Synthesis of ABC 3-Miktoarm Star Terpolymers from a Trifunctional Initiator by Combining Ring-Opening Polymerization, Atom Transfer Radical Polymerization, and Nitroxide-Mediated Radical Polymerization

• Published in: Macromolecules Vol. 37; no. 9; pp. 3128 - 3135
• Main Authors: He, Tao, Li, Dejin, Sheng, Xia, Zhao, Bin
• Format: Journal Article
• Language: English
• Published: Washington, DC American Chemical Society 04.05.2004
• Subjects: Applied sciences; Exact sciences and technology; Organic polymers; Physicochemistry of polymers; Polymerization; Preparation, kinetics, thermodynamics, mechanism and catalysts; Ring opening polymerization; Terpolymer; Polyfunctional compound; End group; Atom transfer polymerization; Priming activity; Experimental study; Methyl methacrylate copolymer; Lactone polymer; Star copolymer; Radical catalyst; Triblock copolymer; Initiator polymer; Free radical polymerization; Caprolactone copolymer; Hydroxyether; Diblock copolymer; Living copolymer; Bromine Organic compounds; Methyl methacrylate; Chemical synthesis; Styrene copolymer
• ISSN: 0024-9297; 1520-5835
• DOI: 10.1021/ma036010c

We report a new method to synthesize ABC 3-miktoarm star terpolymers by combining three different controlled/“living” polymerization techniques:  ring-opening polymerization (ROP), atom transfer radical polymerization (ATRP), and nitroxide-mediated radical polymerization (NMRP). A trifunctional initiator bearing a hydroxy group, an ATRP initiator, and a NMRP initiator was designed and synthesized. The structure was confirmed by 1H NMR, 13C NMR, and mass spectroscopy. ABC star terpolymers were then prepared from the trifunctional initiator by sequential ROP of ε-caprolactone, ATRP of methyl methacrylate, and NMRP of styrene. GPC and kinetic analysis indicated that the polymerizations were controlled. The 3-miktoarm star structure was further confirmed by cleavage of a star terpolymer.