Investigation of Factors Influencing the Chemoenzymatic Synthesis of

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Macromolecules 2005, 38, 4220-4225

Investigation of Factors Influencing the Chemoenzymatic Synthesis of Block Copolymers Matthijs de Geus,† Joris Peeters,‡ Martin Wolffs,‡ Thomas Hermans,‡ Anja R. A. Palmans,‡ Cor E. Koning,† and Andreas Heise*,† Department of Polymer Chemistry and Department of Macromolecular and Organic Chemistry, Technische Universiteit Eindhoven, Den Dolech 2, P.O. Box 513, 5600 MB Eindhoven, The Netherlands Received December 20, 2004; Revised Manuscript Received March 24, 2005

ABSTRACT: The chemoenzymatic synthesis of block copolymers from a bifunctional initiator using enzymatic ring-opening polymerization (eROP) and ATRP in two consecutive steps was investigated. First, a polycaprolactone (PCL) macroinitiator was obtained via an enzymatic ring-opening polymerization initiated by the bifunctional initiator. By carefully managing the water activity in the system, the amount of PCL not initiated by the bifunctional initiator was reduced to