research article aminoalkylated merrifield resins...

Research ArticleAminoalkylated Merrifield Resins Reticulated byTris-(2-chloroethyl) Phosphate for Cadmium Copper andIron (II) Extraction

Mokhtar Dardouri Fayccedilel Ammari and Faouzi Meganem

Laboratory of Organic Synthesis Faculty of Sciences of Bizerte University of Carthage Zarzouna 7021 Bizerte Tunisia

Correspondence should be addressed to Faycel Ammari ammari1971gmailcom

Received 4 February 2015 Revised 1 April 2015 Accepted 2 April 2015

Academic Editor Cun-Yue Guo

Copyright copy 2015 Mokhtar Dardouri et al This is an open access article distributed under the Creative Commons AttributionLicense which permits unrestricted use distribution and reproduction in any medium provided the original work is properlycited

We aimed to synthesize novel substituted polymers bearing functional groups to chelate heavy metals during depollutionapplications Three polyamine functionalized Merrifield resins were prepared via ethylenediamine (EDA) diethylenetriamine(DETA) and triethylenetetramine (TETA) modifications named respectively MR-EDA MR-DETA and MR-TETA Theaminoalkylated polymers were subsequently reticulated by tris-(2-chloroethyl) phosphate (TCEP) to obtain new polymeric resinscalled respectively MR-EDA-TCEPMR-DETA-TCEP andMR-TETA-TCEPThe obtained resins were characterized via attenuatedtotal reflectance Fourier transform infrared spectroscopy (ATR-FTIR) elemental analysis (EA) and thermogravimetric (TGA)thermodynamic (DTA) and differential thermogravimetric (DTG) analysis The synthesized resins were then assayed to evaluatetheir efficiency to extract metallic ions such as Cd2+ Cu2+ and Fe2+ from aqueous solutions

1 Introduction

Recently the solid phase extraction (SPE) has been shown tobe an excellent separation technique due to immiscibility ofresins with aqueous phase low rate of physical degradationminimum release of toxic organic solvents and recyclingoptions [1 2] In SPE the organic extractants are eithersorbed or anchored to an inert polymeric support [3 4]In this context grafted resins have been used in separationof hazardous metallic ions in industrial effluents [5 6] Infact many polymers were reported to contain functionalchelating groups (i) morin (2101584034101584057-pentahydroxyflavone)which was covalently attached to Merrifieldrsquos resin and usedin metal sorption and recognition [7] (ii) chelating ionexchange which was prepared by functionalizing Merrifieldresin with 221015840-pyridylimidazole and used to selectivelyadsorb and separate nickel from other base metal ions insynthetic sulfate solutions [8] and (iii) polymer-supportedtriazoles were used to extract metals such as Cd Fe MgNi and Co from aqueous solutions [9] Indeed it hasbeen reported that adsorption properties and selectivity for

metallic ions depend on the molecular structure of adsorp-tionmaterials particularly polyamine functional groups andnitrogen atoms [10ndash13] Besides other resins modified bythe organophosphorus reagents such as polyethylene iminemethylene phosphonic acid have also been performed toremove copper ions from aqueous media [14] In fact thereare many research articles describing the synthesis procedureof chloromethylated polystyrene or Merrifield resin attachedwith polyamine groups and employed them as adsorbent forheavy metals removal from aqueous solutions [15ndash18]

In the present paper we attempt to investigate modifiedMerrifield resins functionalized by polyamines and phospho-rus derivatives to adsorb metallic ions in an aqueous phase

2 Experimental

21 Materials Merrifield resin (MR reticulated by 2 divin-ylbenzene 200ndash400 mesh 21mmol Clsdotgminus1 Fluka) ethylene-diamine (EDA) diethylenetriamine (DETA) triethylenete-tramine (TETA) and Tris-(2-chloroethyl) phosphate (TCEP)were purchased from Sigma-Aldrich Tetrahydrofuran (THF)

Hindawi Publishing CorporationInternational Journal of Polymer ScienceVolume 2015 Article ID 782841 6 pageshttpdxdoiorg1011552015782841

2 International Journal of Polymer Science

DMF

H2N(CH2CH2NH)nH

CH2Cl CH2NH(CH2CH2NH)nHMR

n = 1 MR-EDA n = 2 MR-DETA n = 3 MR-TETA

80∘C

Figure 1 Proposed synthesis of MR-EDA MR-DETA and MR-TETA resins

and dimethylformamide (DMF)were purchased fromSigma-Aldrich Absolute ethanol triethylamine (TEA) and diethylether were purchased from Prolabo Iodide potassium (KI)CdCl2sdotH2O FeCl

2sdot4H2O and CuCl

2sdot6H2O were purchased

from Fluka

22 Instrumental Analyses Infrared analysis was carried outby using the attenuated total reflectance technique (ATR-FTIR) with a Nicolet FTIR 200 spectrophotometer (ThermoScientific) Elemental analysis of C H and N was performedby Perkin Elmer analyzer CHN Series II 2400 Elementalanalysis of P was performed by ICP-OES analysis on aHORIBA Scientific DTA TGA and DTG analyses werecarried out with a Mettler Toledo TGADSC 1 Star System(power 400 Watts) The amount of remaining metal ionsin solution was evaluated by flame atomic absorption spec-troscopy (FAAS) analysis on a Perkin-Elmer PinAAcle 900 TThe detection limits for Cd2+ Cu2+ and Fe2+ are 08 15 and5mgsdotLminus1 respectively and the corresponding wavelengthsfor the studied metals are 2288 32475 and 24833 nmrespectively

