A novel method for the measurement of chain transfer to monomer constants in styrene homopolymerizations: The pulsed laser rotating reactor assembly

Heidi Kapfenstein-Doak, Christopher Barner-Kowollik, Thomas P. Davis, Johannes Schweer

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12 Citations (Scopus)


The chain transfer to monomer constants (Cm) in styrene bulk polymerizations have been determined in the temperature range between 25 and 90 °C using both thermal polymerization and the novel pulsed laser polymerization (PLP) with extended dark times. This novel technique determines transfer to monomer rate coefficients by combining a pulsed laser setup with a rotating reactor/cuvette assembly. The resulting transfer controlled molecular weight distributions (MWD) were analyzed by the well-known Mayo and chain length distribution (CLD) methods. The results of both experimental methods agree well, which indicates that PLP with extended dark times is a reliable technique to determine transfer to monomer constants. For this reason, we report average values for the activation parameters determined from both thermal and extended dark times PLP experiments: Ea = 21.6 kJ mol-1 and A = 0.22 L mol-1 s-1. These numbers are in excellent agreement with those reported in the literature.

Original languageEnglish
Pages (from-to)2822-2829
Number of pages8
Issue number9
Publication statusPublished - 24 Apr 2001
Externally publishedYes

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