REFERENCES

Adelz.E.S, Ashraf.A.E.B, Mostafa.A.D, Mohamad.A.E.E, and Sami.A.M., Polym Degradn. and Stability., (1993), 42, 1-1 1.

Agarwal.H, and Chandra.S., Indian Joumal of Chemistry., (2004), 43A, 2361-2364.

Aganval.M, Bennett.R.B, Stump.I.G, and D'Auria.J.M.,Anal Chem., (1975), 47,924.

Akaiwa.H and Kawamoto.H., Rev.Anak.Chem., (1982), 6,65.

Ange1ici.R.J and Hopgood.D., J.Am.Chem. Soc., (1968), 90, 25 14- 25 17.

Arafa.1, El-Ghanem.H and Al-Shalapi.R., J.Inorg and Organometallic Polymer.,(2003), 13,69.

Astheimer.L, Schenk.H.J, Whi1te.E.G and Schwochan. K., Sep. Sci Technol., (1983), 18,307.

Aswar.A.S, Bansod.A.D, Aswa1e.S.R and Mandik.P.R., Indian Journal of Chemistry., (2004), 43A, 1892- 1896.

Atsushi Sugh, 0gawa.N and Hashizurne.H., Talanta., (1979), 26,189- 192.

Bajpai.U.D.N, Rai.S, and Bajpai.A., Polym Int., (1993), 32,215-20.

Balasubramaniam.K.P, Karvembu.R, Chinnasamy.V and Natarajan K., Indian Journal of Chemistry., (2005), 44A, 2450-2454.

Bmazak.J.L, Wats0n.H.C and Kendrew.J.C., J.Mol.Biol., (1 965), 2,130-7.

Banerjee.D, Mondal.B.C, Das.D and Das.A.K.,Microchim.Acta., (2003), 141,107.

Bmk.E, 0kamato.Y and Veha.Y., J.Polym. Sci., (1980), 25,35948,

Bao.Y.T, and Pitt.C.G., J Polym Sci A: Polyrn Chem Ed., (1990), 28, 741-58.

Barbucci.R and Campbell.M.J.M., Inorganica Chemica Acta., (1976), 16,113-120.

Basita.T.K, Lenka.S and Nayak.P.L., Macromol.Rep A., (1994), 31,5361.

Bilba.D, Bejan.D and Tofan.l., Croatica Chimica Acta., (1998), 71(1), 155-178.

Bisset.W, Jacobs.H, Koshti.N, Stark. P and Gopalan.A., Reactive and Functional Polymers., (2003), 55, 109-1 19.

Biswas.M, and Mukherjee. A., J. Appl. Polyrn. Sci., (1995), 56,501- 8.

Bolto.B.A., J.Macromol.Sci. Chem A,, (1980), 14,107-12.

Bondar.Y, Kim.H.J, Y0on.S.H and Lim.Y.J, Reactive and Functional Polymers., (2004), 58,2313-2321.

Breslow.R, and Overman. L.E., J.Am.Chem.Soc., (1970), 92,1075-7.

Busev.A.1, Tiptsova.V.G, and 1vanov.V.M. Moscow Mir., (1981),105. (Translated from Russian by Alexander Rosikin).

Cao. S.K, Huang. M.Y, and Jiang Y.X. J Macmmol.Sci. Chem A., (1989), 26,381-9.

Capaka.M, Svoboda.P, and Heltlej's., Tetrahedron Len., (1971), 4787.

Card.R.J, Liesner.C.E, and Nekers.D.C., J.Org Chm., (1979), 44, 729-34.

Chattopadhyay.P, Sinha.C, and Pal Fresenius.D.K, J.Anal.Chm., (1997), 357,368.

Chauhan.G.S, Kumar.S, Kurnari.A and Sharma.R., J. Applied Polymer Science, (2003), 90,3856-3871.

Coleman.A.K., New concepts in the handling of industrial wastes. Chem Ind., (1975), 5 , 5 3 4 4 .

C0lman.P M, Freeman.H.C, Guss.J.M, Murata.M, Nonis.V.A, Ramshaw J A M , and Venkatappa.M.P., Nature., (1978). 275319% 324.

Damasceno.J, Gomes. C.A.T, Reiurnont. J, Sanchez.R., Materials Research., (2002), 5,2201-204.

Das.D, Das. A.K, and Sinha.C., Talanta., (1999), 48, 1013.

Das.D, Dinda.J, Mondal T.K, Sarcat.K.K and Sinha.C., J.Indian Chem.Soc., (2006), 83,861.

Davankov.V.A, and Rogozhin.S.V., J Chromatogr., (1974), 60, 280- 3.

Davies .R.V, Kennedy.J, Lane.E.S. and Willirams.J.L., Appl.Chem., (1959), 9,368.

Dev.K and Rao G.N., Talanta.,(1996), 43,45 1.

Dev.K and Rao G.N.,Analyst.,(l995), 120,2509.

Dev.K and Rao.G.N., Talanta.,(l995a), 42, 591

Dewar.M.J.S, and Talati.A.M., J.Arn.Chern. Soc., (1964), 86,1592- 1595.

Dey .R.K, Acharya.S, Sama1.S. and Ray.A.R., Indian J.of Chemical Technology (2004). 11,695-703.

Donaruma.L.G, Kitoh.S, Walswork.G, Depinto.J.V, and Edzwald.J.K., Macromolecules., (1979), 12,435-8.

Ebraheem. K.A.K and Hamdi.S.T., Reactive and Functional Polymers., (1997), 34, 5-10.

Eisenberg. A, and King.M., Academic Press, Inc., New York, (1977), 2,45.

Figgis. B.N., Introduction to ligand fields,Wiley Interscience, Newyork., (1962), 25.

Flcming.C.A, and Nicol.M.J., Proc Hydrometallurgy., (1981), 81, 1.

F0rd.W.C and Balakrishnan.T., Macmmolecules., (1981), 14,284.

Freedman.H.H., J.Am.Chem. Soc.,(1961), 83,2900-2905.

Fumiss.B.R, Hannaf0rd.A.J. Smith P.W and Tatchell.A.R.,(1994), 'Vogel's textbook of practical organic chemistry' ,Fifth edition, ELBS, London.

Ganeshpure P.A, Satish.S, and Sivaram.S., J Mol Catal., (1989), 5O:Ll-L5.

Garg.C.L,Narasimhan.K.V and Tripathi B.N., J.Inorg.Nucl.Chem., (1971), 33,387-392.

Gh0sh.J.P andDas.H.R., Talnanta., (1981), 28, 274.

Gigy Abraham and Purushothaman.E., Indian J.of Chemical Technology., (2003), 10,175-1 79.

Gitzel.J, Ohno.H, and Tsuchida.E., Polymer., (1986), 27,1781-7.

Gomez.E, Freer.J and Bae2a.J. Bol. Soc. Chil. Quim., (1982), 27, 188-90.

Greger.H.P, Luttinger.L.B, and Leol.E.M., J.Phys Chem.,(1955), 59, 34.

Gmbbs.R.H, and Kroll.L.C., J Am Chem Soc., (1971), 93,3062.

Gupta.K.C, Abdul Kadir.H.K and Chand.S., J.of Macromolecular Science Pure and Applied Chemistry., (2003), 40,475-500.

Gurnule.W.B, Juneja H.D and Paliwal.L.J.,Reactive and Functional Polymers., (2002), 50, 95-100.

Gumule.W.B, Rahangdale.P.K, Paliwal L.J, and Kharat R.B., Reactive and Functional Polymers., (2003), 55,255-265.

Gumule.W.B, Rahangdale P.K, Paliwal L.J, and Kharat R.B, J.Applied Polymer Science., (2003a), 89,787-790.

~ u s t a f s o n . ~ . ~ and Lirio.J.A., J.of Physical Chemistry., (1968),72, 5.

Hirai.H, and Nakamura.Y., Chem Lett., (1974),4,809-14.

Hi1ai.Y and Nakajima.T., J. Applied Polymer Science., (1989), 37, 2275-228 1.

Hodgkin.J, and Eibl. R., React.Polym. Ion Exchange sorbents , (1985), 3,78-93..

Hojo.N, Shirai.H, Chijo.Y, and Hayashi S., J.Polym.Sci. Polym.Chem Ed., (1978), 16,447-55.

Honda. K, Chiba.K, and Hayashi.H., J Macromol Sci Chcm A.,(1989), 26,609-20

Huang Chuch-Jung, Yen Chiah-Chao, and Chang Teh-Chou., J.Appl. Polym.Sci., (1991), 42,2267-77.

Huang.W, Ho.P, and Huaxue Tangbao., (1981), 32,783-843.(CA. 97: 22951r)

Iolinda Aielo, Ghendini.M and Zanchini.C., Inorganica Chimica Acta., (1997), 255,133-137.

Ismail.A.J, Ebraheem.K.A.K, Mubarak.M.S, and Khalili.F.I., Solvent extraction and ion exchange.,( 2003),21,issuel.

Jaffery.G.H, Basselt.J, Mendham.J, and Dennery.R.C.,1994,Vogel"s Text book of quantitative Chemical analysis, Fifth edition, ELBS, London.

Jones. K.C and Grinstead.R.R., Chem Ind., (1977), 637.

Jorgensen. C., Absorption spectra and chemical bonding in complexes, Pergamon press, Oxford, (1962), 15.

Jose.J, J0hn.M and Mathew.B., J.of Macromolecular Science Pure and Applied chemistry., (2003), 40, 863-879.

Joshi.J.D, Patel N.B. and Patel. S.D., Iranian Polymer Journal, (2006), 15(3), 219-226.

Kaliyappan .T and Kannan.P.,Prog. Polym. Sci., (2000), 25,343-370.

Kaliyappan .T, Swaminathan C.S and Kannan.P., Eur.Polym. J.,(1996a), 33, 59-65

Kaliyappan.T, and Kannan.P., J Polym. Sci part A., (1996), 60,947- 53.

K a 1 i ~ w a n . T ~ Anupriya.R, and Kannan.P., Makromol Chem Pun Appl Sci., (19991, A36(4), 517-30.

G1iya~pan.T~ bnnan.P, and Reddy.A.V.R., Polym.Mater., (1994), 11,121-128.

Kaliyappan.T, Rajagopan.& Science., (2003), 90,2083.

and Applied Polymer

Gliyappan.T, Swarninathan C.S, and Kannan.P., Polymer., (1996b), 37,2865-9.

Kellerman.R., Spectroscopy in heterogeneous catalysis, Academic press., (1979), 86.

Kimura.K, Zhuag. J.H, Kida.M, Yamashina. Y, and Sakaguchi. Y., Polymer ., (2003), 35,(5), 455-459.

Kortum.S., 1969,"Reflectance spectroscopy" Springer-verlag,Berlin.

Koster.G, and Schmuckler.G., Anal.Chem. Acta., (1967), 38, 179.

Kratz.M.R, and Hendricker.A., Polymer.,(1986), 27,1641-3.

Kumar.D, Syamal.A, and Gupta.P.K., J.of Indian Chem.Soc., (2003), 89. 3-6.

Kumar.M, Rathore.D.P.S, and Singh.A.K., Analyst,(2000), 125,1221.

Kumaresan.S and Kannan.P., Indian J.of Chern,Tech.,(2003), 10,180- 185.

Kurirnara.Y, Tsuchida.E, and Kaneko.M.J., J.Polym. Sci.Polym. Chem Ed A., (1971),19,3511-9

Kunmura.Y,Yarnada.K, Kanek0.M and Tsuchida.E J.of Polymer SciencepartA-l., (1971), 9,3521-3527.

Lautsch.W, Broswer.W, Biedemann.W, and Gnichtel.H., J.Polym.Sci.,(l955),17,479-510.

Lee.T.S, and Hong.S.I., J Polym Sci Polym Chern Ed.,(1995), 33, 203-10.

Lei.Z, and Wang.Y., Macromol. Rep A.,(1993), 30,233-9.

L e k M . A , Morecellet.J, and MorecelletM., J.Polym Sci. Polym.Chem Ed., (1987),25,223 1-40.

Li Y. Gaofenzi Xuebao. C.A., (1988), 109,7023.

Maeng. K.S, S0ng.H.Y and Back.J.K. NonmunjipChungham Taehekkyo Kongop Kyuk Yonsguso.C.A.(1985), 106,19137d

Mang .X, Natansolin. A and Rochon.P., Supra Molecular Science.,(l996), 3 (4),207- 213.

Mani.R, Mahadevan.V, and Srinivasan.M., British Polm.J.,(1990), 22,177-184.

Mani.R, Mahadevan.V, and Srinivasan.M., J.Macromol. Sci, Pure Appl Chem A,, (1993), 30,55769.

Marciniec.B, Urbaniak.W and Pawlak., J Mol Cata1.,(1982),14,323- 31.

Marcu.M, Cazacu.M, Viad.A., Racels.C., Applied Organomctallic Chemistry., (2003),17,693-700.

Mart.H, and Vilayetoglu. A.R., Polymer Degradation and Stability., (2004), 83,255-258.

Mathur.N.K, Narang.C.K, and Williams.R.E., Polymers as Aids in Organic Chemistry. New York: Academic Press., 1980.

Mauritz.K.A, Hora.C.J, and Hopfinger.A.J.,Adv Chem Ser., (1980),187,123.

Mendez .R, and Pillai.V.N.S, Analyst., (1990),11,213.

Michalska.Z.M, and Ostazewski.B., J.Organomet Chem., (1986), 299, 259-69.

Mishra.A.P, Tiwari.V.K and Singhai.R., Indian J. of Chemistry, (2002), 41A, 2092-2095.

M0hapatra.B.B and Saraf.S.K., J.Indian chem.Soc., ( 2003), 80, 696- 699.

[115] Mondal .B.C, Das.D, and Das.A.K., Anal.Chim.Acta.,(2001), 450,223.

Mondal.R.C, Das.A.K., Indian Journal of Chemistry.,(2002), 41A,1821-1825.

Mondal.B.C, Das.D, and Das.A.K., Talanta., (2002), 56,145.

Moriguchi.Y., Bull. Chem. Soc. Jpn.,(l966),39,2656-65.

Murakami.Y, Suzuki.T, Takegami.Y., Polym J (Tokyo)., (1985), 17,855-61.

Nakajima.A.N, Sakai.J, and Yamauchi., J. Applied Polymer Science., (2006), 102,5372-77..

Nanjundan.S, Unnithan.C.S, Selvakumar.C.S.J, and Penlidis.A., Reactive and Functional Polymers.,(2005), 62, 11-24.

Nather.C, Greve.J, and Jeb.1. Z.,Naturoforch., (2003), 58b, 1-7.

Nayak.S.D, Mahadevan.V and Srinivasan.M., J., Cata1.,(1985) 92,327-39.

Nishikawa.H and Yanada.S.,Bull. Chem. Soc. Japan., (1964), 37, 8- 12.

Noboru.K, Yukihiko.U, Koji.Y.1, and Yoshiro.S., Polymer, (1986), 27,293-8.

Nose.Y, Hatano.M, and Kambara.S., Makromol Chem., (1966), 98, 136-47.

Nozawa.T, Akimoto.Y, and Hatano.M., Makromol Chem., (19721, 158,214.

Nozawa.T, and Hatano.M., Makromol Chem., (1971), 141,31-41.

Nozawa.T, Hatano.M, Yansamot0.T and Kambura.S., Makromol Chem.,(1968),115,10-6.

Okamato.Y, Veba.Y, Dzanibekov.N, and Banks.E., Macromolecules., (1981), 14, 17-22.

Osada., Makromol Chem., (1975), 176, 1893-6.

Palumbo.M, Cosani.A, Terbojerich.M., Peggion. Macromolecules., (1978), 11,1271-5.

Palumbo.M, Cosani.A, Terbojevich.M, and Peggion., Macromolecules., (1978), 10,813-20.

Pan.C, Zhao.Y, Chen.Y. Zhongguo Kexue Jishu Daxuve Xuebao., (1985), 15(4), 439-46 (CA. 105: 208287t).

