A bidirectional ATRP‐NMRP initiator: The effect of nitroxide size on the rate of nitroxide‐mediated polymerization |
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| Authors: | Jean Ruehl Rebecca Braslau |
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| Institution: | 1. Department of Chemistry and Biochemistry, University of California, 1156 High Street, Santa Cruz, California 95064‐1077Department of Chemistry and Biochemistry, University of California, 1156 High Street, Santa Cruz, California 95064‐1077;2. Department of Chemistry and Biochemistry, University of California, 1156 High Street, Santa Cruz, California 95064‐1077 |
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| Abstract: | An N‐alkoxyamine macroinitiator bearing a polymeric nitroxide cap was synthesized and used to investigate the effect of nitroxide size on the rate of nitroxide‐mediated radical polymerization (NMRP). This macroinitiator was prepared from asymmetric double‐headed initiator 9 , which contains both an α‐bromoester and an N‐alkoxyamine functionality. Poly(methyl methacrylate) was grown by atom transfer radical polymerization from the α‐bromoester end of this initiator, resulting in a macroinitiator (Mn = 31,000; PDI = 1.34) bearing a nitroxide cap permanently attached to a polymer chain. The polymerization kinetics of this macroinitiator in NMRP were compared with known N‐alkoxyamine initiator 1 . It was found that the rate of polymerization was unaffected by the size of the macromolecular nitroxide cap. It was confirmed that NMRP using this macroinitiator is a “living” process. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 2015–2025, 2007 |
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| Keywords: | atom transfer radical polymerization (ATRP) block copolymers diblock copolymers kinetics (polym ) living polymerization radical polymerization |
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