Synthesis, Characterization and Dielectric Behavior of (4- Diethanolaminomethyl Styrene-co-Benzylmethacrylate) Polymer and Its Co (II), Ni (II) and Zn (II)-Metal Complexes

Yıl 2018, Cilt: 18 Sayı: 3, 820 - 832, 30.12.2018

Aslışah , Açıkses Fethiye Öksüz

Öz

In this study, 4-diethanolaminomethyl styrene (DEAMSt) and benzyl methacrylate (BMA) copolymer were synthesized. The synthesized copolymer was characterized by spectral techniques such as FT-IR, 1H-NMR, Elemental analysis, SEM, XRD, DSC and TGA. This copolymer obtained is used as ligand and its metal complexes were prepared with Co (II), Ni (II) and Zn (II) metal ions. The copolymer-metal complexes were characterized by the above spectral techniques. In addition, magnetic measurements of copolymer-metal complexes were received. The geometric structures of the copolymer-metal complexes according to magnetic measurements were estimated that have a tetrahedral geometric structure. The ligand was found an amorphous structure and metal complexes were found to be crystal structure by XRD analysis. The composition of the copolymer was determined by 1H-NMR spectra and the composition of
DEAMSt% was found as 23%. The average molecular weights and polydispersity index of the (DEAMSt0.23-ko-BMA) polymer were determined by gel permation choromatography. Glass
transition temperature and thermal behaviors determined by DSC and TGA. The dielectric properties of ligand and copolymer metal complexes were investigated as a function of frequency.

Anahtar Kelimeler

Copolymer-Metal, Ligand, Complexes, Dielectirical, Properties, Copolymer, Magnetic, Measurements

(4-Dietanolaminometil Stiren-ko-Benzilmetakrilat) Polimeri ve Onun Co(II), Ni(II) ve Zn(II)-Metal Komplekslerinin Sentezi, Karakterizasyonu ve Dielektriksel Davranışları

Öz

Bu çalışmada, 4-dietanolaminometil stiren (DEAMSt) ile benzil metakrilat (BMA) kopolimeri sentezlendi. Sentezlenen kopolimer FT-IR, 1H-NMR, element analizi, SEM, XRD, DSC ve TGA spektral teknikler ile karakterize edildi. Elde edilen bu kopolimer ligand olarak kullanılıp Co(II), Ni(II) ve Zn(II) metal iyonları ile metal kompleksleri hazırlandı. Kopolimer-metal kompleksler yukardaki spektral teknikler ile karakterize edildi. Ayrıca kopolimer-metal komplekslerinin magnetik ölçümleri alınarak metal komplekslerin tetrahedral yapıya sahip olduğu görüldü. XRD analizi ile ligandın amorf, metal komplekslerinde kristal yapıda oldukları bulundu. Kopolimerin bileşimi 1H-NMR spektrumu ile tayin edildi ve DEAMSt % bileşimi % 23 olarak bulundu. Jel Geçirgenlik Kromotografisi (GPC) ile (DEAMSt0.23-ko-BMA) polimerinin ağırlıkça ortalama molekül ağırlığı ve heterojenlik indisi tayin edildi. Camsı geçiş sıcaklığı ve termal davranışları, DSC ve TGA ile belirlendi. Daha sonra ligand ve kopoolimer-metal komplekslerinin dielektriksel özellikleri frekansın bir fonksiyonu olarak araştırıldı.

Anahtar Kelimeler

Ligand”, “Polimer-Metal Kompleksi”, “Dielektiriksel Özellikler”, “Kopolimer”, “Magnetik Ölçümler”