23 Extraction Procedure of Metal Cations The synthesizedpolymers (01 g) were incubated with 20mL of aqueoussolution of metal ion at 25∘C for 24 h Aqueous monometallicsolutions of CdCl

2sdotH2O FeCl

2sdot4H2O and CuCl

2sdot6H2Owere

prepared at a concentration of 210minus4molsdotLminus1 in relation witheach metal ion in distilled water (pH = 6-7) The suspensionwas filtrated on filter paper (previously washed several timeswith distilled water until disappearance of conductivity inwashing water) The amount of remaining metal ions wasevaluated by FAAS analysis of the filtrate The extractionpercentage () was calculated using the following equation

Extraction = ((119862

119894minus 119862

119891)

119862

119894

) times 100(1)

where 119862119894and 119862

119891are the concentrations of the metal ion in

initial and final solutions respectively

24 Synthesis of Merrifield Resin with Ethylenediamine Group(MR-EDA) MR-EDA was prepared according to the litera-ture [16] with some modification The synthesis procedure

was performed according to Figure 1 First commerciallyavailable Merrifield resin was suspended in DMF for 10 hfollowed by the addition of EDAThe amine is used in excessto act as the base and increase the rate of reaction Then thereaction mixture was stirred at room temperature for 15 hand then for 24 h at 70ndash80∘C After completing the reactionthe resin was washed several times with deionized water andthenwith absolute ethanol After the obtained resinwas driedunder vacuum at 50∘C for 48 h

25 Synthesis of Merrifield Resin with DiethylenetriamineGroup (MR-DETA) The reaction involved MR DMF andexcess of DETAThe reaction conditions of the product weresimilar to that of MR-EDA (see Figure 1)

26 Synthesis of Merrifield Resin with TriethylenetetramineGroup (MR-TETA) The reaction involved MR DMF andexcess TETA The reaction conditions of the product weresimilar to that of MR-EDA (see Figure 1)

27 Synthesis of MR-EDA Reticulated by Tris-(2-chloroethyl)Phosphate (MR-EDA-TCEP) The synthesis procedure wasperformed according to Figure 2MR-EDAwas suspended inTHF followed by the addition of certain amount of TCEP asmall amount of KI used as catalysts Then a certain amountof TEA used as base was added to the flask The reactionmixture was heated at 70∘C for 72 h The cooled mixturewas filtered and washed with distilled water and with diethylether After the obtained resin was dried in a vacuum at 50∘Cfor 48 h

28 Synthesis of MR-DETA Reticulated by Tris-(2-chloroethyl)Phosphate (MR-DETA-TCEP) The reaction medium con-tained MR-DETA THF KI TCEP and TEA The reactionconditions of the product were similar to that of MR-EDA-TCEP (see Figure 2)

29 Synthesis of MR-TETA Reticulated by Tris-(2-chloroethyl)Phosphate (MR-TETA-TCEP) The reaction medium con-tained MR-TETA THF KI TCEP and TEA The reactionconditions of the product were similar to that of MR-EDA-TCEP (see Figure 2)

International Journal of Polymer Science 3

CH2NH(CH2CH2NH)nH

THF

Tris-(2-chloroethyl) phosphateKI Et3N

O OP

n = 1 MR-EDA-TCEP n = 2 MR-DETA-TCEP n = 3 MR-TETA-TCEP

3

(NHCH2CH2)n

NHCH2

70∘C

Figure 2 Proposed synthesis of MR-EDA-TCEP MR-DETA-TCEP and MR-TETA-TCEP resins

4000 3500 3000 2500 2000 1500 1000 500

16051456

3330

3320

2937

285929383044

1673

1673(d)

(c)

(b)

(a)

696

3332 1673

1265

Tran

smitt

ance

()

Wavenumber (cmminus1)

Figure 3 ATR-FTIR ofMR resin (a)MR-EDA resin (b)MR-DETAresin (c) and MR-TETA resin (d)

3 Results and Discussion

31 Characterization

311 ATR-FTIR Analysis The structures of synthetic chelat-ing resins MR-EDA MR-DETA and MR-TETA can beconfirmed by comparing the ATR-FTIR spectra of Merrifieldresin before and after reaction with polyamines as shownin Figure 3 The spectra showed the disappearance of the 120575CH2-Cl band which appears at 1265 cmminus1 from theMerrifield

resin [15] and the appearance of new bands at 3320 cmminus1and a broad peak at 1670 cmminus1 which could be attributedto the stretching vibration and deformation vibration of N-H respectively accounting for NHNH

2introduced groups

These findings agree with the literature [16] The proposedsynthesis route to the prepared resins is presented schemati-cally in Figure 1

