Unexpected end-groups of poly(acrylic acid) prepared by RAFT polymerization

Authors

  • Marie-France Llauro,

    1. Service Commun de Resonance Magnetique Nucleaire de la Fédération des Polyméristes Lyonnais, FR2151/Centre National de la Recherche Scientifique (CNRS), BP24, 69390 Vernaison, France
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  • Julien Loiseau,

    1. Laboratoire de Chimie et Procedes de Polymerisation, Ecole Physique Chimie Electronique de Lyon/CNRS 43, Bd 11 Novembre 1918, BP 2077, 69616 Villeurbanne Cedex, France
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  • Fernande Boisson,

    1. Service Commun de Resonance Magnetique Nucleaire de la Fédération des Polyméristes Lyonnais, FR2151/Centre National de la Recherche Scientifique (CNRS), BP24, 69390 Vernaison, France
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  • Frédéric Delolme,

    1. Service Central d'Analyses du CNRS, BP22, 69390 Vernaison, France
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  • Catherine Ladavière,

    Corresponding author
    1. Unite Mixte de Recherche 2142–CNRS/bioMérieux Systèmes Macromoléculaires et Immunovirologie Humaine, E. N. S. L., 46, allée d'Italie, 69364 Lyon Cedex 07, France
    • Unite Mixte de Recherche 2142–CNRS/bioMérieux Systèmes Macromoléculaires et Immunovirologie Humaine, E. N. S. L., 46, allée d'Italie, 69364 Lyon Cedex 07, France
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  • J. Claverie

    Corresponding author
    1. University of New Hampshire, Nanostructured Polymers Research Center, Parsons Hall, 23 College Road, Durham, New Hampshire 03824
    • University of New Hampshire, Nanostructured Polymers Research Center, Parsons Hall, 23 College Road, Durham, New Hampshire 03824
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Abstract

Low-molecular-weight poly(acrylic acid) (PAA) was synthesized by reversible addition fragmentation chain transfer polymerization with a trithiocarbonate as chain-transfer agent (CTA). With a combination of NMR spectroscopy and matrix-assisted laser desorption/ionization time-of-flight mass spectrometry, the PAA end-groups of the polymer were analyzed before and after neutralization by sodium hydroxide. The polymer prior to neutralization is made up of the expected trithiocarbonate chain-ends and of the H-terminated chains issued from a reaction of transfer to solvent. After neutralization, the trithiocarbonates are transformed into thiols, disulfides, thiolactones, and additional H-terminated chains. By quantifying the different end-groups, it was possible to demonstrate that fragmentation is the rate limiting step in the transfer reaction. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 5439–5462, 2004

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