Naiyi Ji

Synthesis of polyacrylonitrile-grafted cross-linked N-chlorosulfonamidated polystyrene via surface-initiated ARGET ATRP, and use of the resin in mercury removal after modification

A novel method of surface modification was developed via iron (III)-mediated atom transfer radical polymerization, with activators regenerated by electron transfer (ARGET ATRP) on the surfaces of polystyrene resin-supported N-chlorosulfonamide groups. The well-defined polyacrylonitrile (PAN) was grafted onto the surfaces of the polystyrene (PS). The graft reaction exhibited first-order kinetics with respect to the polymerization time in the low-monomer-conversion stage. The cyano group of PAN-g-PS was modified by NH(2)OH·HCl to yield amidoxime (AO) groups. The AO groups had been demonstrated to be an efficient Hg-specific sorbent, which can remove Hg(2+) from solutions. No interference arose from common metal ions, such as Pd(2+), Ag(+), and Cu(2+). Three adsorption-desorption cycles demonstrated that this resin is suitable for reuse without any considerable change in adsorption capacity.

Samarium(III)-based AGET ATRP of Acrylonitrile Using Ascorbic Acid as Reducing Agent

Atom transfer radical polymerization using activators generated by electron transfer (AGET ATRP) of acrylonitrile (AN) initiated by ethyl 2-bromoisobutyrate (EBiB) was approached for the first time in the absence of oxygen and in the presence of air, using a novel catalyst system based on SmBr3·6H2O/isophthalic acid complexes and using ascorbic acid (VC) as a reducing agent. Both the polymerization in the absence of oxygen and in the presence of air proceeded in a well-controlled manner as evidenced by kinetic studies. Compared with the polymerization in the absence of oxygen, the polymerization in the presence of air provided rather slow reaction rate and showed better control of molecular weight and its distribution under the same experimental conditions. The polymerization apparent activation energies in the absence of oxygen and in the presence of air were calculated to be 47.1 and 51.3 kJ·mol−1, respectively. A slow polymerization rate and a broad polydispersity index were observed using anisole and toluene instead of DMF as solvent. Polyacrylonitrile obtained was successfully used as a macroinitiator to proceed the chain extension polymerization of styrene via AGET ATRP in the presence of air.