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

Type of Content
Journal ArticlePublisher
University of Canterbury. ChemistryCollections
- Science: Journal Articles [1104]
Alternative Title
SP-PLP-EPR Investigations into the Termination Kinetics of n-Butyl Acrylate MacromonomersAbstract
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; terminationANZSRC Fields of Research
03 - Chemical Sciences::0303 - Macromolecular and Materials Chemistry::030304 - Physical Chemistry of Materials34 - Chemical sciences::3403 - Macromolecular and materials chemistry::340306 - Polymerisation mechanisms
03 - Chemical Sciences::0306 - Physical Chemistry (incl. Structural)::030606 - Structural Chemistry and Spectroscopy
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