Functionalized macroporous copolymer of glycidyl methacrylate: The type of ligand and porosity parameters influence on Cu(II) ion sorption from aqueous solutions

Abstract

The removal of heavy metals from hydro-metallurgical and other industries' wastewaters, their safe storage and possible recovery from waste- water streams is one of the greater ecological problems of modern society. Conventional methods, like precipitation, adsorption and biosorption, electrowinning, membrane separation, solvent extraction and ion exchange are often ineffective, expensive and can generate secondary pollution. On the other hand, chelating polymers, consisting of crosslinked copolymers as a solid support and functional group (ligand), are capable of selectively loading different metal ions from aqueous solutions. In the relatively simple process, the chelating copolymer is contacted with the contaminated solution, loaded with metal ions, and stripped with the appropriate eluent. Important properties of chelating polymers are high capacity, high selectivity and fast kinetics combined with mechanical stability and chemical inertness. Macroporous hydrophilic copolymers of glycidyl methacrylate and ethylene glycol dimethacrylate modified by different amines show outstanding efficiency and selectivity for the sorption of precious and heavy metals from aqueous solutions. In this study poly(GMA-co-EGDMA) copolymers were synthesized with different porosity parameters and functionalized in reactions with ethylene diamine (EDA), diethylene triamine (DETA) and triethylene tetramine (TETA). Under non-competitive conditions, in batch experiments at room temperature, the rate of sorption of Cu(II) ions from aqueous solutions and the influence of pH on it was determined for four samples of amino-functionalized poly(GMA-co-EGDMA). The sorption of Cu(II) for both amino-functionalized samples was found to be very rapid. The sorption half time, t1/2, defined as the time required to reach 50% of the total sorption capacity, was between 1 and 2 min. The maximum sorption capacity for copper (2.80 mmol/g) was obtained on SGE-10/12-deta sample. The sorption capacity of Cu(II) ions increases with increasing pH and has maximum at pH ~5. In the experimental pH range, the maximum sorption capacity of Cu(II) ions again is reached on SGE-10/12-deta. By comparing literature data and obtained results it is possible to conclude that amino-functionalized macroporous copolymers based on glycidyl methacrylate are efficient for sorption of Cu(II) ions from aqueous solutions and sorption capacity for copper mostly depends on type of amine with which the basic copolymer is functionalized

Design of amino-functionalized chelated macroporous copolymer [poly(GMA-EDGMA)] for the sorption of Cu (II) ions

“…For that purpose, both the quantity of Cu(II) ions and the corresponding copolymer amino-functionalized groups were determined (Table I), in sorption studies of the Cu(II) ion. 42 Poly(GMA-co-EGDMA)-en contains 1.12 mmol, poly(GMA-co-EGDMA)--dien 0.81 mmol and poly(GMA-co-EGDMA)-trien) 0.65 mmol amino-functionalized groups. 42 Considering the number of amino-functionalized groups (fg) in the copolymer, the quantity of the metal ion is significantly higher in all three cases (Table I).…”

“…42 Poly(GMA-co-EGDMA)-en contains 1.12 mmol, poly(GMA-co-EGDMA)--dien 0.81 mmol and poly(GMA-co-EGDMA)-trien) 0.65 mmol amino-functionalized groups. 42 Considering the number of amino-functionalized groups (fg) in the copolymer, the quantity of the metal ion is significantly higher in all three cases (Table I). The Cu(II) ion is in an excess, so the complete quantity of the Cu(II) ion would not be sorbed.…”

“…Within functional groups, coordination bonding with metal ions is achieved through N, O, P and S atoms. 41,42 Macroporous copolymers based on glycidyl methacrylate (GMA) are especially interesting, since they contain an epoxide ring in their structures. Optionally, the ease of opening the epoxide ring offers the possibility for the introduction of a ligand with an iminodiacetate, thiol, pyrazole or amino group.…”

“…Therefore, the structure of a GMA-based copolymer suggests promising possibilities of numerous applications referring to environmental issues. 41,42,[44][45][46][47][48][49] An incredible number of possible structures that could be synthesized, demands a theoretical evaluation of the most appropriate ligand for the sorption of a particular compound. Recently, through the process of polymerization of GMA monomer together with ethylene glycol dimethacrylate (EGDMA), a macroporous copolymer poly(glycidyl methacrylate-co-ethylene glycol dimethacrylate) (poly(GMA-co-EGDMA)) has been synthesised.…”

New Technology for the Synthesis of New Materials Based on Cellulose and Sorption of Noble Metals

“…The application of synthesized grafted cellulose and lignin copolymers for selective extraction of gold, palladium and platinum from the solution with other metals was done (Bilba et al, 2010;Bojanic et al, 1998cBojanic et al, , 2001Dubiella-Jackowska et al, 2007;Liu et al, 2000;Masllorens et al, 2006;Nastasovic et al, 2006;Navarro et al, 2006;Othman et al, 2005;Sandic & Nastasovic, 2009;Tavlarides et al, 2006). Following copolymers synthesized for this purpose were used: Cell-PVP, Cell-1-Me-PVPJ, Cell-1-Me-PVPCF 3 COO, Cell-PVIm, Lig-PVP and Tan-PVP.…”