Pan.H.K, Yarusso.D.J, Knapp.G.S, and Copper.S.L.,J.Pol ym.Sci. Polym. Phys. Ed., (1982) 21,1389.

Pardeshi.P.K, Pa1askar.N.G and Choudhekar.T.K., J. of Indian Chemical Society (2002), 79,958-959.

Pa1rish.J.R and Stevenson.R., Analytica Chimica Acts., (1975), 70,189-198.

Patel S.A, Shah.B.S, Patel.R.M, and Patel. P.M., Iranian Polymer Journal., (2004), 13(6), 445-453.

Patel.B.K, and Patel.M.M., Indian J. Chem., (1990), 29A, 90-92.

Patel.D.K, Patel.C.G, and Parmer.J.S., Macromol Rep A., (1994), 31.297-301.

Pecht.1, Levitzk.A and Anbar.M., J. Am. Chem. Soc., (1967), 39, 1587.

Penin.D.D and Armarigo W.L.F, (1988)'Purification of laboratory chemicals' Pergamon press, New York.

Phi1ips.J and Fritz.J.S., Anal.Chim.Acta., (1980),121,225.

Pittman Jr. C.V and Hiro.R., J Org Chem., ( 1978), 43,640-3.

Pittman Jr. C.V and Martin.G.V., J. Polym Sci A, Polym Chcm Ed., (1973), 11,2753-65.

Piitman Jr. C.V, Veges.R.L, and Jones.W., Macromolecules., (1971) 4,291-7.

Pittman Jr. C.V, Veges.R.L, Jones.W, and Elder.J., Macromolecules., (1971) 4,302-8.

Pittman. C., Organometallic reactions,Plmum press,Newyork., (1977) 6,36.

Pomerantseva.M.G, Belyakova. Z.V, Shchepinov.S.A, Efimova.L.A, Chemyshev., Zh Obshch Khim., 1984,54(2), 3 5 4 6 (CA.IO1,7258c).

Pratik.E.P.Michae1, Barbe.J.M, Juneja.H.D, and Paliwa1.L.J. Eur. Polym.J.,(2007), 43,4995-5000.

Rakesh K.Sharma., Pure.Appl.Chern., (2001), 73,(1), 181-186.

Ramirez.R.S, and Andrade.J.D.,Polym Prcpr Am Chem Soc, Div Polym Chem.,(1974), 15,391-4.

Ravikumar Reddy.A and Hussain Reddy.K., Proc.Indian Acad.Sci.Chem.Sci.,(2003), 115, (3), 155-160.

Reddy.K.H, Babu.M.S, Babu.P.S. and Dayanand.%, Indian Journal of Chemistry., (2004), 43A, 1233-1238.

Rivas.B.L, and Segue]. G.V., Polymer Bulletin., (2001), 46,271-276.

Rivas.B.L, and Villegas.S., J.Applied Polymer Science., (2003), 90, 3556-3562.

Rivas.B.L, Periera.E.D, and Villoslada.I.M.,Prog.Polym.Sci., (2003), 28,173-208.

Rivas.B.L, Seguel.G.V, and Ancatripai.C., Polymer Bulletin.,(2000), 44,445-452.

Robert B.Jeppsen , Ph.D Thesis.(1999).

Roy P.K, Rawat.A.S, Choudhary.V, and Rai.P.K., J. Applied Polymer Science., (2004), 94,1771-1 779.

Rudolf.P.R, Saldaniaga.C.H, and Clearfield.A., J.Phys.Chem.,(l986), 90,6122-25

[I631 Sadhan Pramanik.P, Dhara.K, and Chattopadhyay.P., Talanta., (2004), 63, 485-490

Saha.B, Iglesias. M, and Strent. M., Solvent Extr.1on Exch., (2000), 18.133.

Salem.N.M, Ebraheem. K.A.K, and Mubarak.M.S.,Reactive and Functional Polymers., (2004), 59,63-69.

Salih.B., J. Applied Polymer Science., (2002), 83, 1406-1414.

Samal.S, Acharya.S, Dey.R.K, and Ray.A.R., Talanta., (2002), 57, 1075-1083. - Samal.S, Mohapatra.N.K, Achariya.S, and Dey.R.K., Reactive and Functional Polymers., (1999), 42,37-52.

Samudranilpal, Proc.Indian Acad.Sci.Chem.Sci.,(2002), 114, (4), 417-430.

Samuelson.O., Ion exchange separations in analytical chernistq. New York: Wiley., 1963.

Sangb ganguly., J.of Indian Chem.Soc., (2004), 81,327-329.

Sankar.R, Vijaya1akshmi.S Subramanian.S, Rajagopan.S and Kaliyappan. T., Eur.Polym. J., (2007), 43,4639-4646.

Sankar.R, Vijaya1akshmi.S Subramanian.S, Rajag0pan.S and Kaliyappan. T., I. Appl Polym Sci., (2008), (in press).

Sasaki.T.,Bull Chem Soc Japan., (1968), 14,24406.

Saxena.R, Singh A.K and Sambi.S.S., Anal.Chim.Acta.,(l994), 295, 199.

Saxena.R, Singh.A.K, and Rathore.D.P.S., Analyst., (1995), 120, 2509.

Schmuckler.G., Talanta., (1965), 12,281-90.

Sevindir.H.C, and Mirzaoglu.R., Macromol Rep A., (1994), 31, 399- 410.

Sharpe A.G. The chemistry of cyano complexes of the transition metals. New York: Academic Press., (1976) (275pp.).

Siddhanta.S, and Das.H.R., Indian J. Chem, Sect A.,(1984), 23,937.

[I811 Sigel.H, and Baukcr.S., Helv Chim Acta., (1968), 51(6), 1246-56.

Singh.D.K and Gupta.K., J.Indian Chem.Soc.,(2002), 79,447.

Sinner.F, Buchmieser.M.R, Tessadri.R, Mupa.M,Wurst.K and Bonn., J.Am.Chem.Soc., (1998), 120,2790.

Siyam.T and Hanna.E., Macromol Rep A.,(1994), 31,349-56.

Stempel .G.H, Gross R.P. and Mariella., J.Am.Chem.Soc., (1950), 72, 2299.

Styra-Brajte1.K and Zeotorzynska.E., Fresenius Z., haLChem., (1987), 112,315

Sugii.A, Ogawa. N and Hashizume.M., Chem.Pharm.Bull., (1978), 26,798.

Sugii.A, 0gawa.N and Hashizume. H., Talanta., (1980), 27,627.

Teranishi.T, Harada.M, Asakura.K, Asanuma.H, Saito.Y, and Toshima.N., J Phys Chem., (1994), 98,7967-75

Tewari.P.K and Singh A.K Talanta.,(2000), 53,823.

Tewari.P.K and.Singh.A.K , Fresenius., J.hal.Chim.,(2000), 367, 562.

Tham~zharasi. S, and Venkata Rami Reddy. A, Balasubramanian. S, Reactive & Functional Polymers, (1999), 40,143-153.

Thamizharasi.S, and Venkata Rami Reddy. A., Polymer., (1992), 33, 2421-3.

T0mic.E.A and Carnpbell.A., J.Polym. Sci., (1962), 62,379-386.

Tsuchida.E, and Nishide.H., ACS Symp.Ser., (1980), 121,147-163.

Tsuchida.E, Tomono.T, and Honda.K., J Polym Sci A Polyrn Chem Ed., (1974), 12,1243-55.

T8uchida.E. and Nishide.H., Advances in Polymer science., (1977), 24,59-73.

Vadolkar.V.B, Tembe.G.L, Ravindranathan.M, Rarn.R.N and Rama.H.S., J.of Macromolecular Science Pure and Applied Chemistry partA,(2004), Vol-A, 7839-858.

Vallcc.B.L, and Ri0ndan.J.F. In: Li CH, Editor. Proceedings of the International Symposium on Proteins. New York:Academic Press., (1978), p. 23-7.

Van Berkel.P.M, Driessen.W.L, Kodhaas.GJAK, Reedijik.J, and Shcrington.D.C., J Chem Soc, Chem.Commun., (1995), 2,147-8.

C

Van Dyke C.K, and Farrell.M.0, Baucher.L.L., Fundam.Res Homogenous Cata1.,(1979), 3,659-69.

Veno.K, and Martell.A.E., J.Phys.Chem.,(l953), 60, 1270-1275.

Vernon.F, and Shah.T., React Polym.,(1983), 1,301.

Vernon.F., Anal Chem Acta., (1976), 87,491-3.

Vemon.L.P, and Seely.G.R., The Chlorophylls., New York: Academic Press, 1966.

Vijayalakshmi.S, Sankar.R, Subramanian.S, Rajagopan .S and Kaliyappan. T., Designed Monomers and Polymers.,(2006), 9, (5),425-437.

Vijayalakshmi.S, Sankar.R, Subramanian.S, Rajag0pan.S and Kaliyappan. T., J. Appl. Polym.Sci., (2007), 104,797-802.

Vijayalakshmi.S, Subramanian.S, Rajagopan3 and Kaliyappan.T., J. Appl Polym Sci., (2006a),101,1506-1510.

Vijayalakshmi.S, SubrarnanianS, Rajag0pan.S. and Kaliyappan.T., J.Appl. Polym.Sci, (2006), 99, 1516-1522 .

Washawsky.A, Firberg.M.B, and Ras.Y.B., Purif Meth., (1980), 9, 209.

Welch.R.C.W, and Rase.H.F., Ind Eng Chem Fundam., (1969), 8, 389-97.

Wu.K.H, Chang.T.C, Wang.Y.T, H0ng.Y.S and Wu.T.S., Eur. Polym.J., (2003), 39,239-245.

[214] Xiansen. Z, Hongzhi. Z, Xinde.F., Gaofenzi Tongxum., (1983),5,375-80 (CA. 100: 176217~).

[215] Xiao.C, Lin.Y, Luo.C,Tian.Z., Wuhan Daxue Xuebao Ziran Kexueban., (1989), 1,81-86 (CA. 110: 231731~).

[216] Zakrzewska-Trmade1.G and Harasimoviez.M., Desalination., (2002), 144,207-212.

[217] Zundel.G, Hydration and intermolecular interaction ipfiared investigations i

with polyelectrolyte membranes Academic Press, Inc., New York. (1969).

LIST OF PUBLICATIONS

1. Studies on Poly(8-hydroxy-4azoquinolinephenyImethacqhte) and its metal complexes, S. Vijayalakshmi, S. Subrarnanian, 3. Rajagopan, and T. Kaliyappan, Journal of Applied Polymer Science, Vol. 99, 15 16-1 522 (2006)

2. Studies of Poly(8-hydroxy-4-azoquinolinephenol-formaldehyde) and its metal complexes, S. Vijayalakshmi, S. Subrarnanian, S. Rajagopan, and T. Kaliyappan Journal of AppliedPolymerScience,Vol. 10 1,1506- 15 1 O(2006)

3. Studies on Poly(8-hydroxy-4azoquinolinephenylacryle) and its metal complexes, S. Vijayalakshmi, R. Sankar, S. Subramanian, S. Rajagopan, and T. Kaliyappan, Designed monomers and polymers Vol. 9 No.5, 425-437,(2006).

4. Synthesis and metal uptake studies poly(8-hydroxy-5-azoquinoline phenylacrylate- formaldehyde) resin and its metal complexes., S. Vijayalakshmi, R. Sankar, S. Subramanian, S. Rajagopan, and T. Kaliyappan Journal of Applied Polymer Science, Vol. 104, 797-802 (2007).

5. Synthesis and chelation properties of new polymeric ligand derived from p l y ( 8-hydroxy-5-azoquinoline hydroxy benzene), S. Vijayalakshmi, R. Sankar, S. Subramanian, S. Rajagopan, and T. Kaliyappan, European polymer journal 43,2007,4639-4646.

Studies on Pol (8-h droxy-4- azoquinolinep K eny l methacrylate) and its Metal Complexes

5 Vijayalakshmi, S. Subramanian, S. Rajagopan, T. Kaliyappan

@tportmmt of Chmrsty, Pond~chmy Enpneenng College, Podlchery -605014, lndu

~rirlved IY July 2U03, accepted 4 Februaty 2Kl5 lhll 10 lW2/appZWI puhl~shed odme m Why IntAence (www mtersnence wdey cam)

ABSTRACT &Hydroxy-4-azoquulohephenyLmetha"yl ate (RHIAQPMA) was prepared and polym~nzed m ethyl melhyl ketone (EMK) at 65'C usmg bmzoyl peroude as lrre rad~cal uubtor Poly(8hydroxy-4-azoq~~1loI1nephenyl~ methacrylate) poly(BH4AQPMA) was charadenred by m hared and nuclear magnehc rmnance techquen The rnrr lvrdar waght of the polymer was detmnmed by gel per mrahon chromatography Cu(I1) and Nl(n) mrnplexes of ?dy(8H4AQPMA) were prepared Elementnl analy~ir of

INTRODUCTION

In recent years, polymer metal complexes gamed con- ,~derable mterest owmg to the11 amachve appllcahons In dlvers~hed helds, such as catalys~, extrachon of metals mcludmg rad~oachve elements, and blrrmor yanic chemistry water and waste water treatmentst-* The complexahon of metal Ions w ~ t h polymer matnces tin taming f u n c h o ~ l l~gands results In supenor prop rrhes compared w ~ t h the sunple compound counter- parts Orgmc polymers when complexed w ~ t h mor- xamc metals unpart 5ex1brhty due to the orgaruc mop rw and stab~ltty due to morgaruc funcbons The chelate forrnlng polymeric I~gands, charactenzed by reactwe funchonal groups contammg 0, N, and S donor atoms and capable of m o r h h n g to different mehl luns, have been extensively studled "" AW later, methacrylates, and thetr >orrespondmg and :hlor~des are vmyl monomers that are read~ly con- rerted to lunchonal monomers, and rad~cal polymer- izahon m suitable salvenb was found to be effechve for a metal- on scavenger Oxme w extens~vely w d m analyhcal chemwhy as a photometric agent and/or extrachon agent h e ~s a selechve and has conse- quently attracted great mterest as a potenhal chelator for h e metelitc ~ o n s Separahon of translhon metal Ions on vanous o m e chelabng m m , mcludmg com- meroal oune, was reported by Pamsh and col-

po.vc\e.arrs suggss ha1 h e mlal.hgand raho ~r. abou~ 1 ? f ie pltcnr.ate xtrr hrIncr chrac laud 3) uhared speara. X-ray dlfhacbm, spearal studies, andmagnetlc moments Thermal anaiy~es of the polymer and plychelates were camed out m au 0 ZWs Wdey Perlod~olr hc 1 Appl Polp B 59 1516-1522,ZW

Key words Ion exchangers, metal-polymer mmplexer, rad- leal polymenzahon

Conrspnhu to T Kahyappan (tkaByappan2MlB yahw mm)

leagues1213 Oune groups bound to polymers via car- bon-carbon bonds prepared by FnedelXrafk alkyla- hon of Amberl~te XE-305 wlth Echloromethyl-8 hydroxyqlunolme have led to hydrophob~c resm of low capaclty Thne materials a h eexh~b~t amazmg shudural vanahons A hydrophlltc oune resm with enhdnced copper Ion exchange capacity has teen syn- thesued from alkylated poly(benzylarmne) and Moromethyl-&hydroxyqwnohe " The elech.omc and EPR stud~es on Spheron-1WO shows a 2 1 mol raho for NI(U) and Co(I1) complexes In continuanon of our research m polymer-metal c o m p l e x e ~ , ' ~ ' ~ the present mveshgahon deals w t h the synthesis, charac- tenzahon and thermal property of new poly(&hy- droxy4azoqumohnephenylmethacryhte) and ~ t s Cu(ll) and NI(II) complexes