Kaynakça

• Açıkses, A., Çömez, N., Biryan, F., 2018. Preparation and characterization of styrene bearing diethanolamine side group, styrene copolymer systems and their metal complexes, Hindawi International Journal of Polymer Science, Vol. 2018, Article ID 6703783, 1-5.
• Açıkses, A., Taşkan, G., Barım, G., 2018. A study on copolymer systems of styrene with diethanolamine side group and methyl methacrylate’’, Hindawi J. of Chemistry, Vol. 2018, Article ID 8957267, 1-12. Acosta, J.L., Morales, E., 1996. Ionic conductive polymer systems base polyether and polyphosphazene blends“, J. Appl. Polym. Sci., 60, p. 1185.
• Alexandratos, S.D., 2007. New polymer-supported ion-complexing agents: Design, Preparation and metal ion affinites of immobilized ligands, J. of Hazardous Materials, A139467-470.
• Amanda, N.P., Spiro, D.A., 2010. Engineering selectivity into polymer-supported reagents for transition metal ion complex formation, Reactive & Functional Polymer, 70, 545-554.
• Bamaszal, L., Weston, J. C. and Kendrew, J. C., 1965. On the nature of allosteric transitions: A plausible model, J. Mol. Biol, 12, 130.
• Belekere, N.N., Misra, S.C.K., Ram, M.K., Rout, D., Grapta, R., Malhatra, B.D., Chandra, S., 1992. Interfacial polymerizatin in semiconducting polypyrole thin films, J. Phys., Condens Matter, 4, 5747-5756.
• Bello-Vieda , N.J., Murcia, R.A., Castro, A.M., Macías, M.A. and Hurtado, J.J., 2017. Coordination polymers containing 1,3-phenylenebis-((1H-1,2,4-triazol-1-yl)methanone) ligand: Synthesis and ε-caprolactone polymerization behavior, Molecules, 22(11), pp.1860.
• Bilici, A., 2009. Oksidatif polikondenzasyon İle aromatik halkalı azometin polimerlerinin sentezi ve karakterizasyonu, Doktora Tezi, Ankara Üniversitesi Fen Bilimleri Enstitüsü, Ankara, 125.
• Botros, S.H., Abd-El-Ghaffar, M.A., Eid, M.A.M., 2006. Synthesis of polymer-metal complexes and their effects on dielectric properties and ageing and UV resistance of SBR vulcanizates, Polymer-Plastics Technology and Engineering, 45, 1347-1355.
• Cazacu, M., Marcu, M., Vlad, A., Rusu, G.I., Avadanei, M., 2004. Chalete polymers. VI: New copolymers of the some siloxane containning bis(2,4-dihydroxybenzaldehyd-imine)Me2+ with bis-(p-carboxyphenyl) diphenylsilane, Journal of Organometalicl Chemistryl, 689(19), 3005-3011
• Coşkun, M.F., Demirelli, K., Güzel, D., Coşkun, M., 2002. Free-radical copolymerization of 3-phthalimido-2-hydroxypropyl methacylate with styrene: The determination of monomer reactivity ratios and thermal analysis studies, J. of Polymers Science: Part A: Polymer Chemistry, Vol. 40, pp. 650-658, 2002.
• El-Arnaouty, M.B., Abdel Ghaffar, A.M., Eid. M., 2013, Proporties of grafted polymer metal complexes as ion exchangers and its electrical conductivity, Polymer Engineering and Science, DOI 10.1002/Pen, 790.
• El-Sonbati A.Z. and Hefni, M.A., 1994. Polymer complexes. Part XXVI—Novel mixed ligand poly-(5-vinyl salicylidene)-1,2- diaminobenzene complexes, Polymer Degradation and Stability, Vol. 43, No. 1, pp. 33–42.
• Gao, B., Wei, X. and Zhang, Y., 2013. Synthesis and luminescence properties of polymeric complexes of Cu(II), Zn(II) and Al(III) with 8-hydroxyquinoline side group-containing polystyrene, Optical Materials, vol. 35, no. 3, pp. 536–542.
• Golikand, A.N. and Didehban, K., 2010. Preparation and characterization of polymer/multiwall carbon nanotube/ nanoparticle nanocomposites and preparation of their metal complexes. Journal of Applied Polymer Science, Vol.118, 113-120.
• Gurnule, W.B., Juneja, H.D., Paliwal, L.J., 2000. Ion Exchange Properties of 8-Hydroxyquinoline biuret-formaldehyde tercopolymer, Ind. J. Chem., 39, pp. 1113–1120.
• He, Y., Wang L. and Cai, C., 2011. Diethanol amine-functionalized polymer-supported palladium (0) complex as catalyst for Suzuki cross-coupling reaction in water,” Journal of Applied Polymer Science, vol. 121, no. 1, pp. 286–291.
• Iseid, S.S., Kuehn, C.G., Lyon, J.M. and Merrifield, R.B., 1982. Specific peptide sequences for metal ion coordination. 1. Solid-phase synthesis of cyclo-(Gly-His)3, J. Am. Chem. Soc., 104, 2632, 2.
• İyibakanlar, G., Oktay, A.,2007. Bazı Polimerlerin Dielektrik Özelliklerinin Frekansla Değişimlerinin İncelenmesi, Havacılık ve Uzay Teknolojileri, Cilt 3, Sayı 1, 11-19.
