred for 30 min. is of utmost importance in design- Each extraction was carried out at pH 3. / Reactive & Functional Polymers 44 (2000) 111 – 120 Table 2 Extraction of Hg 21 from aqueous solution by 10 as a function of pH a Initial Hg 21 concentration (ppm) 3. Extraction (%)51002([remaining Hg 21 ] / [starting Hg 21 ]3 100).0.58 3. . Extraction (%)51002([remaining Hg 21 ] / [starting Hg 21 ]3 100). The kinetics of extraction are probably much faster. The mercury extraction capabilities of the [14]aneS 4 polymer 9 has also been investigated under a limited set of conditions. Baumann et al. but. formed by reaction of a pendant alcohol of the thiacrown with either chloromethylated polystyrene [17] or 4-vinylbenzyl chloride [16]. To further understand this interaction. This number may be higher.58 Percent extraction b 99 99 98 96 99 98 99 97 91 50 3.

Once rinsed and dried. The results show. The extraction of Hg 21 by 10 was not dependent on pH and proved to be much faster than seen in other thiacrown polymer systems. Fig. the recovery of Hg 21 from the resin was determined to be quantitative. In addition. Apparently. We found a convenient method for the removal of Hg 21 from the resin that utilizes the dithizone ligand (Fig. The mercury removal method demonstrated in this report has potential utility in the treatment of industrial wastewater.40 1.51 1. it is reasonable to assume that small amounts of these metal ions are also bound to the resin.53 1. Reaction of polymer 10 with Hg 21 under a variety of conditions demonstrates that the resin efficiently removes Hg 21 ions from acidic aqueous solutions. Efficiency of Hg 21 extraction by polymer 10 in the presence of other metal ions is shown in Table 3. The metal ions (Al 31 . however. Fe 31 . polymer 10 should not only selectively remove Hg 21 from acidic solution. Regeneration of the thiacrown polymer To be considered a legitimate candidate for waste remediation.62 M n 1 :Hg 21 molar ratio 5 5 10 100 Percent extraction b 98 97 98 95 Each extraction was stirred for 30 min. thiacrowns immobilized to a polystyrene–divinylbenzene matrix. the dithizone ligand effectively competes with the sulfur crowns immobilized on the resin for the Hg 21 ion. that these metal ions are unable to effectively compete with Hg 21 for binding sites to the resin. Regeneration of the polymer requires stripping the Hg 21 from the binding sites of the polymer. We are currently investigating alternative methods for stripping the Hg 21 ions from the thiacrown polymer. specifically in regard to US DOE mixed wastes where a selective and cost-effective removal process is required. Baumann et al. Samples of 10 loaded with Hg 21 were treated with a chloroform solution of dtz and the polymer was separated from the orange Hg(dtz) 2 solution by Table 3 Hg 21 ion selectivity data for resin 10 a Metal Pb 21 Cd 21 Fe 31 Al 31 a b filtration. The results show that the resin is selective for removing Hg 21 from acidic solutions. Hg 21 recovery and polymer regeneration were demonstrated. even with a large excess of competing metal ions. the thiacrown was used to treat another aliquot of acidic Hg 21 solution without a significant loss of loading capacity. 3. The resin was also shown to be selective for Hg 21 over a variety of other metal ions. Cd 21 and Pb 21 ) were selected because they are the significant metal ion constituents of the DOE mixed-waste streams and the M n1 :Hg 21 ratios closely resemble those ratios found in the waste. 4.4. No attempt was made to determine the amount of competing metal ions also bound to the thiacrown polymer. Within the experimental error of this method. Extraction (%)51002([remaining Hg 21 ] / [starting Hg 21 ]3 100). Since thiacrowns have some affinity for both Pb 21 and Cd 21 . were synthesized and characterized. 1. . Summary A new class of polymer extractants. Method for recycling polymer 10 using the dithizone ligand.T. 1). / Reactive & Functional Polymers 44 (2000) 111 – 120 119 ing an extractant for environmental remediation applications. but the polymer should also have the potential to be recycled.F. We pH 1.