EXPERIMENTAL

Materials

&hydroxy4-azoqumoLnehydroxyUe was pre- p a d accordmg to Mang and coworkers " Benzoyl per- onde was reay5 t .d~d from a chlomform-&ol mixture Methacrylay1 chlonde was prepared by a re ported procedwle

Monomer synthea~s

Gf L~20'~roq,",%e42~ and 2-butanone 25 mL were placed m a tluee necked

4 d ~ p p l i d polymn -. vol 9. ,516-I= (m, fllpk h t t d w ~ t h a snrrer, thermometer, and v r a h n g P ~ W ~ ~ o m c r l k ~ h e l 7he contents m the flask were cooled tu -?C

hlethactyloylchlondc (1 8 mL. O OW) In 20 mL of 8-hydroxy-4-aroqumolmephenyhethac'ylate [poly- : butanone was added dropwlse w ~ t h constant stir- (8H4AQPMA)I was hltered, washed wlth methanol, r~ng and c m h g The reachon muture was gradually and dned (Yleld 85% ) ~llowed to reach room temperature, and shrnng was ~ontlnued for 2h The quaternary ammonium salt formed was then hltered off The hltnte was washed P"puahon Of

i ~ t h d~shlled water and d n d overanhydroussodlum wiiatt. and the solvent was evaporated In wcuo (veld Y i o e ) The LR and 'H NMR spectra were conskent w~th the ass~gned shucture (Scheme 1)

shydruxy-4-azoqumohephenyImethacrylate (3 5M) In DMF (10 mL) and benzoyl perowde (05g) were placed m a standard reamon tube and deaerated by passmg oxygen free iuhogen gas for 30 mm The reacten tube was closed and kept m a thermostat at 65" for 8h ' h e contents were then cooled and pouted over methanol (100 mL) Thepreap~tated poly

The polymer (6 Gmmol of repeat un~t) was h l v e d m 30 mL of DMF An aqueous solubon of Cu(ll)/ Nl(11) 0 62g acetate was added dropwlse wlth constant shmng, and the pH of the mtuhon was adjusted to 7 wlth d~lute ammonium hydroude soluhon The re- sulhng muture was d~gested m a water bath for 2h and kept overn~ght at room temperature The p m p ltated ~~I~(BH~AQPMA)CU(U)INI(U) complex was fdtered, washed with hot &hiled water, and d n d

The IR spectra of the polymer and polymer metal complexes were recorded usmg KBr pellets The IH

TABLE l UemrnW Analyois far Poly 18HhAQPMAI and 16 Metal Complcxca

Elemental analyr~s lwaght pemnt)

Carbun Hydrop Oxy~en Nlhugen Metal ----- Abbmrhon h p u d fmula Cal' Fd Cal' Fd W a Fd Cal' Fd W a Fd

- - , "~alcukted pemntlp of C, H, N, 0, and metal lorn for polymer-metal mmplexer b a d on the value of x = y = 2 W

a - 2 a, y I 2 01.

Figure 1 IR specha of poly(~H4AQPMAl (a), poly(SH4AQPMA)-Cu (U) (b) , and poly(BH4AQPMAt NI(II) (r).

NMR s p of the polymers were recorded on a IFOL GSX 400 MHz spectrometer in DMSO d, uslng !etramethyKie as the internal standard Molecular n'e~ghts (M., and M,) of the polymers were kkr- mlned by GFC (Water's model 410) using THF as eluent Elemental analyses were performed on a Coleman CHN analyzer. The metal content of poly- mer metal complexes was determined usmg the titr- metnc procedure after dwpmposing the polychelates h v l concentrated HCI, perchloric, HNO, and H,SO,. The vrscosity measurements were made in THF at O"C with an Ubbelohde suspended level viscometer.

The magnetic moments were measured using the h a y method. The diffuse reflectance spcha (500- 2WOnm) were measured on a Varian Car). 5E W-vis

NU( s p p h o t o m e t e r . X-ray &adon experimentr were performed with a Phillp PWlBZO diffractom- eter. Therrnogravirnetnc analysis (TGA) was carried out in a Seiko thermal m1yser. A hng sample was used at a heatng rate of 15'C min-' in air.

RESULTS AND DISCUSSION

The monomer (I) was prepared and polperked in DMF using benroyl peroxide as initiator with a good yleld Polymer metal complexes were obtained in a DMF containing polymer in an aqueous solution of metal ions Cu(II) and NiO in the presence of a few drops of ammonia. The polymers were soluble in DMF, THF, and DMSO, and insoluble in common

TABLE I1 1R Specin1 Dala of PoIy(BH4AQPMAI md Ik Metal Cornplexn

- b p k OH, C-hnr., N-N, Phenok C - 0 Esferic C-0, &N,

I b L 1 0 6 ppm

Fiyn 2 'H NMR spchum of poly(KH4AQPMA)

urganic solvents like benzene, toluene, methanol, and uter All the plychelates are sparingly soluble in THF and DMF The elemental analysis data for p l y - mers and polymer-metal complexes are presented m lahle I The elemental analyse data suggest that the metal to polymer ratio is 1 : 2. The intrinsic \,iscosity

detemed to be O.SldL/g. The number average molecular weight (M,,) atld

wght average moleqlar weight (M,,.) of the wly(BH4AQPMA) were determined by gel perme JhOn chromatography using tetrahydrofuran (M, 1 76 y 10' M,, = 3.94 x 10'). The plydispers~ty urdex M,,,/M,, for poly(BH4AQPMA) is 2.16. The theoreti- cal !,slue of M,/M, for poly(BH4AQPMA) suggests a strong tendency for chain terminahon by radical re- combmation.

The IR s p a of poly(BH4AQPMA) and its p l y - chelates are shown in Flgure 1. The absorption band War 333W cm-' wrresponds to phenolic -OH stretch- log. Ths band disappears in the spectra of the metal complex, estabkhing the involvement of phenolic -OH in the coordination polymer. Ni(U) polychelaks

a slmng band at a higher frequency region (3400 "'I) than that assigned for the phenolic -OH group. fie fad that hnd rwnah even when the poly-

mer metal complex was heated up to 150aC suggesk the coardinahon of H,O molecules to N1(11) polyche- lates. The strong bands at 1750 on-' and 1570 GI-' may be ascribed to C-0 ester and ketomc groups, respechvely. The medum intensity band at 1190 cm-' m the speckurn of the polymer is due to the hydrogen bonded m g system of the ligand. The band around 725 cm-' corresponds to metal-oxygen vibration. The other absorptions observed are presented m Table U. The 'H NMR spedrum of ply(8H4AQPMA) is shown m F~gure 2. SignaL due to aromatic protons appear as broad multiples in the region 8.11-6.236. The s~gnals at 9 126 are due to aromatic -OH. The signals around 3.9-2.016 are due to methylene and methyl protons.

The relationship between the elechonic properties of the metal ion in the complex and the sterwchems- try of the hgand in the environment present was ar- rived at tentatively on the basisof the data availablein the I~terature."-~ The electronic spectrum of Cu (0 polychelates contaq a broad band at 15L50cm1 and a weak band at 23,750an '.The p i t i o n of the band at 15,250m ' is in good agreement with those gener- ally obse~ved for square planar CuN) mmplexes and may be assigned to the kansition hg - 2 ~ 1 1 ( The weak band at 23,750 on-' may be assigned to the symmetry forbidden ligand -+ metal charge transfer

Figure 3 X-ray d~firachon of poly(BH4AQPMA) (a) poiy(BH1AQPMA)Cu (0) (b), and poly(BH4AQPM.4)- Nl(II) Q1

PI* l TGA

TABLE 111 ~nnogravimetnc Data of Poly(SH4.4QPM.4) and Ib Metal chelate#

Tempratwe ('Ci cornponds to

Sample T, (T) 10 30 50 70 90 Char % at 7WC

polr,(BH4AQPMA) 19 275 333 ?45 475 625 0 ~ O I ~ , ( ~ H ~ A Q P M A ) C U ( ~ ) 325 365 4% !dO 620 685 8 pOiv(8H4AQPMAi-N~(n) 265 585 425 585 625 635 6

transthon 2.~'~ A square planar mnhgurahon may be lentahvely ass~gned for the Cu(U) polychelates

The electrontc spectrum of NIOI) polychelates ,bows two broad bands at 16,500 cm" and 14,150 m-' and a weak band at 12,250 cn-I The first two hands may be ass~gned to the translhon )T,(R -r S,(P) and the latter to a spm forb~dden transihon to an upper state ansmg from the 'D state of the free ton Manch and Femol~as have made slnular obsewahms and ass1 ed an octahedral geometry for N I ~ com- F ylrxn" ' Based on the companson of the present data wlth that 01 the l~terature, an octahedral conhg- uiatton may be assigned for the Nl(IIi complex

The e p r spectrum of the cupnc complex shows a strong slgnal charactenshc to that of blvalent copper, k h ~ h IS attnbuted to the square planar cupnc ton m the center w~th the oxygen of the phenohc -OH and heterocycl~c nitrogen groups on the x and y axu Low sptn NIOI) In an octahedral held wtth tetragonal dls- ikrtton LI expected to have a spm orb~t couplmg parameter of g > 0 and, as a consequence, & > g- Thee p r parameters calculated for the N10n complex

are = 244 and g = 2 14 The g values are very consistent with NI(LI) m an octahedral envtmn- ment

Cum) polychelates have a magnetic moment of I BBM, md~cahng the square planar conhgurat~on The magnehc moment of 3 35BM and the paramag- nehc behavlor of Nt(II)complexes suggest d~tor ted octahedral geometry for N I ( ~ polychelates The X-ray dlffractogram of poly(BH4AQPMA) and tb C u O and Nt(1l) complexes are shown ur Flgure 3 The X-ray dlffrachon studas lndlcate that paIy(BH4AQPMA) IS amorphous, whereas I@ polychelates possess good crystalhity The nystallin~ty m polychelates may not be due to any ordermg m poly(BH4AQPM.4) lnduced d u m g metal chelate anchonng, more so since the anchonng of metals to the polymer would ~mply mter cham a o s s h k n g between poly(BH4AQPMA) inter chams, whlch should further reduce rather than en- hance any such ordenng The appearance of crystal- lin~ty m poIy(BH4AQPMA)-metal complexes may be because of the tnherent crystalline nature of the me- tall~c compounds

mplass-+m -hue ~pdy(%QPMA), plly(8H4AQPMA>Cu0. and ~~~IBH~~QPMA)-NI@! chebtE3 a found to be 1%. 325, and 265T. respechvely, The d~fference m tahslbon may be ambd to the crys- lalllnlt)' of the pdymer-md c o m p h and a m acmr- dance wlth X-ray diffradm study 'he TGA tans of FOly(BH4AQPMA), ply(BH4AQmvL4)Eum), and p ly- , ~ H U Q P M A ~ N I O chelate are shown m Flgure 4 The ddlcrenhal t h e d analfical data are presented m ~ a - ble 1u the p0lychekkS b e loseabut SO% werght nte i u ( m plychelate are found to be more stable than VI@) poly chekles ' h e IR IH NMQ e p r, eiedrmuc ~ ~ e d r a , and ma+ momenb studla mnfvmed that ~ h c chelahon of metal ions may pmsibly be occumng khveen two groups from d B e m t plymem chams, as (horn ur Scheme 2

The authors are grateful to RSlC Ill (Madras) Chenna~ for ?mv~dmg whumentai faahha One of the authors, TK, w Rrataiul to DST, Government of India for the award of )oung SoenMt

Reference

1 Kaliyappan T m, P Frog Polym 50 2W. 25 343 I Hum& W 6 , Hu, Q .S Pu, L 1 Org Chem 1999.64.794U i l r r C H Krm J S.5uh.M Y , L e W AnalChimANIW7

119 W l I Vernon. L P, SrPly, C R The Chlorophglls Acadmtc Prmr

Uew YarL 1%6 r Bollo B A I M m m o l 5 0 Chem 1980 A14 107

6 Bollo. B A I m Erch Pdlut Conhol 1979.2.213 7 ?pdemn,C J , FIEnsdroH. H K Angew C h m In1 Ed Engl1962,

11 h .., . 8 R o l h n . L D 1 Am Chem Sa 1975.97.2132 9 hag", R S, Gaul, 1, Z o h k . A , Slamb, D K ]Am C h m Sa

1980.102.1033 10 Rnas. B L Soqual. G V . Geckelrr, K E J Appl Poiym Sa 2m1,

81.1310 11 Kunnura, Y. Tauch!dr, E. M k o , M 1 Polym So 1971, A19,

3511 12 P m h I R A m C h m 1982. Y, 1BW 13 Pam& J R W Prad 1975.24,W 14 Wanhawky, A Deshc, A, R w , G , P a h h m ~ x , A Read

Polym 19M. 2.301 15 %l~yappm, T , Rapgopah S ,bum P 1 AppI PoIymSa ZOg)

2M1.w I6 Phyappan T , Rapgopan, S , K m m P J Awl Palym So ZmP,

91,494 17 Manti. X . Natlnsoljn. A , W o n , P Suprnmol50 1996,3,207 18 S1mpi.C H , G m , R P,Mane&,R PIAmChcmSal9M.

n, zm I9 Lwta I . Managek. 2 . Palova& R J Mawmol h Chem

1975, A9, 1413 20 Mabv~ya. I , Shukla, I' R , Snvastlva. L N 1 horg Nud olcm

1973, 35 1706 21 Mamn,, R I. Mma, S POC Chem Sa. London, W970, A32,

173 22 hynmal A b l e , K S Ind J Chm 1978, A16 45 23 Dub>&.) L M a m , R L horg Chem 1966.7.2203 21 lorgauen C K A h r p h m Sp&a and Chemtcal Bondsng m

Compl~xer Pergamm Pres Word, 1%2 15 25 F'w B N Inhodurnon to hgand ReIda. W d q h t m m w

New York, 1%2, 25 16 Mnnch, W , Fwohrr, W I 1 Chem Sa 1%1,38,192 27 Bortop, 0 . lorgmwn.C K A N Chw Sund 1957 11. 1223

Studies of Poly(8-hydroxy-4-azoquinolinephenol- formaldehyde) and Its Metal Complexes

S. Vijaydaknhmi, S. Subrammian, S. Rajagopan, T. M i y a p p a n

Deplrlmoil of Chcmlslry, Pondlchmy Engineering Collcge, Pondlchemj 605014, lndvl

R~elved 24 Srptember 2W4, accepted 12 May 2M5 DO1 10 lWZIapp22943 Published onhe m Wlley InterSoence (www mtemence wlley con)

ABSTRACP Poly(&hydmxy+quurolnephenol.form aldehyde) restn (BH4AQPF) was prepared by mndens~ng 8 hydroxv Cazqumoltne phenol wlth formaldehyde (1 1 mol mho) m the pmence of oxalic acld Polychelates were obtamed when the DMF mlubon of poiy(BH4AQPF) mn alnlng a kw drop of ammonla was treated w~th the aque- ous d u t ~ o n of CuU) and N I ~ ) ions The polymeric ram and polymer-metal complexes were charactenzed mth e k mental analvrlr and specnal rtu&es lhe elemental analvss

the polvmer-meal compleha 9uggeted that the metal. i - gand ran" was 1 ? Thr U1 rpnra, data ,,I tne pdj. hrtates ~ld~rated that tr m d s werr cwtJnatcd w u ~ g h

the Ntrogen and oxygen of the phenolr --OH group Lhf- fuse reflectance spectra, electron paramagnehc resonance, and magnetlc moment shd~es revcaled that the polymer- metal complexes of the Cu(n) mmplexer were square planar and those of the Ntm) complexen were odahedral X-ray diffract~on studies revealed that the plyrna metal mm- plexes were nystabne The thermal propemen of the ply- m e and polymer-metal complexes were aim e m e d BZmb W t l q Pendxalo Lu J Appl Polym b. 101 1%-1510,ZM

Key words metal-polymer complexes, radical polymew- hon, Ion exchangers, macromonomen, vlscmity