• Kaliyappan, T., Swaminathan C.S. and Kanan, P., 1996. Synthesis and chracterization of new metal chelating polymer and derived Ni(II) and Cu(II) polymer complexes, Polymer. Vol: 37. No: 13, 2865-2869.
• Kimura, H., Murata, Y., Matsumoto, A., Hasegawa, K., Ohtsuka, K., Fulkuda, A., 1999. J. Appl. Polym. Sci., 74, pp. 2273-2279.
• Kliyappan, T., Rajagopan, S., Kannan, P., 2004. New polymeric schiff base and its metal complexes’, Journal of Applied Polymer Science, Vol. 91, pp. 494-500
• . Lee, E. and Jeong, Y.G., 2015. Electrical and dielectric properties of poly(1,3,4-oxdiazole) nanocomposite films with graphene sheets dispersed in layers, Fiber. Polym, 16, pp. 2021.
• Mamdouh, S.M., Azza, E.H.A., Wael, M.A., 2015. Synthesis and characterization of sometransition metals polymer complexes, Journal of Molecular Structure, 1095, pp. 135-143.
• Park, H.H., Choi, Y., Park, D.J., Cho, S.Y., Yun, Y.S. and Jin, H.J., 2013. Enhanced dielectric properties of electrospun titanium dioxide/ polyvinylidene fluoride nanofibrous composites, Fibers Polym, 14, pp. 1521–1525.
• Rahangdale, P.K., Gurnule, W.B., Paliwal, L.J., Kharat, R.B., 2003. Chelation ion–exchange properties of copolymer resins derived from 2-hydroxyacetophenone, oxamide and formaldehyde, Synth. React. Inorg. Met. Org. Chem., 33, pp. 1187-1205.
• Raja, Z., Sharma, A.K., Narasimha Rao, V.V.R., 2004. Inpadence Spectra and dielectric analysis of PMMA-co-P4VPNO polymer films, Materials Letters, 58, 3242-3247, 2004.
• Rivas, B.L., Seguel, G.V. Ancatripai, C., 2000. Polymer-metal complexes: Synthesis, characterization, and properties of poly (maleic acid) metal complexes with Cu(II), Co(II), Nİ(II), and Zn (II), Polymer Bulletin, 44, 445-452.
• Sahni, S.K., Bennecom, R.N., Reedijk, J., 1985. A spectral study of transition-metal complexes on a chelating ion-exchange resin containing aminophosphonic acid groups, Polyhedron, Vol. 4, Issue 9, pp. 1643-1658.
• Sebastian, N., George, B., Mathew, B., 1998. Metal complexes of poly(acrylic acid): synthesis, characterization and thermogravimetric studies, Polym. Degrad. Stab., 60:371–375,
• Seoudi, R., Nada, A.M.A., 2007. Molecular structure and dielectric properties studies of chitin and its treated by acid, base and hypochloride, Carbohydrate Polymers, 68. 728-733.
• Serttekin, S., 2009. Etilendiamin içeren Ni(II), Co(II), Cu(II) sentezi ve yapılarının aydınlatılması, Yüksek Lisans Tezi, Çukurova Üniv. Fen Bilimleri Enstitüsü, Adana. Seven, P., Coşkun, M., Demirelli, K., 2008. Synthesis and characterization of two armed graft copolymers prepared with acrylate and methacrylate using atom transfer radical polymerization, Reactive and Functional Polymers, Vol. 68, pp. 922-930.
• Shahada, L., El-Toukhy, A., Abu-Raqabah, A.T., 1997. Synthesis and characterization of a new chelating polymer and its metal complexes, J. Of Molecular Catalysis A: Chemical, 115, 61-72.
• Sherrington, D.C., Hodge, P., 1988. Syntheses and Separations Using Functional Polymers, Published by John Wiley & Sons, New York. Shinichi, N., 1996. Sumitomo Bakelite Co. Japan, Jpn, Kokai, Tokkyo JP 08, 143(1) 750–770.
• Singru, R.N., Gurnule, W.B., Khati, V.A., Zade, A.B., 2010. Dontulwar, eco-friendly application of p-cresol-melamine-formaldehyde polymer resin as an ion-exchanger and its electrical and thermal study. Desalination 263, 200-210.
• Smitha, B., Sridhar, S. and Khan, A.A., 2005. Solid polymer electrolyte membranes for fuel cell applications, A Review, J. Membr. Sci., 259, 10.
• Sun, C., Qu, R., Ji, C., et al., 2006. Preparation and adsorption properties of crosslinked polystyrene-supported low-generation diethanolamine-typed dendrimer for metal ions, Talanta, vol. 70, no. 1, pp. 14–19.
• Syrlybaeva, R., Movsum-zade, N., Safiullina, I., Puzin, Y. and Movsum-zade, E., 2015. Polymer-metal complexes of polyacrylonitrile and its copolymers: synthesis and theoretical study, Journal of Polymer Research, Vol. 22, No. 6, 2015.
• Takemoto, K., Ottenbrite, N. M. and Kamachi, M., 1997. Functional Monomers and Polymers, Marcel Dakker Inc., New York. Vinodh, R., Ilakiya, A., Elamathi, S., Songeetha D., 2010. A novel anion exchange membrane from polystyrene (ethylene buthylene) polystyren: Synthesis and characterization. Materials Science and Engineering B.167, 43-50
• . Wu, G.M., Lin, S.J., Yang, C.C., 2006. Preparation and characterization of PVA/PAA membranes for solid polymer electrolytes, Membr. Sci., 275, 127.