Homogeneous rare earth coordination catalysts for copolymerization of styrene with acrylonitrile

The study on homogeneous rare earth coordination catalysts, LnL 3 ‐Al( i ‐Bu) 3 ‐CCl 4 , for the copolymerization of styrene with acrylonitrile has been successfully carried out for the first time. Some features and kinetic behavior of copolymerization of styrene with acrylonitrile by Nd(P 204 ) 3 ‐Al( i ‐Bu) 3 ‐CCl 4 system are described. The catalyst sites appear to possess both coordinate anionic and free radical characteristics. The catalytic activity of various rare earth elements in Ln(P 204 ) 3 and ligands in NdL 3 for the copolymerization have the following order, respectively: Yb > Er > Tb ∼ Tm > Ho > Ce > Lu ∼ Sm ∼ La > Pr > Nd, and Nd(naph) 3 > Nd(P 204 ) 3 ∼ Nd(P 507 ) 3 > Nd(acac) 3 ·3H 2 O. An alternating‐rich copolymer of styrene‐acrylonitrile with a high softening point (195–230°C) was obtained by the LnL 3 ‐Al( i ‐Bu) 3 ‐CCl 4 systems in toluene at 80°C.