Summary: The combination of enzymatic polymerization with ATRP for the synthesis of branched (block) copolymers was investigated. Heterotelechelic polycaprolactone macroinimer was synthesized in a one‐pot enzymatic procedure by using 2‐hydroxyethyl α‐bromoisobutyrate as a bifunctional initiator. A polymerizable end group was introduced by subsequent in situ enzymatic acrylation with vinyl acrylate. Branched polymers were obtained by subsequent atom transfer radical polymerization (ATRP).
Enzymatic synthesis of heterotelechelic macromonomers and subsequent self condensing vinyl polymerization by ATRP.
