Functionalized biodegradable polymers via termination of ring‐opening polymerization by acyl chlorides

Abstract

Aliphatic polyesters are an important class of polymeric materials for biomedical applications due to their versatile and tunable chemistry, biocompatibility and biodegradability. A capa-bility of direct bonding with biomedically significant molecules, provided by the presence of the reactive end functional groups (FGs), is highly desirable for prospective polymers. Among FGs, N‐ hydroxysuccinimidyl activated ester group (NHS) and maleimide fragment (MI) provide efficient covalent bonding with –NH– and –SH containing compounds. In our study, we found that NHS-and MI‐derived acyl chlorides efficiently terminate living ring‐opening polymerization of ε‐capro-lactone, L‐lactide, ethyl ethylene phosphonate and ethyl ethylene phosphate, catalyzed by 2,6‐di-tert‐butyl‐4‐methylphenoxy magnesium complex, with a formation of NHS‐ and MI‐functionalized polymers at a high yields. Reactivity of these polymers towards amine‐ and thiol‐containing model substrates in organic and aqueous media was also studied.