A series of support systems for atom transfer radical polymerization of various monomers is disclosed. The complexes of a copper bromide and a multidentate amine physically adsorbed onto silica gel, alumina gel or other polymeric particles mediate living polymerization of non- or low polar monomers, including methacrylates, acrylates and styrenic monomers. The polymers have controlled molecular weights and narrow molecular weight distributions. The catalyst/ligand complex may be easily recovered for subsequent uses. The recycled catalysts have high activities and mediated living polymerizations, producing polymers with controlled molecular weights and low molecular weight distributions. Multidentate amines were also chemically grafted onto silica gels. These grafted catalyst ligand complexes also mediate living polymerizations of monomers such as methacrylates, acrylates and styrenic monomers. Also disclosed is a continuous process for atom transfer radical polymerization using a column reactor packed with a supported catalyst. Homo-polymers and random copolymers with controlled molecular weights may be produced by the reactor in a continuous manner. Block copolymers of different monomers may also be prepared using packed column reactors arranged in series.
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