“Living” Free-Radical Polymerizations in the Absence of Initiators:  Controlled Autopolymerization

The autopolymerization of styrene, styrenic derivatives, and styrene/(meth)acrylate comonomer mixtures in the presence of stable nitroxide free radicals has been shown to be a “living” process. Molecular weight can be controlled by varying the ratio of vinyl monomer to TEMPO and low-polydispersity materials are obtained. Significantly, a definite incubation period is observed during these polymerizations, and the length of this incubation period increases with increasing amounts of TEMPO. The structures of the in situ generated unimolecular initiators which are formed during this incubation period correspond to those expected from a Mayo mechanism for the autopolymerization of styrene. The isolated and purified adducts, 4 and 5, were shown to be effective unimolecular initiators leading to low-polydispersity, controlled molecular weight polymers.