V. 27 (1988) 2164.E.120 T. Polymers 28 (1995) 89. ¨ A. N. Richardson. Reynolds. 65 (1993) 3389. Chem.A.N..A. Oue.H. R. Angew. K. Polymers 31 (1996) 1. Smith. P. Shono. Fish. Amsterdam. Meider. Sevdic. Yordanov. Chem. J. K.M. Sci. p.F.L. Sept. Alexandratos. C. [8] T. 7–11. Kriger. E. Albright. Bruening. Chem. in: Abstract of Papers. Coughlin. Shah. [9] T. R.D. J. Funct. Samoshin. Soc. N. Baumann.L.S. 1991.G. Meider. G. Tarbet. Fox. A. V. Fish. Synthesis of novel [10] [11] [12] [13] [14] [15] [16] [17] [18] [19] [20] [21] [22] [23] [24] [25] [26] [27] [28] [29] .J. Kellogg. G. Chem. Inorg. Sibert. H. Future work also includes the extraction of first row transition metals using the S 4 polymer 9. M. Fish. 9. Tamura.L. 184 (1983) 2431. Breitner. Synth. Fish. K. Acknowledgements This work was performed under the auspices of the US Department of Energy by the Lawrence Livermore National Laboratory under contract number W-7405-ENG-48. Case.J. Inorg. Sevdic. Buter. Chem. 1998. M. L.C. Int. Franz. Polyhedron 10 (1991) 1545.J. Ochrrymowycz. S. A. ENVR 117. M. Schroder. [6] S. D. D. K.J. Ed. 35 (1990) 1. Chem.C. [4] S. Arnold. D. This compound has been used to synthesize 2-hydroxymethyldithia-18-crown-6. Coord. V. Chem. R. B. 65 (1987) 150.L. Cooper. Olmstead. Makromol. Polyhedron 15 (1996) 4241. Talanta 37 (1990) 491. J. Nikishin. Acc.J. Li. Micheau. 21 (1988) 141. Yamashita. R.A. O. 475. Takasu. H. Analyst 113 (1988) 551.M. / Reactive & Functional Polymers 44 (2000) 111 – 120 pendant arm crown thioethers for mercury removal from mixed waste streams. Anal. Polym. Baumann. G. 87 (1965) 4441. J. React. Shpigun. Ohara.B. J. Albright. D. J. T. Kakiuchi.G. M. 34 (1995) 2813. Chen.D. Kantipuly. J. Blake. Chem. 295. 36 (1997) 642. D. R. NV. Meriwether. R.J. K. Situmeang. G.A. G.R. Huang. Reed. J. S. J.H. K. L. Inorg. Am.H.H. Katragadda.G. Nucl. P. Tomoi. Meider.S. Rorabacher. Ed. Izatt.T. Leggett. Kuppers. A. M.J. React.L.H. Adv. Inorg. in: Colorimetric Determination of the Elements. Nucl. 39 (1977) 1409. Storey. J. R. Baumann et al. 1637. Reynolds. Hoffman.K. 1964. D. Chem. G. Org. Res. Heterocyclic Chem 27 (1990) 347.M. Las Vegas.H. H. Inorg. Charlot. The authors thank Hugh Gregg for performing the electrospray mass spectrometry and Carolyn Koester for performing some of the CI mass spectrometry.W. E. Pasteur. Chem. K. H.M.F. Engl. B. Soc. C. E. A. Huang. G. React. Pett. Roundhill. 170 (1998) 93. D. are presently investigating the immobilization of the thiacrowns onto different supports. Mendeleev Commun.I. H. Franz. ¨ R. T. R.I. Sevdic. B. Commun. L. References [1] A. Gesser. Chem. R. 67 (1990) 459. J. 42 (1980) 885. Fekete. Samoshina. K. Tetrahedron 51 (1995) 8175. J. Funct. Lange. P.B. Chem. Inorg. Pogosyan. Devenyi. Chem. Admans. B. Levy. Kamilova. W.M.H. Lavabre.C. Chem. Moyer. Chem. 1997. Polymers 31 (1996) 47. J. Chow.M. Part A 3 (1965) 265. Sloan. S.P.J. Kurita. Blowers. [7] R. Devenyi. Li. J. E. S.G. Devi. J. [2] C. Elsevier. J. 43 (1981) 153. K. N. Stern. Krakowiak. M. Schroder. S.T.M. M. 214th National Meeting of the American Chemical Society. Chem. Commun.S.F. [3] H. B. Cooper.E.M. Kimura. Nucl. M. Tsuda. Albright. Funct. Rev. L.R.A. Abe. ¨ A. Troansky. G.L. Kopytova. Nango.D. Blake. [5] W. Borberle. A. 1996. Bradshaw. Fox. H. Barrett. R. Reid.