Studying the mechanism of thioketone-mediated polymerization via electrospray ionization mass spectrometry

Günzler, F., Junkers, T., & Barner-Kowollik, C. (2009) Studying the mechanism of thioketone-mediated polymerization via electrospray ionization mass spectrometry. Journal of Polymer Science, Part A: Polymer Chemistry, 47(7).

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Abstract

The polymeric product spectrum generated in thioketone-mediated free radical polymerization (TKMP) was analyzed via electrospray ionization mass spectrometry. Poly(n-butyl acrylate) samples were synthesized in the presence of the (commercially available) thioketone 4,4-bis(dimethylamino)thiobenzophenone under variable reaction conditions in toluene solution at 80 °C. To unambiguously assign the mass spectra, the samples are prepared under variation of the monomer (going from n-butyl acrylate to ethyl acrylate) as well as by employing variable thermally decomposing initiators [i.e., 2,2'- azoisobutyronitrile and azobis(cyclohexanecarbonitrile)]. In all mass spectra, significant amounts of the expected cross-termination product, formed via bimolecular termination of propagating macroradicals with the dormant thioketone radical adduct (consisting of a propagating chain and the mediating thioketone) alongside conventional termination products can be identified. As the study was carried out on acrylate polymers, acrylate-specific reaction products arising from intramolecular transfer reactions followed by β-seission of the generated mid-chain radicals are also identified in the mass spectra. In addition, a species congruent with the dormant thioketone radical adduct itself (oxidized to its cationic state) was identified. Products that could potentially be formed via a chain transfer mechanism cannot be identified. The results presented here thus support the earlier suggested TKMP mechanism involving a highly stabilized adduct radical which undergoes significant cross-termination reactions. © 2009 Wiley Periodicals, Inc.

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ID Code: 99213
Item Type: Journal Article
Refereed: Yes
Additional Information: Cited By :17
Export Date: 5 September 2016
CODEN: JPACE
Correspondence Address: Barner-Kowollik, C.; Preparative Macromolecular Chemistry, Institut fur Technische Chemie und Polymerchemie, Universitat Karlsruhe (TH), Engesserstr, 18, 76128 Karlsruhe, Germany; email: chnstopher.bairier-kowollik@polymer.uni-karlaruhe.ed
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Keywords: Controlled/living radical polymerization, End-group characterization, Esi- mass spectrometry, Kinetics (polym.), Thioketone-mediated polymerization (TKMP), Atom transfer radical polymerization, Electrospray ionization, High performance liquid chromatography, Ionization, Mass spectrometers, Mass spectrometry, Monomers, Polymers, Spectrum analysis, Toluene, Free radical polymerization
DOI: 10.1002/pola.23280
ISSN: 0887624X
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: 07 Oct 2016 04:54

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