UV-triggered end group conversion of photo-initiated poly(methyl methacrylate)

Voll, D., Neshchadin, D., Hiltebrandt, K., Gescheidt, G., & Barner-Kowollik, C. (2012) UV-triggered end group conversion of photo-initiated poly(methyl methacrylate). Macromolecules, 45(15).

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The analysis of photo-initiated poly(methyl methacrylate) via electrospray ionization-mass spectrometry (ESI-MS) (synthesized by pulsed laser polymerization (PLP, at λ = 351 nm) of methyl methacrylate (MMA) and benzoin as photoinitiator at 6 mJ/pulse laser energy) evidences the presence of unidentified species. The determination of the origin of these species requires a detailed investigation via size exclusion chromatography-electrospray ionization-mass spectrometry (SEC/ESI-MS) and chemically induced dynamic nuclear polarization-nuclear magnetic resonance spectroscopy (CIDNP-NMR). It was found that post-irradiation of benzoin-initiated poly(methyl methacrylate) leads to α-cleavage of the benzoyl fragment leading to a sequence of cascade reactions, including the formation of an additional double bond within the polymer chain as evidenced via ESI-MS. Furthermore, the reaction products of the benzoyl radical post α-cleavage (e.g., benzaldehyde, phenyl methyl ketone, methyl formate, or methane) as well as the formed macroradical can be followed by CIDNP-NMR, which allows establishing a reaction mechanism for the UV-induced cleavage process. The study thus evidence that-if the integrity of UV initiated polymers is to be kept intact during their synthesis-very low irradiation energies need to be employed. © 2012 American Chemical Society.

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ID Code: 99328
Item Type: Journal Article
Refereed: Yes
Additional Information: Cited By :5
Export Date: 5 September 2016
Correspondence Address: Gescheidt, G.; Institute of Physical and Theoretical Chemistry, Graz University of Technology, Stremayrgasse 9, 8010 Graz, Austria; email: g.gescheidt-demner@tugraz.at
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Keywords: Benzoyl radicals, Cascade reactions, Double bonds, Electrospray ionization mass spectrometry, End groups, Irradiation energy, Laser energies, Methyl formate, Methyl ketones, Methyl methacrylates, Photo-initiator, Polymer chains, Postirradiation, Pulsed laser polymerization, Reaction mechanism, Size exclusion, Acetone, Aldehydes, Electrospray ionization, Esters, Irradiation, Mass spectrometry, Methane, Nuclear magnetic resonance spectroscopy, Polymers, Synthesis (chemical), Acrylic monomers
DOI: 10.1021/ma301275b
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: 30 Sep 2016 04:20

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