Mapping free radical reactivity: A high-resolution electrospray ionization-mass spectrometry study of photoinitiation processes in methyl methacrylate free radical polymerization

Szablan, Z., Lovestead, T. M., Davis, T. P., Stenzel, M. H., & Barner-Kowollik, C. (2007) Mapping free radical reactivity: A high-resolution electrospray ionization-mass spectrometry study of photoinitiation processes in methyl methacrylate free radical polymerization. Macromolecules, 40(1).

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High-resolution electrospray ionization-mass spectrometry (ESI-MS) was applied to study the polymeric product spectrum generated by the pulsed laser polymerization (PLP) of methyl methacrylate (MMA) at temperatures ≤0 °C in the presence of the photoinitiators 2,2-dimethoxy-2-phenylacetophenone (DMPA), benzoin, benzil, benzoin ethyl ether (BEE), and 2,2- azobisisobutylnitrile (AIBN). Termination products, both combination and disproportionation, were identified with high accuracy. Both the benzoyl and acetal fragments generated as a result of DMPA photocleavage were found to initiate and highly likely terminate polymerization. Under the conditions studied, the acetal radical produced upon DMPA photolysis fragments further to yield methyl radicals which seem to act predominantly as terminating moieties. Both the benzoyl and ether fragments produced as a result of benzoin photocleavage were found to act as initiating and probable terminating species, indicating that the ether radical fragment does not act exclusively as a terminating species. Additionally, increasing laser intensity and/or irradiation repetition rate (i.e., energy deposition into the system) results in more complex product distributions of the MMA polymers produced via photoinitiation (with the exception of AIBN). Temperature was determined to have a minor influence on the resulting product distribution under the conditions examined. © 2007 American Chemical Society.

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ID Code: 99161
Item Type: Journal Article
Refereed: Yes
Additional Information: Cited By :45
Export Date: 5 September 2016
Correspondence Address: Barner-Kowollik, C.; Centre for Advanced Macromolecular Design, School of Chemical Sciences and Engineering, University of New South Wales, Sydney, NSW 2052, Australia; email:
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Keywords: Free radical polymerization, Ionization, Mass spectrometry, Photolysis, Pulsed laser applications, Thermal effects, High-resolution electrospray ionization-mass spectrometry (ESI-MS), Methyl methacrylate, Photoinitiation processes, Pulsed laser polymerization (PLP), Acrylics
DOI: 10.1021/ma0616559
ISSN: 00249297
Divisions: Current > Schools > School of Chemistry, Physics & Mechanical Engineering
Current > Institutes > Institute for Future Environments
Current > QUT Faculties and Divisions > Science & Engineering Faculty
Deposited On: 22 Sep 2016 04:50
Last Modified: 11 Oct 2016 04:55

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