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Free-Radical Polymerization Kinetics of 2-Acrylamido-2-methylpropanesulfonic Acid in Aqueous Solution

  • Sabine Beuermann*
    Sabine Beuermann
    Institute of Physical Chemistry, Georg-August-University, Tammannstrasse 6, D-37077, Göttingen, Germany, and Polymer Institute of the Slovak Academy of Sciences, Dúbravská cesta 9, 842 36 Bratislava, Slovak Republic
     Corresponding author. E-mail:  [email protected].
  • Michael Buback
    Michael Buback
    Institute of Physical Chemistry, Georg-August-University, Tammannstrasse 6, D-37077, Göttingen, Germany, and Polymer Institute of the Slovak Academy of Sciences, Dúbravská cesta 9, 842 36 Bratislava, Slovak Republic
  • Pascal Hesse
    Pascal Hesse
    Institute of Physical Chemistry, Georg-August-University, Tammannstrasse 6, D-37077, Göttingen, Germany, and Polymer Institute of the Slovak Academy of Sciences, Dúbravská cesta 9, 842 36 Bratislava, Slovak Republic
    More by Pascal Hesse
  • Tanja Junkers
    Tanja Junkers
    Institute of Physical Chemistry, Georg-August-University, Tammannstrasse 6, D-37077, Göttingen, Germany, and Polymer Institute of the Slovak Academy of Sciences, Dúbravská cesta 9, 842 36 Bratislava, Slovak Republic
  • , and 
  • Igor Lacík
    Igor Lacík
    Institute of Physical Chemistry, Georg-August-University, Tammannstrasse 6, D-37077, Göttingen, Germany, and Polymer Institute of the Slovak Academy of Sciences, Dúbravská cesta 9, 842 36 Bratislava, Slovak Republic
    More by Igor Lacík
Cite this: Macromolecules 2006, 39, 2, 509–516
Publication Date (Web):December 21, 2005
https://doi.org/10.1021/ma051187n
Copyright © 2006 American Chemical Society

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    Abstract

    The SP−PLP−NIR technique, which combines pulsed laser polymerization (PLP) initiated by a single pulse (SP) with time-resolved monitoring of the resulting monomer conversion via near-infrared (NIR) spectroscopy, was used to investigate the kinetics in aqueous solution of 2-acrylamido-2-methylpropanesulfonic acid (AMPS). For initial AMPS concentrations of 2.79 mol·L-1 (50 wt % AMPS) and 1.04 mol·L-1 (20 wt % AMPS), the ratio of (chain length averaged) termination and propagation rate coefficients, 〈kt〉/kp, was measured up to almost complete monomer conversion at temperatures between 10 and 40 °C and ambient pressure. Up to 80% monomer conversion, 〈kt〉/kp is only slightly lowered, whereas there is a clear decrease upon further increasing conversion. Variation of temperature and of pH does not significantly affect 〈kt〉/kp. For estimating individual rate coefficients, 〈kt〉 and kp, in addition chemically initiated polymerizations have been carried out, in which AMPS conversion was monitored via in-line FT-NIR spectroscopy. The resulting 〈kt〉 and kp values, for 40 °C and an initial AMPS concentration of 2.79 mol·L-1, are 2 × 107 L·mol-1·s-1 and 1 × 105 L·mol-1·s-1, respectively. Both rate coefficients are significantly higher at the lower AMPS content of 1.04 mol·L-1. 〈kt〉 at this lower AMPS content may be understood in terms of termination occurring under reaction diffusion control. The lowering in rate coefficients measured at the higher AMPS content is indicative of a reduced poly(AMPS) chain mobility.

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