Reverse ATRP process of acrylonitrile in the presence of ionic liquids

Abstract

AbstractAn ionic liquid, 1‐butyl‐3‐methylimidazolium tetrafluoroborate ([C4mim] [BF4]), was first used as the solvent in azobisisobutyronitrile (AIBN)‐initiated reverse atom transfer radical polymerization (RATRP) of acrylonitrile with FeCl3/succinic acid (SA) as the catalyst system. The polymerization in [C4mim][BF4] proceeded in a well‐controlled manner as evidenced by kinetic studies. Compared with the polymerization in bulk, the polymerization in [C4mim][BF4] not only showed the best control of molecular weight and its distribution but also provided rather rapid reaction rate with the ratio of [C4mim][BF4] at 200:1:2:4. The polymerization apparent activation energies in [C4mim][BF4] and bulk were calculated to be 48.2 and 55.7 kJ mol−1, respectively. Polyacrylonitrile obtained was successfully used as a macroinitiator to proceed the chain extension polymerization in [C4mim][BF4] via a conventional ATRP process. [C4mim][BF4] and the catalyst system could be easily recycled and reused after simple purification and had no effect on the living nature of polymerization. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 2701–2707, 2008