Epoxides as Reducing Agents for Low-Catalyst-Concentration Atom Transfer Radical Polymerization

Activators regenerated by electron transfer atom transfer radical polymerization (ARGET ATRP) conditions utilizing a low concentration of catalyst are successfully applied for the preparation of well‐defined poly(glycidyl methacrylate) without the addition of external reducing agents. The living character of polymerization is evidenced by successful chain extensions with methyl methacrylate and methyl acrylate, again, in the absence of additional reducing agents, yielding block copolymers. The epoxide groups in glycidyl methacrylate or the corresponding polymer can serve as an intrinsic reducing agent to continuously regenerate the CuI‐based ATRP activator from the CuII halide complex present in the systems. The reactivity of various epoxides in the reduction of the CuIIBr2 complex of tris(2‐pyridylmethyl)amine is compared. Epoxides can serve to reduce Cu(II) complexes in low‐catalyst‐concentration atom transfer radical polymerization. The controlled polymerization of glycidyl methacrylate is successfully carried out in the absence of any external reducing agents. The obtained epoxide‐containing polymers are used as macroinitiators in chain extension reactions with methyl acrylate and methacrylate, also without addition of external reducing agents.