1NTRODUCnON

Polymer-metal complexes have been of interest to many reearchers durmg the past three decades m lhght of then ppoteal applicabons m dtvenlhed field.$ such as organlc synthesis, wastewater treatment, hy- drometallurgy, polymer drug grafb, recwvery of trace metal ~ons mcludmg radloachve elements, catalybc reamow, and models for enzymes' A number of polymer-contammg chelahng hgands, mcludmg poly- dentate ammes, m w n ethers, and prphynn, have been reported2 Selechve chelahon of spenhc metal IOIU from a metal ion nuxhrre by usmg a number of tetradentate hgands attached to polystyrene &vmyl- h e was demonstrated by Melby et a1 'Chelahng resm prepared by mplycondensahon of 8-hy- dromaumolme or phenol denvahves lrke 2.armno phenbi, prewrcyhc h i d , or m r a n o l with fonnalde hyde were re rted b Pennmgton and Wdhams'and Anstov et alcYkorblet a1 prepared a selechve Ion- exchange resm by reachng a condensahon product of 24dhydroxyacetophenone and a n t h r d l c ac~d wlth fomldehyde Parmer et a17 synthesized 2,4-dhy- droxy acetophenone fonnaldehyde r a m m an andic medium and stud14 16 chelahon propemes Prepa- nhon of a copper-selechve polymeric Iigand by the

reachon of phenol fonnaldehyde and pprazme was reported by Hodgkm et al" conhnuahon of our reearch9Io m this area, the present amcle deals w ~ t h the synthes~s and charactenahon of poly(&hydmxy- 4azoqumohphenol-formaldehyde) and ~ t s Cum) and NIUI) metal complexes

EXPERIMENTAL

B-Hydroxyqrunolmc and 4armnophenol (Fluka, France) were punhed accordmg to standard proce- dures, the solvents were punhed usmg standard p l t ~ cedures and then used, and B~hydmxy4aqumo- lmeh droxybenzene was prepared accordmg to Mang et a1 ' Synthesis of mammonomer

RHydmxy4azoqwolmehyhxybenzene (5 3 g, 0 O M ) , formaldehyde (Loba, Ind~a) (1 2 g, 0 04M), and oxahc acid [(Merck, Ind~a) 0 18 g, 3 % (wiw)] were added to a round.bottomed flask, sealed, and kept at IWC for 24 h m an 011 bath The formaldehyde resm formed m the flask was washed w ~ t h bhl led water and then dissolved m DMF, and NaCl (10%) soluhon was added to preclpltate the resm Then the resm was hltered and dned The IR and 'H-NMR spectra were consistent w~th the assigned strumre (Scheme 1)

Synthesis of polymer meld complexes

iounu] o f ~ p ~ w p w ~ ~ n o e vol 101,1506-1510 (2006) Polymer metal complexes of CU(U)/NINI were p r e ow ~ d e y ~ a i o d n l s , ~ n c pared m an alkalme medtum at m m temperature

Scheme 1

The polymer (1.37 g, 0.W5M) was dissolved m 30 mL 01 DMF An aqueous solution of Cu(lI)/Ni(n) acetate (0 62 g) was added dropwise with constant stirring, and the pH of the soluhon was adjusted to 7 w ~ t h d~lute ammonium hydrox~de soluhon The rnulhng m ~ x t u r e was digested on a water bath for 2 h and kept avernight at room temperature The precip~tated ~~I~(BH~AQPF)CUO~INI(U) complex was filtered, washed w~th hot dlshlled water, and dried.

The 1R spcira of the polymer and polymer metal complexes were recorded on a Bomem MB 104 FllR spectrometer from M0 m ~LWI anrmi uslng KBr pellets The 'H-NMR spectra of the polymer were recorded on a JEOL CSX rMO MHz spfftrometer usmg D W d , as the solvent and te t ramethylhe as the lntemal stan- dard The molecular weighs (&,and M,,) of the poly- mers were determ~ned by CPC (Water's model 410) usmg THF as the eluent Elemental analyses were performed on a Colemdn CHN a n d p r The metal

Figure 1 LR s W r a of (a) poly(BH4AQPA. (b) ply- (8H4AQFF)-Cum), and (c) ply(BH4AQPF)-Ni@).

content of the polymer metal complexes was deter- mined uslng a titrimetric procedure after decompos- ing the polychelates with concentrated HCI, perchlc- nc, HN03, and HISO,, The visrosity measurements were made in TW at W C with an Ubbelohde s w pended level viscometer. The glasrtrmition temper- atures of the polymers and metal complexes were detemuned by differential scanning colorimehy (DSC) with a h p n t 9W t h e m l analyzer at a heat- mg rate of 15'C/min in air.

The magnetic moments were measured using the Guoy method. The diffuse reflectance spstra ( 5 C - 2WO run) were measured on a Varian Cary 5E W- vis-NIR spettrophotometer. X-ray diffraction experi- ments were performed in a Philips PW1820 diffrac- tometer Thennogravimetric analysis (TCA) was carried out in a S e h I n s b e n t s Inc. A 5-mg sample was used at a heahng rate of 15'C/min in air.

RESULTS AND DISCUSSION

The novel poly(BH4AQPR was synthesized from Bhydmxy4az~qumolurehydmxybenzene and form-

TABLE l ElammW Analpi1 of Poly(BHIAQPF1 and Its Metal Compltxcs

Elemental analyru (wetght percent) Csrbon Hydrcgen Oxygen Nitmgen Metal -----

AWmr*Um Empvidlormula Cal.' Fd Cal.' Fd Cal.' Fd Cal' M. W: Fd

f P o l ~ ( @ f ~ ~ C 1 8 t I ~ I 69.31 69.33 4W 401 11.54 1152 15.15 15.14 - - PoI~(~I~~AQF'F)€u(~I) (C,,H,&N,),<u(II) 56.Y 56.52 2 % 2.97 9.42 9.43 1237 12.3 18.71 18.73 P~YCSH(AQPP).N~(U) [C,&,@$Q,-Nl(fl) 57.36 5737 301 302 9.55 9.53 12.55 1256 17.53 1752

- (HP), ' CaIolLkd -*gr ofC, H, N, 0, and metal iw IOT puIym6metaI-mmp1exes based on the value I = y = 2,OO. Found

x=zmy=2.m.

TABLE I1 IR Spectral Data of Wy(8HUQPR and Ib

Metal Complexes

Sample OH.,. C-N, N-N., M-N.,,

Poly(SH4AQPFl 31CQ,, IW,, IW,,, - Polv(SHAQPWu(ll) - 'mu, l%s,,, n.5 roly(BH4AQPP)-N~(U) i3CQg, 1M15*, 1540,, 735

b-brmd, +-strong

aldehyde m the pmenm of ode acld Polymer metal complexes were obtamed fmm a DMF soluhon of polymer and an aqueous soluhon of the metal ions Cu(ll) and N i O m the prfsence of a few d r o p of ammonu The polymers were soluble m DMF, THF, and DMSO and m l u b l e m common organic solvents hke benzene, toluene, methanol, and water The e le mental analysw data for the polymer and polymer- metal complexes are presented In Table I The elemen- ial analysrs data suggested that the metal to polymer ratio was 1 2 The m h u ~ ~ l c v m i t y [TI! was obtaned by extrapolahng q, /C to a zero concenbahon The ntnnslc v-lty ~ ~ ~ ~ I ~ ( B H ~ A Q P F ) was detemuned to be 0 59 dL/g

The number-average molecular welghtJM,) and the weight-average molecular weight (M,,,) of the polg(BH4AQPF) were d e t e d by gel prmeahon chromatography usmg tetrahydrofuran (M. = I81 and M , = 3 99 x 10') The polydepers~ty Index (M,,l M., for poly(BH4AQPF) was 2204 The theorehcal value of &/(;I. for poly(BH4AQPF) suggested a strong tendency for cham terminahon by radical r e combinahon

The LR spectra of poly(BH4AQPF) and its polyche. late6 are shown m Flgure 1 The IR spectra show a

Figure 3 X-ra diffraction of (a) pdy(SH4AQPF)-Cum), (bl poly(8~1AdpC-Nlm)

medium broad band extendmg from 28W to 3MX) an'' that IS assigned to the overlappmg peaks be- cause of aliphahc C-H stretch [< 3000 an-'), a r e mahc C-H stretch (> 3010 an-'), and ~ntramolecular and intermolecular hydrogen-bonded phenolic 0-H stretch (31W-36W mi-') In the spectra of the p l y - chektes th band deappeared, leanng behutd s h a ~ peaks for aliphahc and aromahc C-H stretdung vi- brahons So there was a loss of phenol~c -OH hydro- gen in coordlnahon with the metal ~ m s The Nifll) polychelates showed a strong band m a hgher-fre quency regon (3300 mi-'), suggeshng the coordm- hon of H,O molecules wlth N I ~ The frequency at lh00-1605 an- ' suggests C-N absorphon and a f r e quency of 9M) cm-I represents a 12,4,6-tetrasubsh-

Figure 4 TGA tram of (a) poly(8H4AQPF). (b) poly(8H4AQPF)-Cuill). and (c) poly(8H4AQPFkNilUl

POLY(IH4AQPF) AND ITS METAL COMPLEXES

TABLE 111 Thermal A n a l p a Data of Poly(BH4AQPFl and 11s Metal Complnes

Temperahue ('C) corresponds lo %mple T, (TI 10 30 M m Above m

tuted phenyl nng I' The other absorphons observed are presented m Table 11 The 'H-NMR spectrum of poly(BH4AQPF) 1s shown In F~gure 2 Signals from aromahc protons appear as broad mulhpiets m the regon 8 11-6 23 B Thesslgnals at 9 53-8 6 Gare a result of ammahc --OH The signal around 2 55 8 resulted from methylme protons

The relahonshp between the electro~c properhes of the metal ion m the complex and the sterwcherms-

hedral geometry of the NI@) plychelates The X-ray diffractogram of poly(BH4AQPF) and 16 Cu(lI)/N~(ll) complexes are shown m Rgure 3 The X-ray d i f f ra~ tlon stumes mdicated that ply(BH4AQPF) was amor phous, whereas 16 polychelates possessed good cry* t a h t y The crystallmity of the polychelates may not have been a result of any ordemg m poly(BH4AQPFJ Induced dunng metal chelate anchomg, more m be cause anchoring of metals to polymer would lmply

*n ul Ihr l~gand m L+r en, lronment prmni war ar- mrerchaln nosrhkmg 01 p l y l b ~ 4 A ~ ~ F ) mtrrchak. .:\ rc at rentanvelv on the bash ol lht datd asallable n whch should hare further reduced r a h than en- the l~terature '>" The electmnrc spectrum of Cu(Il) plychelates contamed a broad band at 15,430 cm-' and a weak band at 23,900 an ' The posihon of the hand at 15,430 an ' was m g o d agreement wtth those generally observed for square phnar Cu(ln curnplexej and could be assigned to the transition BIg - 'A,, The weak band at 23,903 an ' could be as- s~gned to the symmetry forb~dden l~gand - metal charge transfer translhon ''-I9 The Cu(Il) polychelates could be mlgned a square planar conhguratlon

'Ihe eledzonlc spectrum of Nl(I1) plychelates showed two broad bands, at 16,300 cm and 14.350 n ', and a weak band at 12,525 cm ' The hrst two bands could be asslgned to the transrhon fl,(F) - 'T,(P) and the latter to a spmforbidden transition to an upper state ansmg from the 'D state of the free Ion Manch and F e r n o h have made smlar observat~ons and ass1 ed an octahedral geometry for Nl(lI) com- plexeszlTBased on a cornpansan of the present data with that m the Ilterature, the NI(II) complex could be assigned an octahedralcanfigurahon

The EPR spectnun of the mpnc complex showed a rhong agnal charactenshc of that of blvalmt copper, which was attr~buted to the square planar cupnc Ion m the center wlth the oxygen of phenohc --OH and the heterocycl~c rutfogen p u p s on the x and y axes Low-spur N I ~ ) m an octahedral field with tetragonal dlstomon was expected to have a spm orbit couplmg Parameter of g > 0 and la a consequence, g > g' The EPRparameterscakmlPted for the N I ( ~ complex were fi = 2 601 and g' = 2 10 The g values were very conslatent m t h NI@) m an octahedral envlmnment Ihe Cu(m polychelates had a magnetlc moment of

1 48 BM, inhhng a square p h r mnfigurat~on The magnetic moment of 3 35 EM and the paramagnehc behav~or of Ni(ll)mmplexa suggest a distorted &a-

hanced any such ordenng The appearance of crystal- llruty m the poly(BH4AQPF)-metal complexes may have occurred because of the inherently crystalhe nature of the metallic compounds

The glasshanslhon temperaturn 01 ply(BH4AQPF). poly(8H4AQPFKu0, and poly(8H4AQWN1iT &late were found to be 135C, 305"C, and 245f. mpechvely The difference m hamlhorr may be asolbed to the c~~~ta l luuty of the polymer-metal mmplexes and was In accordance with the results of the X-ray dlflrac- bon study The TGA tram of the ply(BH4AQPF), poly(8H4AQpFIcu0, and ply(8H4AQpPN10 che late are shown m Figure 4 and Table U1 All the ply- chelate lost about 90% of thm welght 'Ihe Cum) p l y chelate were found to be more stable than the N I ~ p l y &elates The nt 'H-NMQ @K e b ~ c spxtra, and magnetu moments studm confumed that chehhon of the metal ions may possibly have been occumng between two p u p s from different polymeric chams, shown ln Scheme 2

The authors are giateld to RSlC liT (Madras) Cbm~ for provldmg msmmenld faallhes One 01 h e aulors (T K ) IS

M" I -

DMF

X

M = Curl NP (For NI X = t$O)

Scheme 2

Rra"ful to DST, Government of India, for the award of young Soentlot

References

1 Kahyappan. T . IDnrun, P hog Polym Sn 2W. 25.343 ? Pdswn, C I . F d m f l , H K Angw Chm. Int Ed End

1%2, 11,6 3 Meby. L ! I Am Chem bc l9W. 57.W 4 P m m m . L D , WJlum, M B Ind Ens: Chm 1959.9.759

1961. W. I1 x H c d g h , 1 H , ElbL R Rend Polym Ion EichSarbslb985,3, K3 u b l ~ y a p p m . T . R a p g 0 p m . S .Kuvun.P I AppiPolymSoZM1,

W, 2 w

12 N h B , K Mrud Abrorphm S p c a w o p y 2nd d. N a p Japan, 1964. p 20

13 Lustoh 1, Mnnagek, Z. Palovock, R 1 Mammol 50, Chem 1975, A9.1413

14 Waviyr , I , ShuW., P R. Snvartava. L N 1 Inorg Nud Chem 1 9 n . 35.1706

15 Mnrtiru, R L , Mlaa. S FCC CT,m 5a. Lcmdon,5r 1970, A32. m

16 Syamal, A , Kale, K S Ind J Chem 1978. Al6, (6

17 Dublrkl, L. Madlnl, R L lnarg Chpm 1%. 7, LM3 18 Img- C K Abbolptlon Sprctra and C h d h d m g m

Complexes, Pngma Rrar Oxiord, UK. 1% p 15 19 Fgp, 8 N Infrducuon to Ltgand Reldr. W d q Inlevlace

New Yark. 1 W . p 25 20 Man&. W , Femolns W I 1 Chcm Soc 1%1,3R,192 21 Bortop. 0, lorgman, C K Acta Chem Sund 1957, 11.l223

Drsr ncd Mmomers and Polymrrs Vol 9 No 5 pp 425-437 (2006) 0 "$2006 Also avulablc onl~ne www bnU nUdmp

Studies on poly(8-hydroxy-4-azoquinolinephenylacrylate) and its metal complexes

S VUAYALAKSHMI, R SANKAR, S SUBRAMANIAN, S RAJAGOPAN and T KALIYAPPAN Dcpamtvnr of Chemurry. Pondtchew Englneenng College, Pondreherry 605 014, lndu