On the other hand the ATR-FTIR spectra of the resinsMR-EDA-TECP MR-DETA-TECP and MR-TETA-TCEP(Figure 4) showed the appearance of new bands of symmet-rical and asymmetrical stretching vibration characteristics ofP-O-C observed at respectively 1030 and 1076 cmminus1 Indeednew peak appeared at 1221 cmminus1 and could be attributed tothe stretching vibration of P=O These findings confirmedthe functionalization of the resins by the tris-(2-chloroethyl)phosphate group The proposed synthesis route to the newlyprepared resins is presented schematically in Figure 2

4000 3500 3000 2500 2000 1500 1000 500

6961670

3329

3340

3317 1076

1076

1221

1221

1030

1030

12211076

1030

(g)

(f)

(e)

Tran

smitt

ance

()


Figure 4 ATR-FTIR ofMR-EDA-TCEP resin (e)MR-DETA-TCEPresin (f) and MR-TETA-TCEP resin (g)

Table 1 Elemental analysis results of MR-EDA MR-DETA andMR-TETA resins

Sample name C () H () N ()MR-EDA 7815 518 423MR-DETA 7250 725 503MR-TETA 7290 786 680

312 Elemental Analysis Table 1 presented the N percent-age in chelating resins determined by elemental analysesObtained results showed that the content of nitrogen in MR-EDA MR-DETA and MR-TETA were 424 503 and 680respectively These findings suggest that the resin structureparticularly polyamine chain length and nitrogen atomscomposition influences the N content Besides elementalanalysis showed also that the P content in MR-EDA-TCEPMR-DETA-TCEP and MR-TETA-TCEP resins was 147 144and 152 respectively which confirm the grafting of TCEPgroups on the aminoalkylated resins In fact the polyaminegroups (EDA DETA and TETA) loading in MR-EDA MR-DETA and MR-TETA are 907 1224 and 1769 by weightrespectively In addition TCEP group loading in MR-EDA-TCEPMR-DETA-TCEP andMR-TETA-TCEP is 2764 2708and 2858 by weight respectively

313 TGADTA andDTGAnalyses Thecharacteristic TGADTA and DTG curves of MR MR-EDA MR-DETA MR-TETA MR-EDA-TECP MR-DETA-TECP and MR-TETA-TECP were presented in Figures 5 6 and 7 showing


0 100 200 300 400 500 600

0

20

40

60

80

100(g)(f)(e)

(d)(c)(b)(a)W

eigh

t los

s (

)

Temperature (∘C)

Figure 5 TGA curves of MR resin (a) MR-EDA resin (b) MR-DETA resin (c) MR-TETA resin (d) MR-EDA-TCEP resin (e) MR-DETA-TCEP resin (f) and MR-TETA-TCEP resin (g) heated withthe temperature increment rate 5∘C minminus1 in air

0 100 200 300 400 500 600minus100minus50

050

100150200250300350400450500550600650700

305 330509

Exo

(g)

(f)

(e)

(d)(c)

(b)

(a)

HF

(mw

)

Tg = 184∘C

Tg = 163∘CTg = 204∘C

Tg = 196∘C

Tg = 215∘CTg = 200∘C

Temperature (∘C)

Figure 6 DTA curves of MR resin (a) MR-EDA resin (b) MR-DETA resin (c) MR-TETA resin (d) MR-EDA-TCEP resin (e) MR-DETA-TCEP resin (f) and MR-TETA-TCEP resin (g) heated withthe temperature increment rate 5∘C minminus1 in air

the complexity of the thermal decomposition for chemicallymodified resins The thermal stability of MR resin wasdivided into three regions 190ndash325∘C 325ndash425∘C and above600∘C In fact the exothermic peak which appears nearlyto 320∘C was detected in TGA by a weight loss up to288 in the temperature range 190ndash325∘C that can explainthe elimination of chloromethylated group CH

2Cl [19] In

addition the exothermic phenomena that corresponded toa weight loss up to 23 in the temperature range between325∘C and 425∘C may suggest the thermal degradation ofthe cross-linked structure of MR resin and the polymerseems to be decomposed completely at 600∘C [20] The DTAcurves (Figure 6) ofMR resin showed three exothermic peaksobserved at 305 330 and 509∘C This data may suggestthat the decomposition of the resin took place in steps

50 100 150 200 250 300 350 400 450 500 550 600

(g)

(f)(e)

(d)(c)

(b)

(a)

dW

dT

Temperature (∘C)

302∘C 328∘C 511∘C

Figure 7 DTG curves of MR resin (a) MR-EDA resin (b) MR-DETA resin (c) MR-TETA resin (d) MR-EDA-TCEP resin (e) MR-DETA-TCEP resin (f) and MR-TETA-TCEP resin (g) heated withthe temperature increment rate 5∘C minminus1 in air

The DTA curves of MR-EDA MR-DETA MR-TETA MR-EDA-TCEP MR-DETA-TCEP and MR-TETA-TCEP showedthat the glass transition temperature (119879

