Reverse atom transfer radical polymerization of acrylonitrile

FeCl3 coordinated by succinic acid was used as the catalyst for the first time in azobisisobutyronitrile-initiated reverse atom transfer radical polymerization of acrylonitrile (AN). N,N-dimethylformamide (DMF) was used as a solvent to improve the solubility of the ligand. A FeCl3 to succinic acid ratio of 0.5 not only gives the best control of molecular weight and its distribution but also provides rather rapid reaction rate. Effects of different solvents on polymerization of AN were also investigated. The rate of the polymerization in DMF is faster than that in propylene carbonate and toluene. The molecular weight of polyacrylonitrile agrees reasonably well with the theoretical molecular weight in DMF. The rate of polymerization increases with increasing the polymerization temperature, and the apparent activation energy was calculated to be 64.8 kJ mol(-1). (c) 2005 Wiley Periodicals, Inc.