Laser-induced decomposition of 2,2-dimethoxy-2-phenylacetophenone and benzoin in methyl methacrylate homopolymerization studied via matrix-assisted laser desorption/ionization time-of-flight mass spectrometry

Christopher Barner-Kowollik, Philipp Vana, Thomas P. Davis

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Pulsed laser polymerization (PLP) experiments were performed on the bulk polymerization of methyl methacrylate (MMA) at -34 °C. The aim of this study was to investigate the polymer end groups formed during the photoinitiation process of MMA monomer using 2,2-dimethoxy-2-phenylacetophenone (DMPA) and benzoin as initiators via matrix-assisted laser desorption/ionization time-of-flight (MALDI-TOF) mass spectrometry. Analysis of the MALDI-TOF spectra indicated that the two radical fragments generated upon pulsed laser irradiation show markedly different reactivity toward MMA: whereas the benzoyl fragment-common to both DMPA and benzoin-clearly participates in the initiation process, the acetal and benzyl alcohol fragments cannot be identified as end groups in the polymer. The complexity of the MALDI-TOF spectrum strongly increased with increasing laser intensity, this effect being more pronounced in the case of benzoin. This indicates that a cleaner initiation process is at work when DMPA is used as the photoinitiator. In addition, the MALDI-TOF spectra were analyzed to extract the propagation-rate coefficient, kp, of MMA at -34 °C. The obtained value of kp = 43.8 L mol-1 s-1 agrees well with corresponding numbers obtained via size exclusion chromatography (kp = 40.5 L mol-1 s-1).

Original languageEnglish
Pages (from-to)675-681
Number of pages7
JournalJournal of Polymer Science, Part A: Polymer Chemistry
Issue number5
Publication statusPublished - 1 Mar 2002
Externally publishedYes


  • Initiators
  • Laser-induced polymers
  • Methyl methacrylate
  • Propagation-rate coefficient

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