119892) was respectively

184 163 204 196 215 and 200∘C Besides all resins presenttwo exothermic peaks that could indicate their decompo-sition The substitution at the benzene ring of polystyrenedetermined three degradation stages with different weightlosses depending on the chemical structure of the substituent(Table 2) Hence we have considered the weight losses (119908 lt10) up to 250∘C as insignificant representing the solventand water retained in the sample From Figure 7 and Table 2one can see that the thermal stability of the studied com-pounds decreases in the following order MR-EDA gt MR-TETA gtMR-DETA gtMR-EDA-TCEP gtMR-TETA-TCEP gtMR-DETA-TCEP = MR

32 Metal Ions Extraction by the Synthesized PolymersTable 3 showed that the order of adsorption capacity ofthe chelating resins against Cd2+ Cu2+ and Fe2+ ions wasrespectively MR-TETA gt MR-DETA gt MR-EDA whichagree with the other investigation [16] This increase inadsorption percentage could be explained by the highercontent of nitrogen atoms in functional groups and thusimposed more coordination with metallic ions

The orders of adsorption capacity for Cd2+ are asfollows MR-DETA-TCEP gt MR-EDA-TCEP gt MR-TETA-TCEP MR-EDA-TCEP gt MR-EDA MR-DETA-TCEP gtMR-DETA and MR-TETA gt MR-TETA-TCEP Besides theorders of adsorption capacity for Cu2+ are as followsMR-TETA-TCEP gtMR-DETA-TCEP gtMR-EDA-TCEP andMR-EDA-TCEP gt MR-EDA and MR-DETA-TCEP gt MR-DETA and MR-TETA-TECP gt MR-TETA In addition theorders of adsorption capacity for Fe2+ are as follows MR-EDA-TCEP gt MR-DETA-TCEP gt MR-TETA-TCEP andMR-EDA-TCEP gt MR-EDA and MR-DETA gt MR-DETA-TCEP and MR-TETA gt MR-TETA-TCEP Hence it appears


Table 2 TGA data for Merrifield resin and its substituted derivatives

Sample Weight loss (119882 ) and temperature range (Δ119879 ∘C)Step I Step II Step III

MR Δ119879I = 190ndash325∘C119882I = 2883

Δ119879II = 325ndash420∘C119882II = 2389

Δ119879III = 420ndash550∘C119882III = 4590

MR-EDA Δ119879I = 50ndash250∘C119882I = 64

Δ119879II = 250ndash425∘C119882II = 4579

Δ119879III = 425ndash580∘C119882III = 4607

MR-DETA Δ119879I = 50ndash220∘C119882I = 76

Δ119879II = 220ndash425∘C119882II = 4760

Δ119879III = 425ndash600∘C119882III = 4350

MR-TETA Δ119879I = 50ndash240∘C119882I = 557

Δ119879II = 240ndash435∘C119882II = 5233

Δ119879III = 435ndash600∘C119882III = 4063

MR-EDA-TCEP Δ119879I = 50ndash215∘C119882I = 36

Δ119879II = 215ndash430∘C119882II = 4329

Δ119879III = 430ndash600∘C119882III = 4633

MR-DETA-TCEP Δ119879I = 50ndash190∘C119882I = 394

Δ119879II = 190ndash425∘C119882II = 3510

Δ119879III = 425ndash600∘C119882III = 4620

MR-TETA-TCEP Δ119879I = 50ndash200∘C119882I = 485

Δ119879II = 200ndash430∘C119882II = 4513

Δ119879III = 430ndash600∘C119882III = 4756

Table 3 Extraction percentage results of metal ions by the synthesized polymers

Extraction percentage ( plusmn standard deviation)Metals ions MR-EDA MR-DETA MR-TETA MR-EDA-TECP MR-DETA-TECP MR-TETA-TCEPCd2+ 50 plusmn 07 57 plusmn 05 69 plusmn 07 69 plusmn 09 73 plusmn 08 63 plusmn 07Cu2+ 68 plusmn 11 71 plusmn 12 94 plusmn 15 90 plusmn 11 93 plusmn 13 95 plusmn 13Fe2+ 69 plusmn 17 70 plusmn 16 96 plusmn 14 70 plusmn 15 66 plusmn 13 61 plusmn 13Note each result is the mean from three determinations plusmn standard deviation

that MR-TETA-TECP and MR-TETA resins exhibited goodadsorption selectivity for Fe(II) and Cu(II) respectively

This high adsorption selectivity could be explained bythe high affinity of Fe(II) and Cu(II) ions to the polyamineand organophosphate groups in studied resins On the basisof hard-soft acid-base (HSAB) theory Fe(II) and Cu(II)were classified as intermediate ions Therefore they haveaffinities to two types of soft ligands which contain nitrogenatoms of polyamine groups and hard ones which containoxygen atoms of organophosphate groups The deference ofadsorption capacity of metallic ions such as Cd2+ Cu2+and Fe2+ by the three synthesized polymers MR-EDA-TCEPMR-DETA-TCEP and MR-TETA-TCEP can be explainedessentially by the compatibility factor between the cationssize and the ligands cavity size in polymer matrix whichwas probably influenced by the cross-linking degree Thelength of amine chain and the cross-linking by the TCEP isdirectly proportional However the active sites are less readilyavailable and efficiency of the resin is reduced In fact for Fe2+

which has a less size than Cu2+ the adsorption percentageincreases in the sense MR-EDA-TCEP MR-DETA-TCEPand MR-TETA-TCEP But for Cu2+ which has a higher sizethan Fe2+ the same phenomena decreases in the same senseIn the case of Cd2+ which has a higher size than the twocations Cu2+ and Fe2+ the adsorption percentage is better inMR-DETA-TCEP than in the two resins MR-EDA-TECP andMR-TETA-TCEP In fact in MR-DETA-TCEP the Cd2+ wassimply incorporated in the complex sites compared to the two

other resins It can be explained by the high compatibilitybetween the Cd2+ cations size and the ligands cavity size inMR-DETA-TCEP polymer matrix