Abshoet-Poly(8-hydroxy4-4~~oq~1noI~nephenyIa~rylate prepared fmm acryloyl chlonde wrth con- denmuon products of 8 hydroxyquinolrne and Cammophenol, was polymerized m DMF at 70°C using bcnwyl pcmxlde as milrator Polychelatcs w e n obmned In alhlrne solution of polymenc Irg. and with the aqueous rolut~on of Cum) and NI(II) Polymer was charactenzed by IR and 'H-NMR techn~ques The molecular weight of the polymer was deumuned by GPC The polychelates were chamcmmd by elemental anplys~s, X ray d~ffracnon, IR and elcctronrc spectral shlmes The thermal pmpcrtles of polymer and polychelaus were studred The metal ron uptake pmpmes of the polymer at Lffmnl pH are also srudld

Krywordr Poly(8-hydroxy-4-~~oqu1nol~nephenylacrylate polychelates, oxlne polymers. crystal lmlty, polyma-m~al wmplexes

1. INTRODUCTION

The polychelatu, prepared by chelatron of metal Ions w~th functtonal groups In the polymer rnatnces, have supenor propernes, whrch are mfficult to achleve from comspondlng monomenc metal complexes [ l ] The chelate resln, functtonallzed by rnuln dmtate I~gand, rs often used for these purposes Polychelates have a w ~ d e rangeaf applsuons, such as sem~conductors [2], catalysts [3], or controlled nlease agents for drugs, b~oc~des (41, recovery of mce metal Ions [5] and nuclear chemistry [6] A number of polymer bound chelattng l~gands Including p l y dentate ammes, crown ethers, porphynns and polyaclylam~de ~ m ~ n d a c e t a t e are also r e p o w . Chelanng polymenc reslns are found to be more selectwe by nature ~n the removal of metal ions [7-91 The p o l p a r of vrnyl benzoylacetone was prepared from vlnyl benzaldehyde and

co-polpenzed to polymer, whch readily forms complexes wlth Nr(U), Cu(II),

'To tvhan campondmsc should bc addressed E m l lkal1yappan2001@yahoo wm

Co(I1) and Au(II) [lo]. The free radical polymerization of Cu(I1) complex with Schiff's base ligand containing vinyl group and radical polymerization of methacry- late monomers coordinated to Co(Il) have been reported [I I]. Polymeric Schiff's base chelates based on various functional polymers have been investigated [12- 151. 8-hydroxyquinoline (oxine) is extensively used in analytical chemistry as a pho- tometric agent and or extraction agent. Oxine is selective ~IEI has consequently attracted gnat interest as a potential chelator for these metallic ions. Among the earliest chelating resins to be studied were analogues of EDTA, viz., Dowex A-1, chelex-100 and chelex-20 [16, 171. These resins continue to be useful in a wide variety of systems. Some of the metals extracted from seawater and other systems with chelex-100 and Dowex A-1 are Sc, V, Fe, Co, Ni, Cu, etc. Separation of transi- tion metal ions on various oxine-chelating resins, including commercial oxine, was reported by Panish et al. [18]. In this investigation new azo polymeric ligands and its chelate-forming ability with various divalent metal ions have been studied.

2. EXPERIMENTAL

2.1. Materials

8-Hydroxy-4-azoquinolinehydroxybenzene was prepared according to Mang et al. [19]. Benzoyl peroxide was recrystallised from chloroform-methanol mixture. Acryloyl chloridk was prepared by a reported procedure [20].

2.2. Monomer synthesis

8-Hydroxy-4-azoquinolinehydroxybenzene (5.3 g, 0.02 M), triethylamine (2.78 ml, 0.02 M), hydroquinone (0.5 g) and 2-butanone (25 ml) were taken in a three-necked flask equipped with a stirrer, thermometer and separating funnel. The contents were cooled to -5°C. Acryloylchloride (1.8 ml, 0.02 M) in 20 ml 2-butanone was added drop-wise with constant sliming and cooling. The reaction mixture was gradually allowed to reach room temperature and stining was continued for 2 h. The quaternary ammonium salt formed was then filtered off. The filtrate was washed with distilled water, dried over anhydrous sodium sulfate and the solvent was evaporated in vacuo (yield 85%). The IR and NMR spectra were consistent with the assigned structure (Scheme I).

2.3. Polymerisation

8-Hydroxy-4-azoquinoline phenylacrylate (8H4AQPA, 3.5 M) in 10 ml DMF and benzoyl peroxide (0.5 g) were taken in a standard reaction tube and deaerated by passing oxygen-free nitrogen for 30 min. The reaction tube was closed and kept in a thermostat at 70 f 1°C for 8 h. Then the contents wwe then cooled and poured over methanol (100 ml). The precipitated poly(8-hydroxy 4-azoquinoline phenylanylate) (poly(8H4AQPA)) was filtered washed with methanol and dried (yield 86%).

PoIy(8~hydmxy4-awquvloli~phcnylacryhtc) and 10 metal complurs 427

HNO,

O'C

2.4. Prepamtion of polychelates

The polymer (6 mmol of repeat umt) was dissolved in 30 ml DME An aqueous soluhon of Cu(II)Mi(II) acetate (0.62 g) was added dropwise with constant stining and the pH of the solution was adjusted to 7 with dilute ammonium hydroxide solution. The resulting mixture was digested on a water bath for 2 h and kept overnight at room temperature. The precipitated poly(8H4AQPA)Cu(II)/Ni(II) complex was filtered, washed with hot distilled water and dried. Yield: 80% for Cu(I1) polychelates and 83% Ni(II) polychelates.

Pdy(8~h>.dwd-nzoquinoli~p~nylaeryht~) and its me& complucs 429

2.5. Determination of metal uptake a t different pH

The polymer sample (25 mg) was dissolved in DMF and the pH of the solution was adjusted to the required value by using either 0.1 M HCI or 0.1 M NH3. The solution was stirred and 5 ml of a 0.1 M solution of metal ions (Cu(JQ/Ni(II)) was added and the pH was adjusted to the required value. The mixture was stirred at room temperature for 24 hand filtered. The solid was washed, the filtrate and the washings were combined, and quantitative determination of metal ion concentration was done by following the titration method for Cu(II) and dimethyl glyoxime method for Ni(I1).

2.6. Measurements

The IR spectra of the polymer and polymer metal complexes were recorded using KBr pellets. The 'H-NMR spectrum of the polymer was recorded on a Jeol GSX 400 MHz spectrometer in DMSOG using tebamethylsilane as the internal standard. Molecular weights (M, and M,) of the polymer were determined by GPC (Waters model 410) using tetrahydrofuran (THF) as eluent. Elemental analyses were performed on a Coleman C, H, N analyzer. The metal content of a polymer metal complexes were determined using titrimetric procedure after decomposing the polychelates with conc. HCI, perchloric acid, HNOJ and HzS04. Viscosity measurements were done in THF at 30°C with an Ubbelohde suspended level viscometer.

The magnetic moments were measured using the Guoy method. The diffuse reflectance spectra (500-2000 nm) were measured on a Varian Cary 5E W-Vis-NIR spectruphot~meter. X-ray diffraction experiments were performed with a Philips PW 1820 diffractometer. Thermogravimetric analysis (TGA) was carried out using a Seiko analyzer. A 5 mg samplewas used at a heating rate of 15O"Ctmin in air.

3. RESULTS AM) DISCUSSION

The monomer (I) is prepared and polymerized in DMF using benzoyl peroxide as initiator with a good yield. Polymer metal complexes were obtained in a DMF containing polymer in an aqueous solution of metal ions Cu(II) and Ni(II) in the presence of few drops of ammonia. The polymers were soluble in DMF, THF and DMSO and insoluble in common organic solvents like benzene, toluene, methanol and water. All the polychelates an sparingly soluble in THF and DME The elemental analysis data (Table 1) suggest that the metal to polymer ratio is 1 :2. The intrinsic viscosity [q] was obtained by extrapolating qsw to zero concentration. The intrinsic viscosity of poly(BH4AQPA) obgned was 0.47 N g .

The number-average molecular weight (Mu) and weight-average mo@lar weight (aw) of the poly(BH4AQPA) were determined by GE ugng THF (Mu = 1.76 x I@, z,, = 3.72 x 10'). The polydispersity index (M,/M.) for poly(lH4AQPA)

n m 1. IR spectra of poly(BH4AQPA) (8). poly(8H4AQPA)-Cu(I1) 0) and poly(8H4AQPA). N i O (c).

- - is 2.1 1. The theoretical value of M , / M , for poly(lH4AQPA) suggests a strong tendency for chain termination by radical combination.

The IR spectra of poly(BH4AQPA) and its polychelates are shown in Fig. 1. The absorption band near 3300 cm-' corresponds to phenolic -OH stretching. This band disappears in the spectra of metal complex establishing the involvement of phenolic -OH in the co-ordination polymer. Ni(I1) polychelates show a strong band at a higher frequency region (3400 cm-') than that assigned for the phenolic -OH group. The fPct than this band remains even when the polymer metal complex was heated up to 150°C suggests the coordination of Hz0 molecules to Ni(I1). The smng bands at 1736 cm-I and 1600 cm-' may be ascribed to C-0 ester and ketonic groups, respectively. The medium intensity band at 1190 cm-' in the spectrum of polymer is due to the hydrogen-bonded ring system of the ligand. The band around 720 cm-I cornsponds m metal oxygen vibration. The other absorptions observed arc presented in Table 2. The 'H-NMR s p t r u m of poly(8H4AQPA) is shown in Fig. 2. Signals due to aromatic protons appear as a broad multiplet in the region 7.016.136. The resonance signals around 2.9-2.286 are due to the methylene and methine protons.

'hblt 2 IR spectral data of poly(BH4AQPA) and ~ t s metal complexes

Sample OHsu C=O cstnur N=N,u Phmohc C - 0 Estenc C-Om M-0*

Poly(8H4AQPA) 30%3400(b) 1736(.) 1575(,) 1381 1180 - Poly(8HAQPA)- - 1738(,) IS@)(,) 1378 LIW 720 ctlml <&%H~AQPA)- 3100(t,) 1738(,) 1580(,) 1380 1175 735 NICII)

b, broad, m, m&um, s, strong

Flgw 2 'H-NMR spectrum of poly(BH4AQPA)

The relatlonshp between the electron~c propemes of the metal ~ons In the complex and the stmochenustry of the l~gand ~n the environment present was detemuned tentat~vely on the bass of the data aviulable I h e l r a 2 1 - 2 The electroruc spectrum of Cu(I1) polychelates contiuns a broad band at 15 150 cm-I and a weak band at 23 850 cm-I. The poslt~on of the band at 15 150 cm-I 1s ~n good agreement wlth those generally observed for square planar Cu(U) complexes and may be ass~gnsd to (he transtoon B1, -+ 2 ~ ~ , The weak band at 23850 m-' may be ass~gned to the symmetry forb~dden hgand -+ metal charge-transfer &smm 125-271 A squ& plan& configuratlon~may be tentatively &slgned for the Cu(I1) polychelates. The electron~c spectrum of NI(II) polychelates shows two

Rlgm 3. X-ray Lffr8ctlon of poly(BH4AQPA) (a), poly(BH4AQPA)-Cu(U) (b) and poly(BH4AQPA)- Nl(U) (c).

broad bands at 16 500 cm-I and 14 250 cm-' and a weak band at 12 350 crn-I. The first two bands may be assigned to the transition 'TI@) -+ 3 T I ( ~ ) and the latter to a spin forbidden transition to an upper state arising from the ID state of the free ion. Similar observations have been made and assigned an octahedral geomey to Ni(II) complexes (28.291. Based on the comparison of the present data with that of the literature, an o c t a h W configuration may be assigned to the Ni(II) complex.

The EPR spectrum of cupric complex shows a strong signal characteristics to that of bivalent copper which is attributed to the square planar cupric ion in the center with the oxygen of phenolic -OH and heterocyclic nitrogen groups on the x and y axis. Low-spin Ni(I1) in an octahedral field with tetragonal distortion is expected to have spin orbit coupling parameter of g z 0 and as a consequence gb gg. The EPR parameters calculated for the Ni(I1) complex are gll = 2.425 and gi = 2.12. The g values are very consistent with Ni(LI) in an octahedral environment. Cu(II) polychelates have a magnetic moment of 1.56 BM, indicating the square planar configuration. The magnetic moment of 3.23 BM and the paramagnetic bchaviour of Ni(I1) complexes suggest distorted octahedral geomey for Ni(II) polychelates. The X-ray diffractograms of poly(8H4AQPA) and its Cu(II), Ni(U) complexes are shown in Fig. 3. The X-ray diffraction studies indicate that poly(BH4AQPA) is amorphous, whereas iu polychelates possess good crystallinity.

Poly(8-hydmxy-4-arogui~11wphcnyhc~late) and 18 metal complucs 433

EYgurr 4, fGA w e s of poly(BH4AQPA) (a), poly(BH4AQPA) Cu(U) (b) and poly(BH4AQPA) Nlm) fc)

The crystalllnlty In plychelates may not be due to any ordenng In poly(SH4AQPA) Induced dunng metal chelates anchonng, more so slnce anchonng of metals to polymer would imply ~nterchun cross-l~nlang between ply(SH4AQPA) mterchuns whch should further nduce rather than enhance any such ordenng The appearance of crystallln~ty In ply(BH4AQPA) metal complexes may be because of lnherent crystalhne nature of the metallic compounds The glass-trans~tlon temperatures for poly(SH4AQPA). poly(lH4AQPA)-Cu(II)

and poly(lH4AQPA)-N1(n) chelates are found to be 140, 305 and 275°C respec- tlvely The mfference In translhon may be ascnbed to the crystalll~uty of the polymer-metal complexes and 1s In accordance wlth X-ray bffrachon study The TGA traces of ply(SH4AQPA), poly(SH4AQPA)-Cu(I1) and ply(BH4AQPA)- Nl(11) chelates are shown In R g 4 The d~fferentlal thermal analytical data are presented In Table 3 All the polychelates lose about 90% we~ght The Cu(I1) poly- chelates arc found to be more stable than Nl(II) polychelates The IR, 'H-NMR, EPR, electronrc spectra and the magnetlc moment studres confirmed that the chela- oon of metal Ion mght poss~bly be occurring between two groups h m mfferent polymenc chiuns are shown m Scheme 2

3 I Applrcahon studres

The relahve amounts of the metal Ions taken up by the polymenc resln Increases wlth an rncreaslng pH of the m&um The results reveal opnmum pH of 7 and

nbk 3. Thcnnogmvimctnc data of ply(BH4AQPA) and 1t.s metal chelares

Sample T g PC) Temperature ('C) correspnd~ng to 6 welght loss Char at 7 W C ( 6 ) ~n %n 5n 7n 'XI

P' E

Poly(8-hydmxy4-azogu1noliwphcnyhcryInuJ and its metal complucs 435

BPO II -

70°C

Cu2'1Ni2' - DMF

M = Cu2*INiZ+ (For NI, X = H20)

above for the maximum uptake of copper and nickel using poly(8H4AQPA) as the ion exchanger.

The high selectivity of resin towards Cu(1I) and Ni(lI) is shown in Fig. 5, which shows the sorption behavior of metal ions at different pH. Generally resins containing sulphur and nitrogen atoms as ligands have high affinity for Cu(II)/Ni(II) 130-321. Chelation was assumed to occur on basis of increase in pH, when the resin was shaken with the metal ion solution.

Polymer recovemi with HCI (7 M) from the complexes is good and reproducible. Further, the polymer is stable in the acidic conditions.

Figure 5. Pmentage metal uptake of poly(BH4AQPA) at mffennt pH

Acknowledgements

The authors are grateful to RSIC IIT (Madras) Chennai for providing instrumental facilities. T. K. is grateful to DST, Government of India for the Young Scientist award.

