The recently introduced procedure of quantitatively switching thiocarbonyl thio capped (RAFT) polymers into hydroxyl terminated species was employed to generate narrow polydispersity (PDI ≈ 1.2) sulfur-free poly(styrene)-block-poly(ε-caprolactone) polymers (26,000 ≤ Mn/g·mol−1 < 45,000). The ring-opening polymerization (ROP) of ε-caprolactone (ε-CL) was conducted under organocatalysis employing 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD). The obtained block copolymers were thoroughly analyzed via size exclusion chromatography (SEC), NMR, as well as liquid adsorption chromatography under critical conditions coupled to SEC (LACCC-SEC) to evidence the block copolymer structure and the efficiency of the synthetic process. The current contribution demonstrates that the RAFT process can serve as a methodology for the generation of sulfur-free block copolymers via an efficient end group switch. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010
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