Unraveling the Spontaneous Zwitterionic Copolymerization Mechanism of Cyclic Imino Ethers and Acrylic Acid

Jan Steinkoenig, Patrick A.J.M. De Jongh, David M. Haddleton, Anja S. Goldmann, Christopher Barner-Kowollik, Kristian Kempe

Research output: Contribution to journalArticleResearchpeer-review

12 Citations (Scopus)


We report a high-resolution electrospray ionization mass spectrometric (HR ESI-MS) access route leading to in-depth insights into the spontaneous zwitterionic copolymerization mechanism between cyclic imino ethers (i.e., 2-methyl-2-oxazoline (MeOx), 2-ethyl-2-oxazoline (EtOx), or 2-ethyl-2-oxazine (EtOz)) with acrylic acid (AA), exploiting the characteristic species accumulating during the copolymerization as well as tandem mass spectrometry (MS/MS). We demonstrate preferences in α, ω-end group formation by screening various feed ratios of cyclic imino ethers and acrylic acid (e.g., MeOx:AA = 1:1; MeOx:AA = 2:1; and MeOx:AA = 1:2). Critically, a calibration curve - based on AA-MeOx-AA dimer - was established allowing for the semiquantitative determination of the end-group ratios with different feed ratios of acrylic acid. The formation of previously suggested alternating copolymers was confirmed by MS/MS experiments. Deviations from an ideal alternating composition were found to decrease from MeOx to EtOx to EtOz. The results of (semiquantitative) HR ESI-MS and MS/MS measurements suggest, for the first time presented in such precision, a polymerization mechanism for the spontaneous zwitterionic (alternating) copolymerization indicating optimal monomer ratios and pairings.

Original languageEnglish
Pages (from-to)318-327
Number of pages10
Issue number2
Publication statusPublished - 23 Jan 2018

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