REFERENCES

I. T. Kaliyappan and P. Kannan. Pmg. Polym. Sci. 25,343 (2000). 2. Y. Saegusa. T. Takasluma and S. Nakamura. I. PoIym Sci. Polym Chem Edn. 30.1375 (1992). 3. G. Cdman. I. Am Water Ass. 73.652 (1981). 4. M. Wlumbo. A. Cosaru, M. Terbojench and E. Peggion. J. Am. Chem. Soc. 99,939 (1977). 5. L. Bamaszal, I. C. Weston and J. C. Kendnw. J. Mol. Biol. 12, 130 (1965). 6. S. S. lseid, C G. Kuehn, J. M. Lyon and A. Mernfield, I. Am. Chem Soc. 104,2632 (1982). 7 . C. I. Pedcrson and H. K. Fnnsdroff.Angnu. Chem IN. Edn. Engl. 11.6 (1%2). 8. L. D. Rollman. I. A m C h m . Soc. 97,2132 (1975). 9. R. S. h s g o , I. Gaul, A. Zombcck and D. K. Stamb, I. Am Chem Soc. 102,1033 (1980).

10. B. L. km, H. A. MaNrana X. Ocampo and I. M. Peric. I. Appl. Polym. Sci. 88.1995 (2001). 11. Y. K u r w E. Tsuchida and M. Kaneko, I. h l y m Sci. A19.3511 (1971). 12. M. Y. Khuhawarand A. H. Channar. Mncromol. Rep. A32.523 (1995). 13. D. Wohrie. H. Bohlcn and G. Mcycr, Polym Bull. 11.143 (1984). 14. T. Kdiyappm, S. Rajagopan and P. Kannan, 1. &PI. P o l p Sci. 90,2083 (2003). 15. T. Kdiyappn. S. Rpjagopnn and P. Kannan. Appl. h lym. Sci. 91.494 (2004). 16. C. Kantipuly, S. Kauagsdda, A. Chow and H. D. Gesser, T a h I a 37.813 (1978).

Poly(8-hydm~y4-aroguinolinephenyl1~rylate and its tnctal complexes 437

17. 7. Kaliyappan, R. Anupriya and P. Kannan, Makmmol. Chem Pun Appl. Sci. 36.517 (1999). 18. J. R. Panish. Ann Chem 54.1890 (1982). 19. X. Mang, A. Namsolin and P. Rochon, Supramol. Sci. 3,207 (1996). 20. G. H. Stempel, R. P. Gross and B. Mariella, I. Am, Chem. Soc. 72,2299 (1950). 21. I. Luston, 2. Managck and R. Palovcick, I. Macmmol. Sci. Chem. A9, 1415/1975). 22. Malaviya, P. R. Shukla and L. N. Srivastava I. Inorg. Nucl. Chcm. 35,1706 (1973). 23. R. L. M d n ~ and S. Mioa, Pmc. Chcm Soc. London ,432,473 (1970). 24. A. Syamal and K. S. Kala, Ind. I. Chem. A16.46 (1978). 25. L. Dubicki and R. L. Mamni, Iwrg. Chem. 7.2203 (1966). 26. C. K. lorgensen, in: Absorption Spectra d Chemical Bonding in Complexes, p. 15. Pergamon,

Oxford (1%2). 27. B. N. Figgts. In: introduction to L i g d Fields, p. 25. Wilcy-Interscience. New York, NY (1x2). 28. W. Manch and W. I. Pernolias, J. Chem Soc. 38, 192 (1961). 29. 0 . Bostop and C. K. Jorgcnson. Acfa Chrm. S c d . 11.1233 (1957). 30. A. Sugi and N. Ogawa, Chem Pharm. Bull. (Tokyo) 24.1349 (1976). 31. A. Sugi. N. Ogawa and M. Hisamitsu. Chem Pharm. Bull. (Tokyo) 26.798 (1978). 32. J. E Dingman Jr., K. M. Gloss, E. A. Milano and S. Slggia, A d . Chem. 46,774 (1974).

Synthesis and Metal Uptake Studies on Pol (hhydroxy- bazoquinoline hen lacrylate- formaldehyde^ Resin and its Metal e amp r exes

S. Vijayalabhmi, R. Sanku, S. Subnmanian, S. Rajagopan, T, W y a p p a n

Deprrtmmt of Chmtlslrq, Pondlchmy Englnemng College, Pad~chmy 605014, lndi

ABSTRACT 8-hydroxy5~azoqu1noI1nephenylacrylah- the metal to Lgand raho u about 1 2 The palymer meial lormaldehydr (BHSAQPA-F) macmmonomer was p w complexes were a h charactenzed by LK XRD, m p & c pared from acryloylchbnde, wlth cundewhon products moments, and thermal analyms The eff& of pH and of Bhy~fraqalwoIwphenol~brmaldehyde, and ply- elRbolyte on the metal uptake behavlor of Be ream were merued m DMF at 7PC uslng benzoyl perox~de as free also studled %I \rl>ley Penodtrah inc I ~ p p l Polyn h rad~cal mbator Poly(BH5AQPA-F) was characterued by 101 797-802. ZW ~ntrared and nuclear magnet resonance spearoscop~c trchques Polychelates were obtamd m a h h e soluhon Key w o h Bhydroxydazoquolure. diffuse reflectance 01 plynenc llgand wlth the aqueous soluhon of CuOll spemm, thermal analyua, metal uptake, apedrmoplc and N I ~ ) Elemental analysis of polychelales suggests that sNdles

INTRODUCTION

Chelabng polymen can play an unportant role tn solv- mg envuonmental p r o b h Qlelabng resm a bask caUy an o p polymer c o n m g donor atoms that can succensfully mteract wlth the metal lorn through coordmte bond and polymer backbone makes them more &ent by offemg large surface area

Polymer metal complexes have been of mterest to many researchen dunng the past three decades tn the l~ght of the11 pomhal a llcdhons m dlvenlfied

PP held.! hke orgatuc synthesis, waste water keahnent,' hydrometallurgy,' polymer drug grafts.' recovery of trace metal ~ O I I S , ~ and nuclear chermstry"h add17 bon, they are F& used as m d e k for enzymes ''

The determwhon of trace toxic metal ions and the11 removal w~th chelatvlg polymers have gamed great Importance m envuonmental appllcahom b u s e of theu hqh degree of selectivity, hgh load- ing capacity, vnsahhty, dunbhty, and enhanced hydmphihaty9 Olelahng ion-exchange resins wth s@c chelabng gmups attached to polymers have found extensive use m the separahon and precon- m k a h o n of metrl im lCIZ

In recat ycars, the development of su~table func- honalued chektmg resm for trace meal preconcen-

lo& of A@ed Polymm SdsKe, Vd 1M, 797-SCn (m7) 02W W~ky P e n d ~ d . Inc c; - '*! InterScience'

tratlon and separahon prov~des a new unpehls to extrachon approach El-Sonbah and coworkers have studied the new sohd polymer metal complexes of several stencally hmdered heterocychc h g a n d ~ ' ~ ' ~ Most of the workers charactenzed N=N-Inkage by the presence of a band m the regon 1570-1579 a n ? m LR spectrum As the chelabng resm contams a weak baslc functional group hke phenohc -OH, it s expected that the sorphon of the metal depend on the pH of the m&um In conhnuahon of our research work m polychelates,'617 m hs arhcle, we report synthess, charactemahon, and apphcahon study on poly(&hydroxy-5azoq~1l1ohephenylany- late-formaldehyde) [poly(BHSAQPA-F)] resm and I@

metal complexes

MPERIMENTAL

Benzoyl pernude (BDH, In&) was ~~ from chloroform/methanol nuxture 8-hydroxy qurnolme (BDH, In&) was rec@alhzed fmm m e b o L Aayl- oyl chlonde and 8-hydmxy-5-aquuqhe hydro7 b e were prepared by the procedure reported la'

A nuxture of 1 11, Bhydroxy-Saqrunohe hydmxy- benzene and 3Wo formah dubon, and 3°W/WJ of oxahc and were placed m a mund-bottom tlaak sealed and put m an 011 bath at 100°C for 24 h The

OXALIC ACID I 4 HCHO -

100 .c

m Scheme l Synthesrr of macromonomer B-hydroxy 4 a z o q u o h e p h e n y l a q l u t t f o ~ d e

flask was then cooled to room temperature and desealed and wata was decanted The sohd ranam- mg m the tlask a dlssohred m NJJ-dlmethyl fonnam- ~de, and the resulhng soluhon was added dropww to large ex- of 10% aqueous sodturn chlonde solu- hon with cmutant s m g 'Ihen, the red compound was hltered and washed wera l tunes with dishlled water unhl free of chlonde Lon and dned at 60°C

deaerated by passmg oxygen fm Nihogen for 30 mm ' h e reachon tube was closed and kept m a thermostat at 70°C for 8 h A large excess of metha- nol was added to the contenb and the precipitated poly(BH5AQPA-F) was bltered, washed wtth metha- nol, and punhed by N,N-d~methyl formamidefmeth- aml mixture Polymer was dried under reduced pnssure at 64°C for constant we~ght

Synthma of poly(8HSAQPA-Fl metal chelates

8HSAQPA-F (26 & O W , Inethykmme (278 mL, Po'Y"'er were p'Tared at room tan-

0 OW, h y d q w o n e (0 5 g), and DMF (25 mL) were peTature by soluhon *que A Wlal procedw

am a thmeck flask equpped a smr fOr the preparamn of ~ l Y " ' ~ ~ m ) cht?late a as hi-

thermometer, and separpm b e , , and the lows P o ~ ~ ~ ~ H ~ A Q P A - R (5 m ~ l of repeat m

were cmled to 0 to -5°C Acryloyl chlonde (1 8 mL, mL) and the pH thesolubm was adpted

OO?M) was added dropwlre wlth constant shmng at to mth amurn hyhx'de aquears tRnperatuR ne muture was then mhhon of Cum) acetate (2 m o i ) was added drop

~hrred for another 2 h at n a m temperature and the wise to the plymer with mnstant sw quaternary ammoruurn salt was h~tered off he ~II- mublre was Qeted On a for hate was thomugNy washed with dst~IIed water and and kept Over at room temperature The pre- dried over anhydrous and the clpitated Poly(RH5AQPA-&metaI cmpler was fd-

a remwed to get a mbd IR 1~ IH.NMR spec- t d , washed with hot bidled water, followed by

wm cavusmt with the awped structure methanol, and dned at W C m wuo A slmllar pma-

(Scheme 1) dure was adopted for the p p r a h o n of NI(II) chelate Y~eld 83% for Cum) and 85% for N O

8H5AQPA-F (3 5M) m DMF and benzoyl perox~de IR specha were warded on a Bomem MB 104 mR (05 g) w m t~h n a standard reachon tube and spectmphotometu usmg KBr pellets The 'H-NMR

SYNTHESIS AND METAL UFTAKE STUDIES ON POLY(8HSAQPA.F)

TABLE l Elmental Analvsls for Polv(8H5AOPA.F) and Itl Metal Comolnls , -

Elemental malvas (wnght prm4 Carbon Hvdrwm Orvsm Nahmm Meal

~ , - - - , - . . . - . 0- ----- Abbrwuuon Empzncal formula Cal a Fd 0 1 ' Fd Cd' Fd Cal' Fd 6 1 ' Fd

PoIy(BH5AQPA.R CI*H,X)&~ 6887 6886 395 3% 145 1452 1268 12.66 - - PoIyI8HSAQPA~F)CuIll) lC~rH,iOJrl~).€u(Il) 5794 5793 3 07 308 12 19 12 17 1067 1068 16 13 16 14 Poly(8HSAQPA FtN10ll ( C I P H ~ ~ O ~ ~ I ) ~ - N ~ I ~ I lH10)~ 5876 5873 3 11 312 1237:1239 1UB2 1084 1494 1492

'Calculated percentage of C. H. N, 0 md metal Ions for polymer-metal complexes based on the value of r = y = 2 W, Found x=202,y=201

spectra were recorded on a JEOL-GSX 400 MH: spedromPter m deuterated DMSO as solvent using TMS as lntemal standard The molecular we~ghts [M, and M,) were determined by gel permeahon chromatograph (Waters model 401) The d h s e re- flectance specha of the polychelates were recorded on a Carl-Zews VSU-ZP spectrophotometer The mgnetlc moments were detemuned by Guoy meth- od and corrected for the dlamagnehsm of the com- ponents uslng Pascal's constant The thermogravi- memc analys~s of the polymer was performed on a Mettier 20W TA thermal analvzer The C. H, and N

Effect of pH on metal ion uptake

The ophmum pH of the metal Ion uptake was deter- mmed wlth a bakh eqdlbrahon (eduuque Excess of metal Ions Cu(n)/N~(ll) (10 mL, 01M) were shaken with 25 mg of the resrn for 24 h The pH of the mluhon was adlusted before equlllbrahon over a range of 1-10, wlth weak ac~d/base The complex was hltered off, and the concentrahon of the Cu(II) ton remamlng m the filtrate was detemuned by ~odometncally and Ni(Il) by gravunetncally

contents were determmed wlth an Elemental ana- lyzer (Elementar, van0 EL, Hanau. Germany) RESULTS AND DISCUSSION

The polychelates were m l u b l e m common organlc solvents but moderately soluble m DMF The ele-

Metal uptake studlm of polymer m the pmence of elcctmlytea

mental analysw data for poly(BH5AQPA-F) and metal complexes are presented m Table I The ele-

The wlvmer s a m ~ l e (25 ma m 25 mL of DMFl was mental amlvsw data suaested a metal to volvmer addid an e1elect;olyhc soluhon (25 mL) of a known raho of I 2, and ~t e ;good agreement ;I& the concenhahon The pH of the soluhon was adlusted calculated values by usmg 0 1M HC1 or 0 1M NHJ The soluhon was Vwcos~ty measurements were done by usmg shrred for 24 h at mom temperature To h soluhon, Ubbelohde suspended level vlscometer The mtnnsic 10 mL of 0 1M solution of metal ~cn CU(Q/NI(II] was v~scosity [q] was obtalned by extrapolatlng q.p/C to added and the pH was adpted b the requued zero concenhahon and it was found to be 0 61 dL/ value The mutun was agam shned at 25°C for 24 h g The resulk reveal that the molecular welght of and hltered The mhd was washed and the Cum) ion the polymer w moderately high The number aver- content was detRrmned ~adunetncallly and NI by age molecular we~ght (M,) and the welght average gravunetncdy The amount of the metal Ion uptake molecular we~ght (M,) of the macromonomer of the polymer was calculated from the difference (BHSAQPA-F) were determmed by gel permeahon behvem a blank expemmt w~thout the polymer and chromatography usmg tetrahydrofuran as solvent, the readmg m the achtal expnmenb The expen- and found M,, = 143 x l d , M, = 279 x ld and nenb were pe*ormed m the presence of several elec- for the polymer[poly(8H5AQPA-F)] (M.) = 163 tmlytes wlth Cu(U) and Nl(4 low x lo', (M,) = 3% x 10' and the polydrspers~ty

TABLE I1 IR S p h a l Data of PolylBHSAQPA-F) and Its Metal Complexer

b p l e OH, C+ster.,. N=N, Phmohc C-0 M-N, M-0..

