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Three‐arm star block copolymers of ε‐caprolactone and acrylic acid: Synthesis and micellization behavior
Authors:Jin‐Xia Liu  Cong Yuan  Ze Su  Ting‐Ting Xu  Liu‐He Wei  Zhi Ma
Institution:1. The College of Chemistry and Molecular Engineering, Zhengzhou University, Zhengzhou 450001, People's Republic of China;2. Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032, People's Republic of China
Abstract:A series of well‐defined three‐arm star poly(ε‐caprolactone)‐b‐poly(acrylic acid) copolymers having different block lengths were synthesized via the combination of ring‐opening polymerization (ROP) and atom transfer radical polymerization (ATRP). First, three‐arm star poly(ε‐caprolactone) (PCL) (Mn = 2490–7830 g mol?1; Mw/Mn = 1.19–1.24) were synthesized via ROP of ε‐caprolactone (ε‐CL) using tris(2‐hydroxyethyl)cynuric acid as three‐arm initiator and stannous octoate (Sn(Oct)2) as a catalyst. Subsequently, the three‐arm macroinitiator transformed from such PCL in high conversion initiated ATRPs of tert‐butyl acrylate (tBuA) to construct three‐arm star PCL‐b‐PtBuA copolymers (Mn = 10,900–19,570 g mol?1; Mw/Mn = 1.14–1.23). Finally, the three‐arm star PCL‐b‐PAA copolymer was obtained via the hydrolysis of the PtBuA segment in three‐arm star PCL‐b‐PtBuA copolymers. The chain structures of all the polymers were characterized by gel permeation chromatography, proton nuclear magnetic resonance (1H NMR), and Fourier transform infrared spectroscopy. The aggregates of three‐arm star PCL‐b‐PAA copolymer were studied by the determination of critical micelles concentration and transmission electron microscope. © 2013 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013
Keywords:atom transfer radical polymerization  micelles  ring‐opening polymerization  star polymers
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