Abstract Star-shaped poly(ε-caprolactone) (PCL) polymers were synthesized and fully characterized by gel permeation chromatography, matrix-assisted laser desorption/ionisation time-of-flight mass spectrometry (MALDI-TOF MS) as well as 1 H NMR spectroscopy. First a series of four-armed PCLs with different molecular weights was prepared and analyzed with the mentioned analytical techniques revealing that the applied ring-opening polymerization was controlled and defined star-shaped polymers could be synthesized. Subsequently, also the synthesis of six-armed PCL polymers was investigated with the conclusion that also these starshaped polymers could be prepared in a controlled fashion.
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