Poly (8HSAQPA.P) rmrWnr 17@ 1% 1375 PolyCSHSAQPA.F'&u(ll) 1735~ 1555' 1380 720 5% Paly (SH5AQPA.P) -NIN) 3100. 1735~ l55P 1385 735 525

' Blold :Medium %

h y m 1 'H-NMR spedrum of polg(BH5AQPA F)

~ndex (M,)I(M,) = 2 16 for ply(BH5AQPA-F) sug- gests for cham t e m a h o n by rad~cal combmahon

Chuactmuhon

The 1R spffhum of p l y (BHSAQPA-FJ shows a me- durn b m d band m the regon NX-3200 an-lwhch may be aw'gned to phenobc -OH s t r e t h g The phenohc -OH band IS not present m the sp&a of Cu(m polychelater T ~ I S lnd~cates the loss of phenol~c -OH and parhupahon of oxygen of the -OH p u p m metal mordmahon The absorpbon band around IMW17W on-' due to C=N of qumohe alro undergo a shlft, wluch IS due to N of q u o h e cmr h h n g wlth the metal

NI(Q polychelates show a strong band around 34W an-', and tfur band remam even when the polymer metal complexes were heated up to 19°C T ~ I S suggests coordmahon of water moleculn to

N I ~ ply(BH5AQPA-FJ shows strong bands at 1730 an- ' , wluch may be assigned to C=O of ester "-a The other absorphm are presented m Table Il

The 'H-NMR spgtnun of ply(BIi5AQPA-FJ (F% 1) charactenzed by a mulhplet around 6 5 7 6 ppm was due to aromahc protons, and the s ~ p l at 795 ppm m y be ass~gned to protons of Ar-OH The res- onance s~gnals at 185 and 2 2 ppm may be assigned to methylene and rnethme protons, mpechvely As the polychelatn were not soluble In common or- ganlc solvents, the 'H-NMR spectra of the polych~ latn were not reported

The fuse reflectance spectrum of Cu(ll) p l y chelate5 contam two bands, one at 14,800 an- ' and another at 22.W an", wluch may be ass~gned to d- d hansihon correspondurg to E,-Tzg translhon

In the electronic specha, the N I ~ chelate plymels arehc@&bytimebardsat99jOan ' , 1 5 7 ~ a n I, and 24,625 cm-I, whlch may be ass~gned to ' A ~ ~

TABLE PI ThumcpwKtrir DaU of Poly(8HSAQPA-Fl md Ih Metd Chelate

Tempramre (Ci mrrrsponds to

hP't T, ('C) 10 30 M 70 90 Char % at XXI C

Pdy(SH5AQf'A-Fl 165 98 2RO 420 490 MXI 0 P~~~MSAQPA-F)-~~(U) IBO 3% 1180 fm - 10 P ~ ~ ( U H S A W A . ~ N I ( U ) % za as 570 - 37

SYNTHESIS AND METAL W A K E STUDLES ON WLY(8HSAQPA-F) 801

Scheme 2 Spthes~s oi poly(8-hydroxy-Sazquolme phenylaaylate-fddehyde) rean and its CuINl com- plexes

- qW and Vwn - vlm ~ I ~ , ~e~pechvely GmeraUy, oadhedrd spm hee N I O mmplexes a h h t three bands m ther ele3mruc sp&a ""

Cum) polychelates have a mapehc moment of 175 BM, md~cahng square pianar conhgurahon The magnehc moment of 3 81 BM and the paramagnehc behanor of Nl(1I) complexes suggest distorted octa- hedral geometry for Nt(U) polycheiates '""

The X-ray d~ffrachon studies mdlcate that p ly(& HSAQPA-F) s amorphous whereas lb polychelates possess good crystalhne nature The ctystalim~ly m prlychelates may not be due to any ordenng m p l y (BHSAQPA-F) tnduced d u m g metal chelates anchor- "& more so smce anchomg of metab to polymer

would lmply mtercham awhkmg h e m p l y (8H5AQPA-FJ mterchams, wh~ch 6 h d d turther re duce rather h n enhance any such o~denng The a p warance of crvstaUmtW m WIVIBH~AQPA-F~ metal complexes may be b e c k df Aerent c & a l h e na- ture of the metalhc compounds

The TGA data for p l y (8H5AQPA-F) and p l y - chelaks are present@ m Table Ill The thermal ana- lyhcal data mhcate dist m poly(BH5AQPA-F) loss of welght b e p at 120°C and degradahon of the ply- mer OCM at W C whereas the polychelates were very stable up to 7WC, and th~s md~cate hgher thermal stablhty of the plychelatm compared wlth the parent polymer (Scheme 2)

The results of the batch eqrul~bnum study, carned out with the polymer sample of ply(8HSAQPA-F), are shown m the Flgure 2 From h study certam generahhons may be made about the behavlor of the polymer sample By keeping the concentrahon of Cum) and NI(U) hxed, when the pH of the soluhon was vaned, the resm showed lgher uptake percent- age of C u m and Nl(11) at pH 7 The amount of metal 10% taken up by the poly(8HSAQPA-F) In- creases w ~ t h the mcreasmg pH of the medium The m a p t u d e of the mcmse, however, s different for d~fferent metal cahons

Inlluence of elecbolytes on metal upuke

Table 1V reveals that the amount of metal Ions taken up from a gven amount of a polymer depends on the nature and concentrahon of the electrolyte pres-

TABLE N Ptreenbg Mttll Uptake of Poly(8HSAQPA-PI

w ~ l h D~ffennt Elatrolvtw at Dtffmnt pH

~ e h l ton pH (mol L") NsCi NaS04

cu2+ 3 001 n 3a 005 15 52 01 90 56

5 001 V9 710 005 852 80 01 W i9

7 001 95 % 005 96 % 5

;/;. ; , ; , ; , , , I N ? + 01 97 96

3 001 e4 40 005 81 42 0 1 82 46

5 001 83 71

a I I 005 86 79

I 01 88 82 W 7 001 853 90

Offi 35 92 Pigwe 2 McW ~rm uptake behav~or of poly(BH5AQPA-R 01 90 95 m n at dlterent pH

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€w3'ER Eumpcln Polymer Journal43 (2W7) 4 6 3 9 4 4 JOURNAL

Synthesis and chelation properties of new polymeric ligand derived from 8-hydroxy-5-azoquinoline hydroxy benzene

R Sankar, S. Vijayalakshmi, S Subramaman, S. Rajagopan, T. Kaliyappan '

8-Hydroxy-hzoqonohne phcnyl mcthacrylatbfonnaldehyde (BHSAQPMA-F) macromonomer was prepared from mcthaayloyl chlondc wth wndc~atlon products of 8-h)drox).S.w.cqumoltnc phenol-fonnaldchyde. and ~ l y m e d in DMF at 70 T using bcntoyl wrou& as free rad~cal ~nltlalor P~I~I~HSAQPMA.FI uas characvrucd br lnfrared and nuclear mapchc A n a n 6 s&troscop~c cechnlqucs Polychelata & c ob&cd when the DMF sohaon oithc rcsln wnmlnc fnu droos of ammoma was trcaled mth the aaueous solut~on of CullIl/N~(Ill Elemental anahs~s of thc miv- chelatea &at the metal to hgand taho was abouil 2 The 1R spsVa of ~olychclater s u m t the& metals'wck cwrdrnatcd through (he oxygen of the phenoltc-OH group and n~tro* of the qu~nolme hgand-The D R S and mapew moment data lndleate a souare olanar for Cullll wmolcx whereas anahedral for NU) mmolcr The TGA data re& the t h l ttab~hty of th; rend and the polych~latts'~-ray d~ffractlon study revealcd ;be lnkrporatlon of the metal lorn s~@l~fieantly enhanced the d e p of crystallln~ty The sorpuon propma of the chelare-fomg m~n towards vanous dlvalent mnal ions [Cull) and NI(II)] wm studled as a funn~on of pH and electrolyte O 2007 Elvvln Ltd All nghtr rescrvcd

In m t years there have ban a growing lnterest tn design and synthnts of polymer-metal wmplexes due to thnr s p a 1 properttes and potentla1 applica- tlons m mrpbon, waste water treatment, organlc synthesa, hydromctallurgy, catalysa and raovery of ma metal elements [I41 Polymer-metal wm-

plexes are m general word~nattng polymers contain. mg one or more electron donor atoms such as N, S, 0 and P that can form coordinate bonds \nth most of the toxlc heavy metals A polymeric Ilggand e usu- ally used to selecttvely b ~ n d a spx16c metal ion tn mtxtwe to isolate unporlant metal 1011s from waste- water and aqueous media One type that has been cxtens~vely used ln the separatron and p m n a n l r a - clon of metal ~ o n s 1s chelatmg Ion exchange m t n wth s@c chelattng group attackd to polymer [S-71 Among polymers tho% c o n t m q nltrogcn as donor atoms have been synthesmd and used m complexatlon of wansibon metal cations Various

Wl&M576. ar fma mnm 0 lW7 Blrmn Ltd All nghU nscr dog I0 l O l f 4 ~ n u ~ ~ k W l M 0 1 5

Author's personal copy

nitrogen containing ligands such as salicylaldimi- nate derivatives (83, oligoethylcneimine 193, vinyl- m i n e 1101 imidazok derivative [Ill quinoline [I21 have been uscd in preparation of rains.

8-Hydroxy quinoline ( o ~ n e ) is a ligand whose reactivity towards metal ions is well known from the literature [13,14] and it is widely uscd as wm- pkxing agents. Sighai et al. described the kinetic parameters of Ni(I1) and Cu(I1) chelate with 8- hydroxyquinoline 1151. The intcrsction of heavy metal ions and 8-hydroxy quinoline wuld be used to enrich the heavy metals in water and their analy- sii [Ib]. Mannich polymers containing 8-hydroxy quinoline as the pendant chelating agent with d ier - ent spam groups possessed good chelating proper- ties at pH v d w gnater than 6 1171. The SchiR basc transition metal complexes are a family of attractive oxidation catalysts; Sivagamasundari and Rameh synthes i i Ru(I1) complexes containing bidentate schiffs bases and studied their catalytic activity towards oxidation of organic substrates in the pres- ence of N-methylmolphol'ie.N-oxidc [IB]. In wn- tiuation of our interest in synthesis of new quinol'ie m d s 119-223, we describe herein the synthesis of new azo based quinoline ligand and its chelate forming ability with various divalmt metal ions at different pH and electrolyte.

h y l p e r o ~ d e (Ruka) was nerystalliscd from chlorofonn/mnhanol mixture. 8-Hydroxy quinol'ie (Fluka) was r s r y s t a l l ' i from methanol. Methac- ryloyl chloride was prepared by the reported proce- d u n 1231.

2.2, Synrhuir of 8-hydroxy-krroguinoline hydroxy benzene

8-Hydroxyquinol'ie (4.35 & 0.03 M) was dis- solved in wnc. HCI (20 ml) and kept below 5 'C in an ice both. pAmiiophenol (3.27 g. 0.03 M) was dimlvcd in wnc. HCI (201111) by heating and the solution formed was woled down quicldy to a tempentun blow 5OC with vigorous stirring to obtain a loiutiw. To hii solution was added sodium nitrite (2.55 & 0.03 M) in 20ml of water. A h airfins at 0-5 'C for 30 min a yellow solution was obtained. To hii 8-hydroxyquinolie solution Was added slowly whik 8tining. Thc mixture was

then s t i d for half an hour and then neutralized with saturated N a g 0 1 aqueous solution. Thc prod uct pwipitaud out from the solution and was collected by filtering (7 & yield 80%) of 8-hydroxy- 5.azoquinoline hydroxy bnuene was obtained after rcnystdlising the crude product from ethanol [24].

2.3. Synfhesu of 8-h)Woxy.S-a:oquinoline phenol. formaldehyde

A mixtun of 1:2, 8-hydroxy-5-azoquinolinc hydroxy bnuene and 37% formalin solution, and 3°/4W/W) of oxalic acid were placed in a round-bot- tomd Bask, scaled and kept in an oil bath at I00 'C for 24 h. The flask was then woled to room temper- ature, desealed and water was decanted. The solid remaining in the Rask was dissolved in NJ- dmethyl formamide and the resulting solution was added drop wise to large e x w of 1!Yh aqueous sodium chloride solution with constant s i i g and the red compound was filtered washed several t i e s with distilled water until free of chloride ion and dried at 60 'C in Vacuo. Yield: 83%.

2.4. Synthesir of 8-hydroxy-5-a:oguinoline phmyl mefhacrylale-formaldehyde (BHSAQPMA-F)

8-Hydroxy-5-azoquinolinephenol-formaldehyde (8HSAQPF) (2.6 g, 0.02 M), triethylamine (2.78 ml, 0.02 M), hydroquinone (0.5 g) and DMF (25 ml) were t a k a in a three necked flask equipped with a stirrer, thermometer and separating funnel and the wntents were cooled to 0 to -5 TC. Mcthacryloyl chloride (1.8 ml, 0.02 M) was added drop wise with constant stirring at that temperature. The reaction mixture was then s i i for another 2 h at room temperature and the quaternary ammonium salt was hltnrd off. The Gltrate was thomugbJy washed with distilled water, d i d over anhydrous sodium sulphate and the solvent was m o v c d to get a solid. The IR and 'H NMR spxtra were consistent with the assigned structure. Yield: 7%

8-Hydroxy-5-azoguinolim phmyl methacrylate- formaldehyde (3.5 M) in DMF and bmoyl p m x - ide (0.5 g) wm taken in a standard rraction tube and deaerated by passing oxygen fm nitrogen for 30 min. The reaction tube was closed and kept in a thermostat at 70 T for 8 h. A large cxcarr of methanol wss added to the contents and the p m i p

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itated poly(8HSAQPMA-F) was filtered, washed with methanol and purified by N.Ndiiethy1 form- amide/methanol mixture. Polymer was dried under nduced pressure at 60'C for constant weight. Yild: 77%.

2.6. Synthesis of poly(8HSAQPMA-F)-merol chelntes

Polymer metal chelatcs were prepand at room temperature by solution technique. A typical proa- dure for the preparation of polymer-Cu(I1) chelate was as follows. Poly(8HSAQPMA-F) (5mmol of repeat unit) in DMF (75 ml) and the pH of the solu- tion was adjusted to 7 with dilute ammonium hydroxide. An aqueous solution of Cu(I1) acetate (2.5mmol) was added drop wise to the polymer solution with conslant stirring. The mixture was then digested on a water bath for 2 h and kept over night at room temperature. The precipitated p l y - (BHSAQPMA-F)-metal complex was filtered, washed with hot distilled water, followed by metha- no1 and dried at 60 T i n vacuo. A similar procedure was adopted for the preparation of Ni(1I) chelate. Yield: 83% for Cu(1I) and 81% for N(I1).

2.7. Trms~tion metal ion selecriuity of poly(BH5AQPMA-F) o f dperent pH

The optimum pH of the metal ion uptake was determined with a hatch equilibration technique. Excess of metal ions Cu(lI)/Ni(II) (IOml, 0.1 M) were shaken with 25 mg of the resin for 24 h. The pH of the solution was adjusted before equilibration ovcr a range of 1-10 with weak acidbase. The pre- apitetcd complex was Gltned OK, and the wnccn- tration of the Cu(I1) ion remaining in the filtrate was determined by iodomevically and Ni(I1) by gravimetrically.

2.8. Trmirion metal ion seleclivity of poly(8HSAQPMA-F) in the presence of elecfrolyfes

The polymer sample (25 mg in 25 ml of DMF) was added in an e l m l y t i c solution (25 ml) of a known wnanuation. The pH of the solution was adjusted by using 0.1 M HCI or 0.1 M NH,. The s o l u t i ~ was stirrcd for 24 h s t room trmperature. To this solution lOml of 0.1 M solution of metal ion Cu(IIm(ll) was added and the pH was adjusted to the rcquircd value. The mixture was again a t i d at 25 T for 24 h and filtered. The solid

was washed and the Cu(I1) ion content was deter. mined iodimctricallly and Ni by gravimevically. The amount of the metal ion uptake of the polymcr was calculated from the diBmna between a blank experiment without the polymer and the m d m g in the actual e x p h e n t s . The experiments w a e d o m e d in the prseoce of several ekctrolyts with Cu(I1) and Ni(I1) ions.

