Calixarene‐centered amphiphilic A2B2 miktoarm star copolymers based on poly(ε‐caprolactone) and poly(ethylene glycol): Synthesis and self‐assembly behaviors in water

Abstract

AbstractNovel calixarene‐centered amphiphilic A2B2 miktoarm star copolymers composed of two PCL arms and two PEG arms with calix[4]arene as core moiety were synthesized by the combination of CROP and “click” chemistry. First, a heterotetrafunctional calix[4]arene derivative with two hydroxyl groups and two alkyne groups was designed as a macroinitiator to prepare calixarene‐centered PCL homopolymers (C4‐PCL) by CROP in the presence of Sn(Oct)2 as catalyst at 110 °C. Next, azide‐terminated PEG (A‐PEG) was synthesized by tandem treating methoxy poly(ethylene glycol)s (mPEG) with 4‐chlorobutyryl chloride and NaN3. Finally, copper(I)‐catalyzed cycloaddition reaction between C4‐PCL and A‐PEG led to A2B2 miktoarm star copolymer [C4S(PCL)2‐(PEG)2]. 1H NMR, FT‐IR, and SEC analyses confirmed the well‐defined miktoarm star architecture. These amphiphilic miktoarm star copolymers could self‐assemble into multimorphological aggregates in water. The calix[4]arene moieties with a cavity <1 nm on the hydrophilic/hydrophobic interface of these aggregates may provide potential opportunities to entrap guest molecules for special applications in supermolecular science. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010