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

Abstract

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 polymer's 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.