Preparation and characterization of some transition metals complexes with styrene containing diethanolamine side groups and benzyl methacrylate copolymers

In this study, 4- diethanolaminomethyl styrene (DEAMSt) monomer was prepared by reaction of 4-cloromethyl styrene with diethanol amine. Then, the copolymers in three different combinations of 4-diethanolaminomethyl styrene (DEAMSt) monomer with benzyl methacrylate (BMA) monomer were synthesized by free radical polimerization method at 60 °C in presence of 1,4 dioxane as solvent and AIBN as initiator. Synthesized copolymers were characterized by FT-IR, 1H-NMR, elemental analysis, SEM, XRD, DSC and TGA techniques. The resulting copolymers were used as ligand and prepared complexes with Co (II), Ni (II) and Zn (II) metal ions. The copolymer-metal complexes were characterized by elemental analysis, FT-IR, SEM, XRD, magnetic masurements, and the thermal behaviors of the copolymer-metal complexes were determined by using TGA, DTA and DSC techniques. The compositions of DEAMSt and BMA in the copolymers were determined by 1H-NMR spectrums and DEAMSt % in the copolymer compositions were estimated as (0.23, 0.49, 0.70), respectively. Also, according to magnetic measurement of copolymer-metal complexes Ni(II) and Co (II) complexes are paramagnetic, that of Zn (II), was found that was the diamagnetic. According to the magnetic measurements it has been suggested that geometry structure for all complexes is tetrahedral and the rates ligand to metal in the complexes were found to be 2:1. Both Poly(DEAMSt0.49-co-BMA) and Poly(DEAMSt0.49-co-BMA)-Zn complex were heated up to various temperatures. As temperature increases, a decreasing in the intensities of O-H stretching bands at 3125-3429 cm-1 resulting from hydrogen bond was observed and shifted to high frequency. Gel permeation chromatography was used to determine the average molecular weights and polydispersity index of Poly(DEAMSt0.23-co-BMA) and Poly(DEAMSt0.49-co-BMA) ligands. GPC results could not be obtained because the Poly(DEAMSt0.70-co-BMA) ligand was not soluble in any solvent. The molecular formula and were estimated from elemental analysis C, H, N % and the amounts of metal by mole (%) in the complexes were estimated by SEM-EDX measurements. Then, SEM images were recorded and morphological structures of ligands and metal complexes were determined. The ligands and metal complexes were characterized to be amorphous by XRD analysis, also, metal complexes were found to exhibit crystal structures by heating for 1 hour at 100 °C. The SEM and XRD analysis of metal complexes confirmed that metal ions participates to the structure of the ligand. The dielectric measurements of ligands and theirs metal complexes were investigated depending on frequency. While the dielectric constant and dielectric loss factor values were decreased with frequency increasing the conductivity values estimated that increases with frequency increasing. Keywords: Ligand, Polymer-Metal Complexes, Dielectric Properties, Copolymer, Magnetic Measurements.