| Abstract: | The mechanism of group transfer polymerization (GTP) of methacrylates in THF is investigated by using data on kinetics of homo- and copolymerization, polymer microstructure and molecular weight distribution. By comparison with corresponding data on anionic polymerization it is concluded that the mechanisms of monomer addition to the active chain end is very similar for both anionic and group transfer polymerization and that GTP is ionic in character. On the other hand, GTP uniquely is characterized by the existence of a catalyst exchange equilibrium. The position of this equilibrium determines the rates of polymerization, and the dynamics determine the molecular weight distribution. |
