Guangxi Zong

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.

FeCl3/Acetic Acid-mediated Reverse Atom Transfer Radical Polymerization of Acrylonitrile

Reverse atom transfer radical polymerization (RATRP) has been successfully applied in the synthesis of polyacrylonitrile (PAN) with FeCl3/acetic acid as catalyst in the presence of conventional initiator azobisisobutyronitrile (AIBN) at 65°C in N,N-dimethylformamide (DMF). A FeCl3 to acetic acid ratio of 1:2 not only gave better control on polymers molecular weight and its distribution, but also provided a rapid polymerization rate compared with any other molar ratio of FeCl3 to acetic acid. The polymerization rate increased with increasing temperature and the apparent activation energy was calculated to be 80.6 kJ·mol−1. In comparison with dimethyl sulfoxide, acetonitrile, cyclohexanone and ethyl acetate, DMF was considered to be the best solvent of the polymerization for its polarity. Analysis of 1H-NMR further confirmed the living nature of the polymerization.

Reverse Atom Transfer Radical Polymerization of Acrylonitrile Catalyzed by FeCl3/Lactic Acid

Reverse atom transfer radical polymerization (RATRP) of acrylonitrile (AN) was carried out using azobisisobutyronitrile (AIBN) as initiator, ferric trichloride anhydrous (FeCl3)/lactic acid (LA) as catalyst system; a ratio of FeCl3/LA was 1:2 gave the best control. RATRP of AN with N,N-dimethylformamide (DMF) as solvent gave the moderate polymerization rate and the narrowest polydispersity index (PDI). When FeCl3 was replaced by CuBr2, RATRP of AN showed a longer induction period. When Cu was added to the CuBr2-based catalyst system, the induction period was reduced. 1H-NMR spectra of PAN verified the possibility of controlled/living polymerization for future chain extension.

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.

Preparation of polyacrylonitrile via AGET ATRP initiated by CCl4

Abstract A commercially available alkyl halide carbon tetrachloride (CCl4) was used as the initiator for activator generated by electron transfer atom transfer radical polymerization (AGET ATRP) of acrylonitrile (AN) in N,N-dimethyl formamide (DMF). Environmentally benign ascorbic acid (VC) was chosen as the reducing agent and copper bromide (CuBr2) as the catalyst precursor together with iminodiacetic acid (IDA) as the ligand. The polymerization proceeded in a controlled manner as evidenced by kinetic of AGET ATRP of AN, a linear increase of number-average molecular weight (Mn) with monomer conversion and low polydispersity index (PDI) throughout the reactions. The monomer (AN) conversion increased with the increase of VC and CCl4. The value of PDI increased with the increase in concentration of VC. For an increase of CCl4, the value of PDI decreased first and then increased. 1H-NMR spectrum of PAN further confirmed the “living”/controlled feature of AGET ATRP of AN.