4 Conclusions

In the present paper three chelating resins were synthesizedvia chemical grafting of polyamine groups on Merrifieldresin leading to resin polymers namedMR-EDAMR-DETAand MR-TETA In fact these chelating resins are reticulatedby tris-(2-chloroethyl) phosphate (TCEP) to access to newpolymers calledMR-EDA-TECPMR-DETA-TECP andMR-TETA-TECP respectively These synthesized polymers werecharacterized by ATR-FTIR EA TGA DTA and DTGanalysis and were tested for their ability to extract metallicions from aqueous solutions particularly for Cu2+ Fe2+and Cd2+ The obtained results show that MR-DETA-TECPexhibited good efficiency towards Cd2+ (73) while MR-TETA-TCEP andMR-TETAwere efficient against Cu2+ (95)and Fe2+ (96) respectively However further approachesare still required in order to highlight and understand theinvolvement of polymermodifications and their mechanismsfor metallic extractions as well as their application in envi-ronmental conditions

Conflict of Interests

The authors declare that there is no conflict of interestsregarding the publication of this paper


Acknowledgment

The authors would like to thank the Tunisian Ministry(Research Unit 05UR12-05) which financed this project

References

[1] Z Mester R Sturgeon and J Pawliszyn ldquoSolid phase microex-traction as a tool for trace element speciationrdquo SpectrochimicaActa Part B Atomic Spectroscopy vol 56 no 3 pp 233ndash2602001

[2] MMerdivanM ZDuz andCHamamci ldquoSorption behaviourof uranium (VI) with NN-dibutyl-N-benzoylthiourea Impreg-nated inAmberlite XAD-16rdquoTalanta vol 55 pp 639ndash645 2001

[3] E P Horwitz Proceedings of the International Workshop onthe Application of Extraction Chromatography in RadionuclideMeasurements IRMM Geel 9-10 EUR 18974 EN Institute forReference Materials and Measurements 1998

[4] P KMohapatra S Sriram V KManchanda and L P BadhekaldquoUptake of metal ions by extraction chromatography usingdimethyl dibutyl tetradecyl-13-malonamide (DMDBTDMA)as the stationary phaserdquo Separation Science and Technology vol35 no 1 pp 39ndash55 1999

[5] P Liu Y Liu and Z Su ldquoModification of poly(hydroethylacrylate)-grafted cross-linked poly(vinyl chloride) particlesvia surface-initiated atom-transfer radical polymerization (SI-ATRP) competitive adsorption of some heavy metal ionson modified polymersrdquo Industrial and Engineering ChemistryResearch vol 45 no 7 pp 2255ndash2260 2006

[6] E A Moawed M A A Zaid and M F El-Shahat ldquoMethyleneblue-grafted polyurethane foam using as a chelating resin forpreconcentration and separation of cadmium(II) mercury(II)and silver(I) from waste waterrdquo Analytical Letters vol 36 no 2pp 405ndash422 2003

[7] G Pina-Luis G A Rosquete Pina A C Valdes GonzalezA O Teran I R Espejel and M E Dıaz-Garcıa ldquoMorinfunctionalizedMerrifieldrsquos resin a newmaterial for enrichmentand sensing heavy metalsrdquo Reactive and Functional Polymersvol 72 no 1 pp 61ndash68 2012

[8] A I Okewole E Antunes T Nyokong and Z R TshentuldquoThe development of novel nickel selective amine extractants221015840-Pyridylimidazole functionalised chelating resinrdquo MineralsEngineering vol 54 pp 88ndash93 2013

[9] A Ouerghui H Elamari S Ghammouri R Slimi F Meganemand C Girard ldquoPolystyrene-supported triazoles for metal ionsextraction synthesis and evaluationrdquo Reactive and FunctionalPolymers vol 74 no 1 pp 37ndash45 2014

[10] R R Navarro K Sumi N Fujii and M Matsumura ldquoMercuryremoval from wastewater using porous cellulose carrier modi-fied with polyethyleneiminerdquoWater Research vol 30 no 10 pp2488ndash2494 1996

[11] I M El-Nahhal N M El-Ashgar M M Chehimi et alldquoMetal uptake by porous iminobis(N-2-aminoethylacetamide)-modified polysiloxane ligand systemrdquo Microporous and Meso-porous Materials vol 65 no 2-3 pp 299ndash310 2003

[12] Y Baba K Ohe Y Kawasaki and S D Kolev ldquoAdsorp-tion of mercury(II) from hydrochloric acid solutions onglycidylmethacrylate-divinylbenzene microspheres containingamino groupsrdquo Reactive and Functional Polymers vol 66 no10 pp 1158ndash1164 2006

