Copolymerization of (Meth)acrylates with Olefins Using Activators Regenerated by Electron Transfer for Atom Transfer Radical Polymerization (ARGET ATRP)

Summary: Controlled copolymerization of polar (meth)acrylates with non-polar olefin monomers (1-octene, norbornene, vinylcyclohexane) was studied by ARGET (activators regenerated by electron transfer) ATRP (atom transfer radical polymerization). When a normal ATRP of n-butyl acrylate (nBA) and 1-octene was conducted, the polymerization resulted in relatively low conversion, limited control over the polymerization process and high polydispersity (PDI > 1.6). This was due to formation of a dormant species, by reaction of 1-octene radicals with Cu(II) deactivator, that could not be reactivated. However, in ARGET ATRP with 10 ppm amounts of Cu-based catalyst, higher yields and a better controlled copolymerization was obtained (PDI < 1.4), because the low concentration of Cu(II) deactivator reduced the formation of the non-reactive dormant species. The influence of the amount of Cu catalyst, ligand structure, initiators with different halogens, the reaction temperature, and monomer feed ratio were also investigated for ARGET ATRP. In copolymerization of (meth)acrylates with non-polar alkenes, the level of control and the total conversion in ARGET ATRP were higher than those for normal ATRP.