Synthesis of poly(ϵ‐caprolactone)‐ block ‐poly( n ‐butyl acrylate) by the combination of ring‐opening polymerization and atom transfer radical polymerization with Ti[OCH 2 CCl 3 ] 4 as a difunctional initiator. II. Synthesis and characterization of poly(ϵ‐caprolactone)‐ block ‐poly( n ‐butyl acrylate) copolymers

The kinetics and controllability of the Ti[OCH 2 CCl 3 ] 4 ‐initiated atom transfer radical polymerization (ATRP) of n ‐butyl acrylate were investigated. Then, with Ti[OCH 2 CCl 3 ] 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