Photoinduced Cu(0)‐Mediated Atom Transfer Radical Polymerization

Photoinduced Cu(0)‐mediated atom transfer radical polymerization (ATRP) of methyl methacrylate is investigated by using Cu(0)/ N,N,N′,N″,N″ ‐pentamethyldiethylenetriamine as the catalyst, ethyl 2‐bromopropionate as the initiator, and dimethyl sulfoxide as the solvent. The effect of light on the conventional Cu(0)‐mediated ATRP and molecular weight characteristics of the obtained polymers are described. Although the polymerization can be achieved in the absence of light, low initiation efficiency of the process is observed. By introducing UV light and additional Cu(II) deactivator, not only the rate of polymerization is increased, but also well‐controlled polymers with narrow‐molecular‐weight distributions at ambient conditions are obtained. The chain extension study clearly confirms high end‐group fidelity of the polymer that is active in the further polymerization process.