Star, star-block, and miktoarm star biodegradable polymers were synthesized by an “arm-first” strategy, ring-opening polymerization and one-pot azide-alkyne click reaction.

Based on the combination of the “arm-first” and “core-first” strategies, the miktoarm star-shaped copolymer PLLA2PCL2 and the inverse star-block copolymer (PCL-b-PLLA)2-core-(PCL-b-PLLA)2 were designed and synthesized by the combination of ring-opening polymerization (ROP) and a click reaction. The miktoarm star-shaped copolymer PLLA2PCL2 was synthesized by a click reaction of an azido macroinitiator PLLA2(N3)2 and HC≡C-PCL. The inverse star-block copolymer (PCL-b-PLLA)2-core-(PCL-b-PLLA)2 was synthesized by a click reaction of an azido macroinitiator (PCL-b-PLLA)2(N3)2 and HC≡C-PCL-b-PLLA. The structures of these star polymers were confirmed by nuclear magnetic resonance (NMR), Fourier-transform infrared (FT-IR) spectroscopy and gel permeation chromatograph (GPC). The inverse star-block copolymer could be used to study the potential relationship between polymer structure and properties, which has a unique structure and good crystallization properties.