Controlled Copolymerization of <i>n</i>-Butyl Acrylate with Nonpolar 1-Alkenes Using Activators Regenerated by Electron Transfer for Atom-Transfer Radical Polymerization

Abstract

Controlled copolymerization of n-butyl acrylate with 1-octene was achieved by ARGET (activators regenerated by electron transfer) ATRP (atom transfer radical polymerization) in anisole. When a normal ATRP of n-butyl acrylate and 1-octene was conducted, the polymerization resulted in relatively low conversion (<50%), 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 were obtained because the low concentration of Cu(II) deactivator reduced the frequency of producing the nonreactive dormant species. When n-butyl acrylate and 1-octene were copolymerized with 10 ppm of CuCl2/TPMA vs monomer and 10 mol % of Sn(EH)2 vs initiator, a copolymer was prepared in higher yield and with low polydispersity (PDI < 1.4).