[13] A Denizli S Senel G Alsancak N Tuzmen and R SayldquoMercury removal from synthetic solutions using poly(2-hy-droxyethylmethacrylate) gel beads modified with poly(ethyl-eneimine)rdquo Reactive and Functional Polymers vol 55 no 2 pp121ndash130 2003

[14] N Ferrah O Abderrahim M A Didi and D VilleminldquoRemoval of copper ions from aqueous solutions by a new sor-bent polyethyleneiminemethylene phosphonic acidrdquoDesalina-tion vol 269 no 1ndash3 pp 17ndash24 2011

[15] C Girard I Tranchant V Gorteau L Potey and J HerscovicildquoDevelopment of a DNA interaction test with small moleculesstill grafted on solid phaserdquo Journal of Combinatorial Chemistryvol 6 no 2 pp 275ndash278 2004

[16] R Qu J Liu C Sun Y Zhang C Ji and P Yin ldquoRemoval andseparation of Hg(II) ions from aqueous solutions by macro-porous polystyrene-co-divinylbenzene-supported polyaminechelating resinsrdquo Journal of Chemical amp Engineering Data vol55 no 11 pp 4650ndash4659 2010

[17] C Xiong and C Yao ldquoSynthesis characterization and appli-cation of triethylenetetramine modified polystyrene resin inremoval of mercury cadmium and lead from aqueous solu-tionsrdquo Chemical Engineering Journal vol 155 no 3 pp 844ndash850 2009

[18] J Li G Yang Y Qin X Yang and Y Cui ldquoRecyclable Mer-rifield resin-supported thiourea organocatalysts derived fromL-proline for direct asymmetric aldol reactionrdquo TetrahedronAsymmetry vol 22 no 6 pp 613ndash618 2011

[19] W Mo H Liu H Xiong M Li and G Li ldquoPreparationof CuCl110-phenanthroline immobilized on polystyrene andcatalytic performance in oxidative carbonylation of methanolrdquoApplied Catalysis A General vol 333 no 2 pp 172ndash176 2007

[20] G Lisa E Avram G Paduraru M Irimia N Hurduc andN Aelenei ldquoThermal behaviour of polystyrene polysulfoneand their substituted derivativesrdquo Polymer Degradation andStability vol 82 no 1 pp 73ndash79 2003

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DMF

H2N(CH2CH2NH)nH

CH2Cl CH2NH(CH2CH2NH)nHMR

n = 1 MR-EDA n = 2 MR-DETA n = 3 MR-TETA

80∘C

Figure 1 Proposed synthesis of MR-EDA MR-DETA and MR-TETA resins

and dimethylformamide (DMF)were purchased fromSigma-Aldrich Absolute ethanol triethylamine (TEA) and diethylether were purchased from Prolabo Iodide potassium (KI)CdCl2sdotH2O FeCl

2sdot4H2O and CuCl

2sdot6H2O were purchased

from Fluka

22 Instrumental Analyses Infrared analysis was carried outby using the attenuated total reflectance technique (ATR-FTIR) with a Nicolet FTIR 200 spectrophotometer (ThermoScientific) Elemental analysis of C H and N was performedby Perkin Elmer analyzer CHN Series II 2400 Elementalanalysis of P was performed by ICP-OES analysis on aHORIBA Scientific DTA TGA and DTG analyses werecarried out with a Mettler Toledo TGADSC 1 Star System(power 400 Watts) The amount of remaining metal ionsin solution was evaluated by flame atomic absorption spec-troscopy (FAAS) analysis on a Perkin-Elmer PinAAcle 900 TThe detection limits for Cd2+ Cu2+ and Fe2+ are 08 15 and5mgsdotLminus1 respectively and the corresponding wavelengthsfor the studied metals are 2288 32475 and 24833 nmrespectively

23 Extraction Procedure of Metal Cations The synthesizedpolymers (01 g) were incubated with 20mL of aqueoussolution of metal ion at 25∘C for 24 h Aqueous monometallicsolutions of CdCl

2sdotH2O FeCl

2sdot4H2O and CuCl

2sdot6H2Owere

prepared at a concentration of 210minus4molsdotLminus1 in relation witheach metal ion in distilled water (pH = 6-7) The suspensionwas filtrated on filter paper (previously washed several timeswith distilled water until disappearance of conductivity inwashing water) The amount of remaining metal ions wasevaluated by FAAS analysis of the filtrate The extractionpercentage () was calculated using the following equation

Extraction = ((119862

119894minus 119862

119891)

119862

119894

) times 100(1)

where 119862119894and 119862

119891are the concentrations of the metal ion in

initial and final solutions respectively

24 Synthesis of Merrifield Resin with Ethylenediamine Group(MR-EDA) MR-EDA was prepared according to the litera-ture [16] with some modification The synthesis procedure

was performed according to Figure 1 First commerciallyavailable Merrifield resin was suspended in DMF for 10 hfollowed by the addition of EDAThe amine is used in excessto act as the base and increase the rate of reaction Then thereaction mixture was stirred at room temperature for 15 hand then for 24 h at 70ndash80∘C After completing the reactionthe resin was washed several times with deionized water andthenwith absolute ethanol After the obtained resinwas driedunder vacuum at 50∘C for 48 h

