Journal
JOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY
Volume 47, Issue 6, Pages 1636-1650Publisher
WILEY
DOI: 10.1002/pola.23273
Keywords
living radical polymerization (LRP); stimuli-sensitive polymers; supramolecular structures; water-soluble polymers
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Funding
- National Natural Scientific Foundation of China (NNSFC) [20534020, 20674079, 20874092, 50425310]
- Specialized Research Fund for the Doctoral Program of Higher Education (SRFDP)
- Program for Changjiang Scholars and Innovative Research Team in University (PCSIRT)
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Amphiphilic ABC miktoarm star terpolymers consisting of polystyrene, poly(epsilon-caprolactone), and poly(N-isopropylacrylamide) arms, PS(-b-PNIPAM)-b-PCL, were synthesized via a combination of atom transfer radical polymerization, ring-opening polymerization (ROP), and click chemistry. Difunctional PS bearing an alkynyl and a primary hydroxyl moiety at the chain end, PS-alknyl-OH, was prepared by reacting azido-terminated PS with an excess of 3,5-bis(propargyloxy)benzyl alcohol (BPBA) under click conditions. The subsequent ROP of epsilon-caprolactone using PS-alknyl-OH macroinitiator afforded PS(-alkynyl)-b-PCL copolymer bearing an alkynyl moiety at the diblock junction point. Target PS(-b-PNIPAM)-b-PCL amphiphilic ABC miktoarm star terpolymers were then prepared via click reaction between PS(-alkynyl)-b-PCL and an excess of azido-terminated PNIPAM (PNIPAM-N-3). The removal of excess PNIPAM-N-3 was accomplished by clicking onto alkynyl-functionalized Wang resin. All the intermediate and final products were characterized by gel permeation chromatography, H-1 NMR, and FTIR. In aqueous solution, the obtained amphiphilic ABC miktoarm star terpolymer self-assembles into micelles possessing mixed PS/PCL cores and thermoresponsive shells, which were further characterized by dynamic laser light scattering and transmission electron microscopy. (C) 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 1636-1650, 2009
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