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    Single-Pulse Pulsed Laser Polymerization–Electron Paramagnetic Resonance Investigations into the Termination Kinetics of n-Butyl Acrylate Macromonomers (2012)

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    Type of Content
    Journal Article
    UC Permalink
    http://hdl.handle.net/10092/7379
    
    Publisher's DOI/URI
    https://doi.org/10.1002/pola.26295
    
    Publisher
    University of Canterbury. Chemistry
    Collections
    • Science: Journal Articles [1104]
    Authors
    Barth, J.
    Buback, M.
    Barner-Kowollik, C.
    Junkers, T.
    Russell, G.T.
    show all
    Alternative Title
    SP-PLP-EPR Investigations into the Termination Kinetics of n-Butyl Acrylate Macromonomers
    Abstract

    The termination of model mid-chain radicals (MCRs), which mimic radicals that occur in acrylate polymerization over a broad range of reaction conditions, has been studied by singlepulse pulsed-laser polymerization (SP PLP) in conjunction with electron paramagnetic resonance (EPR) spectroscopy. The model radicals were generated by initiator-fragment addition to acrylic macromonomers that were preformed prior to the kinetic experiments, thus enabling separation of termination from the propagation reaction, for these model radicals propagate sparingly, if at all, on the timescale of SP-PLP experiments. Termination rate coefficients of the MCRs were determined in the temperature range 0–60 °C in acetonitrile and butyl propionate solution as well as in bulk macromonomer over 0–100 °C. Termination rate coefficients slightly below those of the corresponding secondary radicals were deduced, demonstrating the relatively high termination activity of this species, even when undergoing MCR-MCR termination. For chain length 10, a reduction by a factor of 6 is observed. Unusually high activation energies were found for the termination rate coefficient in these systems, with 35 kJ mol⁻¹ being determined for bulk macromonomer.

    Citation
    Barth, J., Buback, M., Barner-Kowollik, C., Junkers, T., Russell, G.T. (2012) Single-Pulse Pulsed Laser Polymerization–Electron Paramagnetic Resonance Investigations into the Termination Kinetics of n-Butyl Acrylate Macromonomers. Journal of Polymer Science Part A: Polymer Chemistry, 50(22), pp. 4740-4748.
    This citation is automatically generated and may be unreliable. Use as a guide only.
    Keywords
    ESR/EPR; kinetics (polym.); macromonomers (acrylate); mid-chain radicals; radical polymerization; termination
    ANZSRC Fields of Research
    03 - Chemical Sciences::0303 - Macromolecular and Materials Chemistry::030304 - Physical Chemistry of Materials
    34 - Chemical sciences::3403 - Macromolecular and materials chemistry::340306 - Polymerisation mechanisms
    03 - Chemical Sciences::0306 - Physical Chemistry (incl. Structural)::030606 - Structural Chemistry and Spectroscopy
    Rights
    https://hdl.handle.net/10092/17651

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      Barth, J.; Buback, M.; Russell, G.T. (University of Canterbury. Chemistry, 2012)
      Since at least the 1940s, workers have been seeking to understand the kinetics of the fundamental radical-polymerization reaction of termination. This quest has not proven to be easy. Just under a decade ago, two game-changing ...
    • Chain-Length-Dependent Termination in Radical Polymerization of Acrylates 

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      An online database created and curated by an IUPAC subcommittee is introduced. It is designed to act as central access point for finding reliable kinetic data on radical polymerizations. The database can be accessed via a ...
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