25 Synthesis of Merrifield Resin with DiethylenetriamineGroup (MR-DETA) The reaction involved MR DMF andexcess of DETAThe reaction conditions of the product weresimilar to that of MR-EDA (see Figure 1)

26 Synthesis of Merrifield Resin with TriethylenetetramineGroup (MR-TETA) The reaction involved MR DMF andexcess TETA The reaction conditions of the product weresimilar to that of MR-EDA (see Figure 1)

27 Synthesis of MR-EDA Reticulated by Tris-(2-chloroethyl)Phosphate (MR-EDA-TCEP) The synthesis procedure wasperformed according to Figure 2MR-EDAwas suspended inTHF followed by the addition of certain amount of TCEP asmall amount of KI used as catalysts Then a certain amountof TEA used as base was added to the flask The reactionmixture was heated at 70∘C for 72 h The cooled mixturewas filtered and washed with distilled water and with diethylether After the obtained resin was dried in a vacuum at 50∘Cfor 48 h

28 Synthesis of MR-DETA Reticulated by Tris-(2-chloroethyl)Phosphate (MR-DETA-TCEP) The reaction medium con-tained MR-DETA THF KI TCEP and TEA The reactionconditions of the product were similar to that of MR-EDA-TCEP (see Figure 2)

29 Synthesis of MR-TETA Reticulated by Tris-(2-chloroethyl)Phosphate (MR-TETA-TCEP) The reaction medium con-tained MR-TETA THF KI TCEP and TEA The reactionconditions of the product were similar to that of MR-EDA-TCEP (see Figure 2)


CH2NH(CH2CH2NH)nH

THF


O OP


3

(NHCH2CH2)n

NHCH2

70∘C


4000 3500 3000 2500 2000 1500 1000 500

16051456

3330

3320

2937

285929383044

1673

1673(d)

(c)

(b)

(a)

696

3332 1673

1265

Tran

smitt

ance

()




31 Characterization



2introduced groups



4000 3500 3000 2500 2000 1500 1000 500

6961670

3329

3340

3317 1076

1076

1221

1221

1030

1030

12211076

1030

(g)

(f)

(e)

Tran

smitt

ance

()








0 100 200 300 400 500 600

0

20

40

60

80

100(g)(f)(e)

(d)(c)(b)(a)W

eigh

t los

s (

)

Temperature (∘C)


0 100 200 300 400 500 600minus100minus50

050

100150200250300350400450500550600650700

305 330509

Exo

(g)

(f)

(e)

(d)(c)

(b)

(a)

HF

(mw

)

Tg = 184∘C

Tg = 163∘CTg = 204∘C

Tg = 196∘C

Tg = 215∘CTg = 200∘C

Temperature (∘C)



2Cl [19] In


50 100 150 200 250 300 350 400 450 500 550 600

(g)

(f)(e)

(d)(c)

(b)

(a)

dW

dT

Temperature (∘C)

302∘C 328∘C 511∘C










MR Δ119879I = 190ndash325∘C119882I = 2883

Δ119879II = 325ndash420∘C119882II = 2389

Δ119879III = 420ndash550∘C119882III = 4590

MR-EDA Δ119879I = 50ndash250∘C119882I = 64

Δ119879II = 250ndash425∘C119882II = 4579

Δ119879III = 425ndash580∘C119882III = 4607


Δ119879II = 220ndash425∘C119882II = 4760

Δ119879III = 425ndash600∘C119882III = 4350


Δ119879II = 240ndash435∘C119882II = 5233

Δ119879III = 435ndash600∘C119882III = 4063


Δ119879II = 215ndash430∘C119882II = 4329

Δ119879III = 430ndash600∘C119882III = 4633


Δ119879II = 190ndash425∘C119882II = 3510

Δ119879III = 425ndash600∘C119882III = 4620


Δ119879II = 200ndash430∘C119882II = 4513

Δ119879III = 430ndash600∘C119882III = 4756







4 Conclusions





Acknowledgment


References




























CeramicsJournal of







Biomaterials




Journal of


Journal of





CoatingsJournal of

Advances in








MaterialsJournal of


Nano

materials




CH2NH(CH2CH2NH)nH

THF


O OP


3

(NHCH2CH2)n

NHCH2

70∘C


4000 3500 3000 2500 2000 1500 1000 500

16051456

3330

3320

2937

285929383044

1673

1673(d)

(c)

(b)

(a)

696

3332 1673

1265

Tran

smitt

ance

()




31 Characterization



2introduced groups



4000 3500 3000 2500 2000 1500 1000 500

6961670

3329

3340

3317 1076

1076

1221

1221

1030

1030

12211076

1030

(g)

(f)

(e)

Tran

smitt

ance

()








0 100 200 300 400 500 600

0

20

40

60

80

100(g)(f)(e)

(d)(c)(b)(a)W

eigh

t los

s (

)

Temperature (∘C)


0 100 200 300 400 500 600minus100minus50

050

100150200250300350400450500550600650700

305 330509

Exo

(g)

