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3-Aminopropyl-functionalized silica support (APSS) has been used as a solid support for the heterogeneous atom transfer polymerization of methyl methacrylate (MMA), to poly(methyl methacrylate) (PMMA), mediated by adsorbed RuCl2(PPh3)3 as catalyst. This system displays characteristics of a living radical polymerization as indicated by (i) an increase in the number-average molecular weight (Mn) with conversion, (ii) relatively low polydispersity indexes (PDI), and (iii) linear first-order rate plots. When PMMA of Mn = 20 000 g mol-1 was targeted, the reaction reached 91% conversion after 4 h with a measured Mn = 21 500 g mol-1 and PDI = 1.49. It was found that polymerization of MMA mediated by RuCl2(PPh3)3 in the presence of APSS does not require the addition of an aluminum alkoxide (e.g., Al(OiPr)3) as an activating reagent. The rate of reaction is higher than for similar homogeneous reactions; however, the polydispersity indexes are also higher. The ruthenium content of polymers thus produced is typicall...

Atom transfer polymerisation of methyl methacrylate can be effected using solid supported copper(I) pyridylmethanimine catalysts which facilitate easy removal and reuse of the catalyst.