A Priori Prediction of Mass Spectrometric Product Patterns of Photoinitiated Polymerizations

Philipp Jöckle, Judith Radebner, Michael Haas, Iris Lamparth, Harald Stueger, Norbert Moszner, Andreas Neil Unterreiner*, Christopher Barner-Kowollik

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review


We introduce a method for the a priori prediction of mass spectra of complex poly(methyl methacrylate)s initiated by photoinitiators featuring multiple cleavage points. The method is based on permutation mathematics using multinomial coefficients to predict the probability of each poly(methyl methacrylate) species' isotopic pattern contribution to the overall mass spectrum. The method assumes a statistical behavior for the cleavage of the photoinitiator. The excellent agreement of the predicted mass spectrum based on multinomial coefficients with the experimental mass spectrum confirms a multipoint cleavage mechanism of the assessed photoinitiators. We exemplify our method for the prediction of mass spectra of poly(methyl methacrylate)s initiated by four tetraacylgermane derivates and one bisacylgermane, recorded after visible light pulsed-laser polymerization by high resolution Orbitrap electrospray ionization mass spectrometry (ESI-MS). The excellent agreement of our approach with experimental data suggests that a wide array of polymer mass spectra of polymers initiated by initiators capable of multiple cleavage events can be quantitatively predicted.

Original languageEnglish
Pages (from-to)132-136
Number of pages5
JournalACS Macro Letters
Issue number2
Publication statusPublished - 20 Feb 2018

ASJC Scopus subject areas

  • Organic Chemistry
  • Polymers and Plastics
  • Inorganic Chemistry
  • Materials Chemistry

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