Amino-funkcionalizacija polimera na bazi metakrilata i njihova interakcija sa oksianjonima Cr(VI), Tc(VII), Re(VII) i Mo(VI) u vodenim sistemima

Abstract

Cilj ove doktorske disertacije je bio ispitivanje uticaja stepena umreženja i makroporoznosti na strukturne karakteristike i termička svojstva neporoznih i makroporoznih metakrilatnih homopolimera i kopolimera sintetizovanih suspenzionom (ko)polimerizacijom. Pored toga u disertaciji je ispitivana mogućnost primene kopolimera glicidilmetakrilata (GMA) i etilenglikoldimetakrilata (EGDMA) sa različitim udelom umreživača funkcionalizovanih dietilentriaminom (skraćeno PGME-deta) za uklanjanje oksianjona teških metala i radionuklida Cr(VI), 99Tc(VII), Re(VII) i Mo(VI) iz vodenih sistema. Šaržnom metodom pri nekompetitivnim uslovima je ispitan uticaj nekoliko ključnih faktora na kapacitet i kinetiku sorpcije u ovim sistemima: vremena kontakta, početne koncentracije metala u rastvoru, pH rastvora, temperature i parametara porozne strukture kopolimera. Polimeri su okarakterisani fizičkohemijskim metodama: mikroanalizom, skenirajućom elektronskom mikroskopijom sa energetski disperzivnom spektroskopijom x-zraka (SEM/EDS) i transmisionom elektronskom mikroskopijom (TEM), infracrvenom spektroskopijom (FTIR-ATR), živinom porozimetrijom, adsorpciono–desorpcionim izotermama N2 na 77 K i termijskom analizom (TG/DSC) sa masenom spektrometrijom (MS). Rezultati dobijeni ispitivanjem sorpcije Cr(VI), 99Tc(VII), Re(VII) i Mo(VI) iz vodenih rastvora na amino-funkcionalizovanim kopolimerima u laboratorijskim uslovima bili su osnova za proučavanje kinetičkih reakcionih i difuzionih modela, adsorpcionih izotermi i termodinamike sorpcije, da bi se dobio uvid u mehanizam procesa i ocenila efikasnost ovih sorbenasa.

The goal of this doctoral dissertation was to investigate the influence of crosslinking extent and macroporosity on structural characteristics and thermal properties of nonporous and macroporous methacrylate-based homopolymers and copolymers synthesized by suspension (co)polymerization. Also, the possible application of the copolymers of glycidyl methacrylate (GMA) and ethylene glycol dimethacrylate (EGDMA) with different crosslinker content functionalized with diethylene triamine (abbreviated PGME-deta) was investigated for the removal of heavy metal and radionuclide oxyanions Cr(VI), 99Tc(VII), Re(VII) and Mo(VI) from aqueous systems. The influence of several key characteristics on sorption capacity and kinetics: contact time, initial metal concentration in the solution, solution pH, temperature and parameters of porous structure, was investigated using batch method under noncompetitive conditions. Polymers were characterized using physicochemical methods: microanalysis, scanning electron microscopy with energy-dispersive x-ray spectroscopy (SEM/EDS) and transmission electron microscopy (TEM), infrared spectroscopy (FTIR-ATR), mercury porosimetry, N2 adsorption‒desorption isotherms at 77 K and thermal analysis (TG/DSC) with mass spectrometry (MS). The obtained results of Cr(VI), 99Tc(VII), Re(VII) and Mo(VI) sorption from aqueous solutions on the amino-functionalized copolymers in laboratory conditions were the base of the analysis of the surface reaction-based and pore diffusion-based kinetic models, adsorption isotherms and thermodynamics of sorption, in order to gain insight into the mechanism of the process and evaluate the efficiency of these sorbents.