IR spectra were recorded on a Bomm MB 104 R - I R spcctrophotometer using KBr pllets. The 'H NMR spcrra were nmrded on a JEOL-GSX 400 MHZ spectrometer in dmterated DMSO as sol- vent us'ing TMS as internal standard. The molecular weights (M, and M.) were determined by gel per. meation chromatograph (Waters model 401). The C, H and N wntents were determined with an Ele- mental analyzer (Elementar, vario EL, Hanau, Ger- many). The viscosity measurements were made in THF at 30 'C with an Ubbelohde suspended level vixometer. The magnetic moments were deter- mined by Guoy method and corrected for the dia. magnetism of the components using Pascal's constant. The diffuse retlectance spectra (500- 2000nm) were measured on a Varian Caly 5E UV-vis-NIR spcctrophotometer. X-ray di&action experiments were performed in Phiiips PW1820 dif- fractometer. The thermo gravimetric analysiis of the polymer was performed on a Mettler 2OOO TA ther- ma1 analyzer.

3. ResultP and discussion

The macromonomer (11) containing polymeriz- able vinyl goup was synthesized from S-hydroxy- 5-azoquinoline hydroxy benzene (I) and formaldehyde in the presence of oxalic acid. The macromonomcr (111) was polymerized in DMF medium using bm. zoyl peroxide as f r e radical initiator with a good yield (Scheme I). Polymer-metal complexes wcre obtained in DMF containing polymer in an aqueous solution of metal ions Cu(I1) and Ni(I1) in the pres. en= of a few drops of ammonia The polymers were soluble in DMF, THF, aMJ DMSO, and insolubk in common organic solvents like benzene, toluene, methanol, and water. AU the polychelatcs were sparingly soluble in THF and DMF. The elemental analysii data for polymers and polymer-mtal com- plexes w m presented in Table I. Theelemental data

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suggest that the metal to polymer ratio wasl:2 and it was in good agrerment with the calculated values.

The intrinsic viscosity [IT] was obtained by extrap- olating q,JC to p r o concentration. The intrinsic v~scosity of ply(8HSAQPMA-F) was found to be 0 .64d~g-I . The results reveal that the polymer was moderately high molecular weight. The number average molsular weight (M,) and weight average molecular weight (M,) of the poly(BH5AQPMA- F) were determined by gel permeation chromatogra- phy uing tetrahydrofuran and were M. = 1 . 8 5 ~ 10'; M, = 3.96~ 10'. The polydispersity index (M,/M.) for polfi8HSAQPMA.F) is 2.1. The result was in aocordanet with the viscosity value. The the-

oretical value of MJM. for polfi8HSAQPMA.F) suggests a strong tendency for chain termination by radical recombination.

The IR spenra of pdfi8HSAQPMA-F) and its polychclates were shown in Fig. 1. The medium absorption band in the region 3400-3000 an-] mr- responds to phenolic-OH stretching. The phenolic- OH stretching disappears in the spectra of polyche latcs, indicating aordination. NiII) polychclate show a strong absorption band in 3250 cm-I owing to coordination of water mol& to metal ions [25,26]. This band remains even when the polyche lates were heated upto 1% "C, poly(BH5AQPMA- F) shows strong bands at 1745cm-I and 1163 an-', which may be assigned to CEO ester and C-0 esteric groups, respectively. The band around 725 an-' and 525 cu~'corresponds to metal-nitro- gen and metal+xygcn vibration. nc IH-NMR s p e c t ~ m of p ~ i y ( 8 ~ ~ ~ ~ ~ ~ ~ . ~ )

(Fig. 2) characterized by a multiplet around M.M was due to aromatic protons, and the signals at

Fig. I IR rpstra of (a) p l y poly(8HJAQPMA.F). (b) poly- (8HSAQPMA-F)CU(II) md lc) ~~~(SHSAQPMA.F)-NI(II).

Tlbk l h m u l d y l L 81. of poly(8HJAQPMA.F) and iU mctnl cornpluea

Abbnnbo. Empirical fornula Elerncntnl pnslysk (weight prcml) m a Hydrogen O l y m Natmm M r ~ l

01.' Fd. ~ d . ' Fd. c.I.' Fd. &I.' Fd. w.' Fd.

POlfi8HSAQPMAF) ( C B H I P I N J ~ 69.51 6955 4.35 4.39 13.91 13.88 12.11 12.18 - - P o M 8 H S A Q P M A ~ l I ) (Cdo4@N4N$.CU(Il) 58.9 58.55 3.43 3.51 11.78 12.05 10.31 10.22 15.58 15.68 Poly(8HSAQPMAP).Nin) C~I@,NI) ,~Ni i l l ) (H@), 5704 56.99 3.80 3.W 15.22 15.18 9.98 9.94 13.96 13.99

p u p of C. H, N, 0 md motnl iw, for polymer-mcul mmp*rm buad on the nh. of r = y - 2 found: x r 2.02, Y-2.01.

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9.256 may be asrigned to protons of AI-OH. The rmwce signals at 4.2 and 2.96 may be assigned to methykne and methine protons, respxtively. As the polychelatcs were not soluble in common organic solvents, the 'H-NMR spectra of the ply- chelatu wore not rrportcd.

The di5uae reflectance spectra of Cu(1I) and Ni(I1) polychelatcs wcrc shown in Fig. 3. The e l w tronic spectrum of Cu(I1) polychelates contains two hands, one at 15,050~11-' and another at 22.150cm-', which may be assigned to 6d transi. tion wmsponding to E, - T2, transition. A square planar conhguration may bc tentatively assigned for Cu(I1) plychelate in the present casc [27]. In the electronic spectra, the Ni(l1) polychelate shows three bands at 23.500 an-' , 15,150 cm-I, and

Fag 2 'H NMR ipDtrvm of ply(8HJAQPMA-F)

9,950m", which may be assigned to 3 ~ 2 a p , - 3T2d.9 and 'Tzdn - 'Tla,, transitions, respec- tively. Genemlly, octahedral spin free Ni(I1) com. plexes exhibit three bands in their electronic spectra [28,29].

Magnetic susceptibility measurements of transi- tion metal complexes give an indication of the geometry of the li&ds around the central metal ion. The Cu(I1) polychelate had a magnetic moment of 1.82 BM which fall in the normal range (1.75- 2.20 BM) expected for magnetically dilute Cu(I1) complexes, indicating a square planar configuration [30]. The magnetic moment of 3.92 BM and the paramagnetic behaviour of Ni(I1) complexes sug- gest a distorted octahedral geometry of the Ni(I1) polychelate [3 1,321.

The X-ray diiiractogram of pob(8HSAQPMA. F) and its c~(I I ) /N~(~I) c o m ~ l e x ~ s were shown in Fig. 4. The X-ray diffraction indicated that poly(SH5AQPMA.F) was amorphous, whereas their polychelates possessed good crystallinity. The crystallinity of polychelates may not be due to ordering in polymer induced during metal chelates anchoring, more so, since anchoring of metals to the polymer would imply inter chain cross-linking between polymeric chains, which should further reduce rather than enhance any such ordering. The appearance of crystallinity in polychelatcs may be due to the inherent crystallime nature of the metallic compounds.

The TGA traces of poly(SH5AQPMA-F) and its Cu(1I) and Ni(I1) complexes were shown in Fig. 5.

ifyq i ' I

lam urn, *,m yrrm zrm w W.n-lm.I) Fi. 4 X-my d i k t o p m af (a) pMSHSAQPMA.F), (b)

Fis 3. DRS l p ~ m of (n) poly(SH5AQPMA.F~~l l ) md (b) ply(SHSAQPMA.n.Ni(l1) and (c) ~OI~(SHSAQPMA-P> pdHlH5AQPMA.F)- N111). CNll).

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The transition tcmpcratw (Td for ply(8- HSAQPMA-F), ply(8HSAQPMA-F)-Ni(I1) and poly(8HSAQPMA.F)-Cu(11) w8s found to be 175, 355 and 390 "C, respectively (Fig. 6). The diaemcc in transition may be ascribed to the crystallinity of the polymer-metal complexes and is in aocordancc with the X-ray diffraction study. Loss of weight begins at 140 *C and the degradation ofthe polymer occurs at 700 OC whereas the polychelates were very stable up to 7W°C and this indicate higher thermal stability of the polychelatcs compared with the par- ent polymer. Cu(I1) polychelares are found to be more stable than Ni(I1) polychelatcs. The 1R. NMR, magnetic moments, elemental analysis of

Ftp. 5 TGA miva of (I) poly(8HSAQPMA.F). (b) p l y . (IIHSAQPMA-FkNi(11) sad (s) poly(8HSAQPMA.F)Cu(11)

Fig. 6. DSC a m of ( I ) poiy(SHJAQPMA.F), (b) p l y . (IIHSAQPMA.F)-CqI) md (e) polfi8HJAQPMA-FkN(lI).

Scheme 2. Synrheals oi polfi8-hydrory.5-uaqwnohe phmyl mnh.crylau-formddchyds) mlo and its Cu(ll)iN~(lI) wmplnct

the polychelatcs and the structure of the polymeric ligand, it appears that the chelation of metal ions may occur between two groups from d117ercnt poly- meric chains as shown in Scheme 2.

3.1. Effect of pH on metal ion uptake properties

The effect of pH on the metal uptake of the chc. luting agents on sold polymeric materials is a very important parameter. Ionization of the chelating ligand and the stability of the metal-ligand com- plexes vary when changing the pH. Fig. 7 shows a typical bebaviour of pH-sensitive polymer. In gen- eral, the metal uptake was seen to aignifimtly increase with incnasing pH [33]. Thii refull a u l d be explained by metal-ion competition with protons at varying pH; when the pH increased, the e l m o n pair of the nitrogen of quinoline ligand from p l y - (8HSAQPMA.F) was more available to interact with the metal ions. Similarly; at higher pH, thearo- matic -OH prmntcd a higher metal-ion atfinity to form polymer-metal complexes. Complex stability depends strongly on the pH, at low pH, where the majority of the quino'nc groups arc protonated, the metal-ion a b i t y is poor and the complex s o - bilily is low. As the pH increases, the &ly and stability of the polymer-metal complexes incrwcs. The magnitude of b r e ~ s c , however, was different for different metal cations. Thc results indicate

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on the n a t w and conccn~ation of the elcctrolytc prmnt in the solution. In the presence of chloride and sulfate ions the uptake of Cu(I1) and Ni(11) ions increases with an increasing concentration of the electrolytes. This o h t i o n can be explained on the bask of the stability constant with these metal ions [34,35].

3.3. Resin regenenpion

To be viable material for chelation system, the resin must be chemically stable The poly(8 :k , , , , , , , HSAQPMA-F) 7 M HCI. Polychelates could easily were placed be regenerated in a desorption with

sa medium and stirred for 2 h at room temperature.

Fil. 7. Mstl ioo uptake bshavlow of poly(8HSAQPMA-F) The defheiated polymcr undeKWmt complexation

m m at diamnt DH. with the original efficimcy. To obtain resin reusabil- ity, the sorption-dcsorption cycle war repeated four times with the same adsorbent. More than 95% of

Cu(1I) was absorbed selectively to the higher extent ~ l p " ~ f ~ e ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ 2;: over the pH range. ity of the polymer under acidic conditions.

3.2. Inpucnce ofelectrolytes on rneral ion uptoke g, c m c l h properties

A resln ,gHSAQPMA.Fj based on condensat~on Table 2 reveals thdt the Ions reaction of 8-h~drox)-5-azoqumohnc phenyl meth-

Iden UP froma P e n O f a pol'mcr acrylav \nth formaldcb)de m rhc presence of oxaitc acid catalyst has been synthesized and metal com-

PaernUsc M r U Upuks dpoly(8HSAQPMA-Fl wth d~Lreal alarol)m at diliermt pH

McUl ion pH Ehtrolpe (mol L ') Pemntapc of the mMI tan tnkcn up m

plexes were prepared. These complexes have been characterized and were assigned a metal to ligand ratio of 1:2. The prepared ligand possessed high thermal stability which shows good chemical stabil. ity that facilitates thcchelation at neuml pH values. The thermal stability ofpolymcr and itspolychelates follows the order poly(BH5AQPMA.F)-Cu(lI) > poly(8HSAQPMA.F)-N$n) 2 poM8HS-AQPMA-F). The above mentioned results strongly recommend the use of the prepared polymeric ligand in metal ion removal of study of Cu(1I). Finally, it may be concluded that the ion-exchange ability of this poly- mer with various divalent metal ions in an aqueous medium at pH 6 and above could be effectively used for the removal of heavy metals from water and wastewater.

The authors thank SAIF, IIT, Chennai (Ma- dras), India for providing instrumental facilitia. One of the authors (T.K) is grateful to DST, Gov- ernment of India for the award of young scientist.

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Ref-

[I] KILylpprn T, Kmnm P Rog Polym Sn 2W0,25 343 I21 Flm RC. Zukeu 1 laorg Chnn 2MI.U) 2466 [31 bnupvly C. KItra iadh S, Chaw A. O w c r HD Tnlanta

1990.37 491 141 Akchh A. Shemagon DC Chsm Rcv 1981.81 557 [51 Rlvw 81, M u o z C J Appl Polym Sn 2037,104 1769 I61 E b n h m M K . Hamdl ST Rcrcc Funa Palym 1997.34 5 [7] LLyrpprn 1. S w m ~ m t h m CS. K w a n P Bur Polym J

1997.33 59 [8J Alcllo I, O h d m M, Zenchmn C lnorg a m Acta

19992% 133 (91 T r o c h ~ m d A. Kolvr EN, W a ~ a q a s k a M Rcsst Polym

1988.7 197 (101 JMW L, Momllet J, Dclporv M, M o m l k M Eur Polym J

I'R218 IIR5 - ... . . . [I 11 Van k k c l PM. DnPvn WL. K o d h w GJAA, Rcldllk J,

Shrmnoon DC J Chcm Soc Chcm Commun 1995 147 [I21 K a h y a p p ~ 1 , Anupnya R, K p m n P J M m Sa Purr

Appl C h m 1999,A36517 (131 Phdllp. IR Chrm Rev 1956,552721 1141 Parnah JR Ann Chcm 1982.54 18% 1151 Mlahrs. AK. T1w.n VK, Sm&i R lndkan 1 Chrm

2M2,41A 2W2 1161 Llu X, Zhun D. Chsng D C h m Abtr 2W0.133 3474h 1171 Sslm NM, E b n h a n KAK. Mutarak MS Reset Funcl

Polm 2W.59 63

[I91 V ~ y W h r m S. Suk- S, I U j a p w S, Ka11yapp.n T J Appl Polym Sn 2W6,99 1516

D l Vl~nyahkahm~ S, Subrunvllan S, I U ~ a g o w S, Wlysppsn T J Appl Polm Sn 2W6.101 1546

I211 V~~aynlJrshmt S. &nku R. Subnmsm S. R q a ~ o p n S. Kal!yrppm T Dm Monomer8 P o l p UYM.9 425

I221 Vl)lys!&hl S, & n h R, Svbramuuan S, R~).(opln S, Ksllyappm T J Appl Polym SCI 2007,104 797

P31 Stempel GH, C r a s RP, Mnnclla RP 1 Am Chcm S a 1950.72 2299

[24] Mang X. Ntiaa~olm A. Rochon P Supnmol sa 1996.3 4207

1251 Nakmalu K l a f n n d A h r p i ~ o n S p x r o m p y 2 cd Nakdo, Japan, 1964

[261 Fmdmnn HN J Am Chcm S a 1%1.93 29M I271 Paul Mshcndrs R, Paul MR, Paul MN J Mmomal Sa

Chcm 1986,23 1503 1281 Flgg. BN Introdunlon lo Ltgmd Flclds, Vol 2 New

yark Wlley Intcrsamce. lW2 I291 Man& W, Femollas WJ J C h m Soe 1961.38 192 001 SsrLsr AR, Bandyopsday RK Synth R a n loor M a Org

Chcm 1990,20 167 [31] Hahswsy BJ J C h m Soe A 1972 11% I321 El-Sonbss AZ. Hcfnl MA Polym Dcg Stab IW4,43 33 1331 DN K, R m GN Tslanta 1996,43 451 1341 Pakl BS. Paul SR Makromol Chcm 1979,180 1159 1351 Pakl HS. Paul SR J M~kmmol Scl Chnn 1982.106 1383