Mapping poly(butyl acrylate) product distributions by mass spectrometry in a wide temperature range: Suppression of midchain radical side reactions

Junkers, T., Koo, S. P. S., Davis, T. P., Stenzel, M. H., & Barner-Kowollik, C. (2007) Mapping poly(butyl acrylate) product distributions by mass spectrometry in a wide temperature range: Suppression of midchain radical side reactions. Macromolecules, 40(25).

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Abstract

The polymer product spectra of poly(butyl acrylate), polyBA, samples obtained by full conversion bulk polymerization in the temperature range of 60-140 °C in presence of the chain transfer agent (CTA) octylthiol is analyzed via electrospray ionization-mass spectrometry (ESI-MS) and quantitative 13C NMR. The combination of both these analytical techniques allows for very detailed information on the reaction products associated with the formation of midchain radicals to be obtained. At 60 °C, highly uniform polyBA is generated that consists of the structure alkyl - S - (BA)n - H. With increasing temperature, several other peaks emerge that can be assigned to either conventional termination product or to the three different β-scission products of the so-called midchain radicals that are known to be formed in acrylate polymerization via transfer to polymer reactions. Because of the formation of β-scission products that were formed by scission to either side of the radical functionality, intermolecular transfer to polymer presumably plays an important role in the present system. For the 140 °C sample, 1.37 mol % of quaternary carbons on the polymer backbone are identified with only a small fraction of the chains carrying an unsaturated end group. As much higher levels of branching and unsaturation are expected under the same conditions from conventional free radical polymerization, it is concluded that the chain transfer agent is capable of suppressing the midchain radical side reactions to a large extent. © 2007 American Chemical Society.

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ID Code: 99150
Item Type: Journal Article
Refereed: Yes
Additional Information: Cited By :58
Export Date: 5 September 2016
CODEN: MAMOB
Correspondence Address: Barner-Kowollik, C.; Centre for Advanced Macromolecular Design, School of Chemical Sciences and Engineering, University of New South Wales, Sydney, NSW 2052, Australia; email: c.barner-kowollik@unsw.edu.au
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Keywords: Chemical analysis, Electrospray ionization, Mass spectrometry, Nuclear magnetic resonance spectroscopy, Polymerization, Chain transfer agent (CTA), Midchain radical, Temperature range, Polymers
DOI: 10.1021/ma071471+
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: 11 Oct 2016 05:12

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