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).

View at publisher


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.

Impact and interest:

61 citations in Scopus
60 citations in Web of Science®
Search Google Scholar™

Citation counts are sourced monthly from Scopus and Web of Science® citation databases.

These databases contain citations from different subsets of available publications and different time periods and thus the citation count from each is usually different. Some works are not in either database and no count is displayed. Scopus includes citations from articles published in 1996 onwards, and Web of Science® generally from 1980 onwards.

Citations counts from the Google Scholar™ indexing service can be viewed at the linked Google Scholar™ search.

ID Code: 99150
Item Type: Journal Article
Refereed: Yes
Additional Information: Cited By :58
Export Date: 5 September 2016
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:
References: Nikitin, A.N., Hutchinson, R.A., (2005) Macromolecules, 38, pp. 1581-1590; Theis, A., Feldermann, A., Charton, N., Davis, T.P., Stenzel, M.H., Barner-Kowollik, C., (2005) Polymer, 46, pp. 6797-6809; Junkers, T., Theis, A., Buback, M., Davis, T.P., Stenzel, M.H., Vana, P., Barner-Kowollik, C., (2005) Macromolecules, 38, pp. 9497-9508; Asua, J.M., Beuermann, S., Buback, M., Castignolles, P., Charleux, B., Gilbert, R.G., Hutchinson, R.A., Herk, A.M.V., (2004) Macromol. Chem. Phys, 205, pp. 2151-2160; Nikitin, A.N., Castignolles, P., Charleux, B., Vairon, J.-P., (2003) Macromol. Rapid Commun, 24, pp. 778-782; Boschmann, D., Vana, P., (2007) Macromolecules, 40, pp. 2683-2693; Farcet, T., Belleney, J., Charleux, B., Pirri, R., (2002) Macromolecules, 55, pp. 4912-4918; Postma, A., Davis, T.P., Li, G., Moad, G., O'Shea, M.S., (2006) Macromolecules, 39, pp. 5307-5318; Ahmad, N.M., Heatley, F., Lovell, P.A., (1998) Macromolecules, 31, pp. 2822-2827; Chiefari, J., Jeffery, J., Mayadunne, R.T.A., Moad, G., Rizzardo, E., Thang, S.H., (1999) Macromolecules, 32, pp. 7700-7702; Plessis, C., Arzamendi, G., Alberdi, J.M., Herk, A.M.V., Leiza, J.R., Asua, J.M., (2003) Macromol. Rapid Commun, 24, pp. 173-177; Arzamendi, G., Plessis, C., Leiza, J.R., Asua, J.M., (2003) Macromol. Theory Simul, 12, pp. 315-324; Busch, M., Müller, M., (2004) Macromol. Symp, 206, pp. 399-418; Peck, A.N.F., Hutchinson, R.A., (2004) Macromolecules, 37, pp. 5944-5951; Willemse, R.X.E., van Herk, A.M., Panchenko, E., Junkers, T., Buback, M., (2005) Macromolecules, 38, pp. 5098-5193; Azukizawa, M., Yamada, B., Hill, D.J.T., Pommery, P.J., (2000) Macromol. Chem. Phys, 201, pp. 774-781; Yamada, B., Azukizawa, M., Yamazoe, H., Hill, D.J.T., Pommery, P.J., (2000) Polymer, 41, pp. 5611-5618; Sato, E., Emoto, T., Zetterlund, P.B., Yamada, B., (2004) Macromol. Chem. Phys, 205, pp. 1829-1839; Plessis, C., Arzamendi, G., Leiza, J.R., Schoonbrood, H.A.S., Charmot, D., Asua, J.M., (2000) Macromolecules, 33, pp. 5041-5047; Rantow, F.S., Soroush, M., Grady, M.C., Kalfas, G.A., (2006) Polymer, 47, pp. 1423-1435; Barner-Kowollik, C., Davis, T.P., Stenzel, M.H., (2004) Polymer, 45, pp. 7791-7805; Szablan, Z., Lovestead, T.M., Davis, T.P., Stenzel, M.H., BarnerKowollik, C., (2007) Macromolecules, 40, pp. 26-39; Lovestead, T., Hart-Smith, G., Davis, T.P., Stenzel, M.H., BarnerKowollik, C., (2007) Macromolecules, 40, pp. 4142-4153; Grady, M.C., Simonsick, W.J., Hutchinson, R.A., (2002) Macromol. Symp, 182, pp. 149-168; Quan, C., Soroush, M., Grady, M.C., Hansen, J.E., Simonsick, W.J., (2005) Macromolecules, 38, pp. 7619-7628; Penzel, E., Götz, N., (1990) Angew. Makromol. Chem, 178, pp. 191-200; Strazielle, C., Benoit, H., Vogl, O., (1978) Eur. Polym. J, 14, pp. 331-334; Szablan, Z., Junkers, T., Koo, S.P.S., Lovestead, T.M., Stenzel, M.H., Davis, T.P., Barner-Kowollik, C., (2007) Macromolecules, 40, pp. 6820-6833; Zammit, M.D., Davis, T.P., Haddleton, D.M., Suddaby, K.G., (1997) Macromolecules, 30, pp. 1915-1920; Buback, M.; Günzler, F.; Russell, G. T.; Vana, P. Presented at the 29th Australasian Polymer Symposium, Hobart 11th to 15th February 2007; Conference Handbook; p 51polyBA macromonomer has been synthesized by polymerization of BA in butyl acetate solution (5 w%) at a low initiator concentration. The polymerization was continued for 45 min at 140 °C A complete characterization of the macromonomer obtained will be published in an upcoming studyUR -
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 > Institutes > Institute for Future Environments
Current > QUT Faculties and Divisions > Science & Engineering Faculty
Deposited On: 22 Sep 2016 04:50
Last Modified: 28 Jun 2017 14:02

Export: EndNote | Dublin Core | BibTeX

Repository Staff Only: item control page