Supported atom transfer radical polymerization of methyl methacrylate mediated by CuBr–tetraethyldiethylenetriamine grafted onto silica gel

Silica‐gel particles grafted with tetraethyldiethylenetriamine were synthesized as support for CuBr for the heterogeneous atom transfer radical polymerization of methyl methacrylate (MMA). The immobilized CuBr mediated a living polymerization of MMA, demonstrated by an increase in molecular weight with conversion and low polydispersity. An excessive amount of catalyst (typically, CuBr/initiator = 1.5) was required to achieve a living process because of the limited mobility of the supported catalyst. The silica‐gel concentration had a strong effect on the polymerization. The recycled catalyst still mediated a living process but showed a reduced catalytic activity due to the presence of Cu(II). After being regenerated by a reaction with Cu(0), the catalyst regained its activity. © 2001 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 39: 1051–1059, 2001 Silica‐gel particles grafted with tetraethyldiethylenetriamine were used as support for CuBr for the heterogeneous atom transfer radical polymerization of methyl methacrylate (MMA). The immobilized CuBr mediated a living polymerization of MMA, demonstrated by an increase in molecular weight with conversion and low polydispersity. The CuBr/initiator ratio and silica‐gel concentration had a strong effect on the polymerization. The recycled catalyst still mediated a living process but showed a reduced catalytic activity.