Anionic polymerization and copolymerization of acrylonitrile initiated by systems based on bicyclic tertiary amines and ethylene oxide

It is shown that the products of interaction of ethylene oxide and bicyclic amines containing tertiary nitrogen atoms at the tops of bicyclic structures efficiently initiate the anionic polymerization of acrylonitrile. As opposed to all known initiators of this process, the mentioned initiating systems contain no metal atoms or atoms of elements heavier than oxygen. The polymerization of acrylonitrile under the action of the ethylene oxide–bicyclic amine system in a polar medium (dimethyl sulfoxide) at room temperature occurs in the homogeneous regime over several minutes, while, in a weakly polar solvent (tetrahydrofuran), polymerization occurs in the heterogeneous regime over several hours. The reaction may become homogeneous in a mixture of these solvents at both room temperature and a lower temperature. The number-average molecular masses of the polymers, depending on polymerization conditions, are in the range from 25 × 103 to 480 × 103 and their polydispersity indexes are from 1.55 to ~3.40. It is found that the copolymers of acrylonitrile with oxygen-containing acrylic monomers, as well as with ethylene oxide, can be prepared.