Synthesis of poly(ϵ-caprolactone)-block-poly(n-butyl acrylate) by the combination of ring-opening polymerization and atom transfer radical polymerization with Ti[OCH2CCl3]4 as a difunctional initiator. II. Synthesis and characterization of poly(ϵ-caprolac

Abstract

The kinetics and controllability of the Ti[OCH2CCl3]4-initiated atom transfer radical polymerization (ATRP) of n-butyl acrylate were investigated. Then, with Ti[OCH2CCl3]4 as the initiator, poly(ϵ-caprolactone)-block-poly(n-butyl acrylate) (PCL-b-PBA) copolymers were synthesized by the combination of the ring-opening polymerization (ROP) of ϵ-caprolactone and ATRP of n-butyl acrylate. With different sequential combinations of ROP and ATRP, three routes were used to synthesize PCL-b-PBA copolymers. The composition characterization results demonstrated that the first-ROP-then-ATRP route was most efficient; it was followed by the in situ ATRP and ROP route and then the first-ATRP-then-ROP route. Furthermore, with a Haake Rheomix reactor (Thermo Electron Corp., Karlsruhe, Germany), the PCL-b-PBA copolymers were in situ synthesized in a poly(methyl methacrylate) matrix. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010