(f)

(e)

(d)(c)

(b)

(a)

HF

(mw

)

Tg = 184∘C

Tg = 163∘CTg = 204∘C

Tg = 196∘C

Tg = 215∘CTg = 200∘C

Temperature (∘C)



2Cl [19] In


50 100 150 200 250 300 350 400 450 500 550 600

(g)

(f)(e)

(d)(c)

(b)

(a)

dW

dT

Temperature (∘C)

302∘C 328∘C 511∘C










MR Δ119879I = 190ndash325∘C119882I = 2883

Δ119879II = 325ndash420∘C119882II = 2389

Δ119879III = 420ndash550∘C119882III = 4590

MR-EDA Δ119879I = 50ndash250∘C119882I = 64

Δ119879II = 250ndash425∘C119882II = 4579

Δ119879III = 425ndash580∘C119882III = 4607


Δ119879II = 220ndash425∘C119882II = 4760

Δ119879III = 425ndash600∘C119882III = 4350


Δ119879II = 240ndash435∘C119882II = 5233

Δ119879III = 435ndash600∘C119882III = 4063


Δ119879II = 215ndash430∘C119882II = 4329

Δ119879III = 430ndash600∘C119882III = 4633


Δ119879II = 190ndash425∘C119882II = 3510

Δ119879III = 425ndash600∘C119882III = 4620


Δ119879II = 200ndash430∘C119882II = 4513

Δ119879III = 430ndash600∘C119882III = 4756







4 Conclusions





Acknowledgment


References




























CeramicsJournal of







Biomaterials




Journal of


Journal of





CoatingsJournal of

Advances in








MaterialsJournal of


Nano

materials




0 100 200 300 400 500 600

0

20

40

60

80

100(g)(f)(e)

(d)(c)(b)(a)W

eigh

t los

s (

)

Temperature (∘C)


0 100 200 300 400 500 600minus100minus50

050

100150200250300350400450500550600650700

305 330509

Exo

(g)

(f)

(e)

(d)(c)

(b)

(a)

HF

(mw

)

Tg = 184∘C

Tg = 163∘CTg = 204∘C

Tg = 196∘C

Tg = 215∘CTg = 200∘C

Temperature (∘C)



2Cl [19] In


50 100 150 200 250 300 350 400 450 500 550 600

(g)

(f)(e)

(d)(c)

(b)

(a)

dW

dT

Temperature (∘C)

302∘C 328∘C 511∘C










MR Δ119879I = 190ndash325∘C119882I = 2883

Δ119879II = 325ndash420∘C119882II = 2389

Δ119879III = 420ndash550∘C119882III = 4590

MR-EDA Δ119879I = 50ndash250∘C119882I = 64

Δ119879II = 250ndash425∘C119882II = 4579

Δ119879III = 425ndash580∘C119882III = 4607


Δ119879II = 220ndash425∘C119882II = 4760

Δ119879III = 425ndash600∘C119882III = 4350


Δ119879II = 240ndash435∘C119882II = 5233

Δ119879III = 435ndash600∘C119882III = 4063


Δ119879II = 215ndash430∘C119882II = 4329

Δ119879III = 430ndash600∘C119882III = 4633


Δ119879II = 190ndash425∘C119882II = 3510

Δ119879III = 425ndash600∘C119882III = 4620


Δ119879II = 200ndash430∘C119882II = 4513

Δ119879III = 430ndash600∘C119882III = 4756







4 Conclusions





Acknowledgment


References




























CeramicsJournal of







Biomaterials




Journal of


Journal of





CoatingsJournal of

Advances in








MaterialsJournal of


Nano

materials






MR Δ119879I = 190ndash325∘C119882I = 2883

Δ119879II = 325ndash420∘C119882II = 2389

Δ119879III = 420ndash550∘C119882III = 4590

MR-EDA Δ119879I = 50ndash250∘C119882I = 64

Δ119879II = 250ndash425∘C119882II = 4579

Δ119879III = 425ndash580∘C119882III = 4607


Δ119879II = 220ndash425∘C119882II = 4760

Δ119879III = 425ndash600∘C119882III = 4350


Δ119879II = 240ndash435∘C119882II = 5233

Δ119879III = 435ndash600∘C119882III = 4063


Δ119879II = 215ndash430∘C119882II = 4329

Δ119879III = 430ndash600∘C119882III = 4633


Δ119879II = 190ndash425∘C119882II = 3510

Δ119879III = 425ndash600∘C119882III = 4620


Δ119879II = 200ndash430∘C119882II = 4513

Δ119879III = 430ndash600∘C119882III = 4756







4 Conclusions





Acknowledgment


References




























CeramicsJournal of







Biomaterials




Journal of


Journal of





CoatingsJournal of

Advances in








MaterialsJournal of


Nano

materials




Acknowledgment


References




























CeramicsJournal of







Biomaterials




Journal of


Journal of





CoatingsJournal of

Advances in








MaterialsJournal of


Nano

materials










CeramicsJournal of







Biomaterials




Journal of


Journal of





CoatingsJournal of

Advances in








MaterialsJournal of


Nano

materials



research article aminoalkylated merrifield resins...

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