New Experimental Procedure To Determine the Recombination Rate Constants between Nitroxides and Macroradicals

Abstract

A new experimental procedure for the determination of the recombination rate constant, kc, between a propagating macroradical and a nitroxide is proposed. It is based on a single pulse−pulsed lamp polymerization where the main chain growth breaking event between two consecutive pulses is the recombination of the macroradicals with the nitroxide. The recovered polymer is analyzed by size exclusion chromatography, and the parameters of the molar mass distribution are used to determine kc, in a similar way as that traditionally applied in the determination of the chain transfer rate constants, i.e., the Mayo method using the number- or weight-average degrees of polymerization and the full chain length distribution method. We named the technique RNR−PLP−SEC for radical nitroxide recombination−pulsed lamp polymerization−size exclusion chromatography. The particular polystyryl macroradical−SG1 nitroxide system was tested to validate it. To apply a consistency check, the experimental parameters have been varied according to the recommendations made by the IUPAC for the measurements of the propagation rate constants via PLP. The recombination rate constant kc was measured over a temperature range where no cleavage of the formed alkoxyamine might occur. At 40 °C kc = 2.6 × 105 L mol-1 s-1, and the value increased from 1.1 × 105 L mol-1 s-1 at 15 °C to 4.0 × 105 L mol-1 s-1 at 82 °C. The extrapolation at 120 °C led to 5.3 × 105 L mol-1 s-1, in good agreement with the values already reported in the literature.