Single-pulse pulsed laser polymerization-electron paramagnetic resonance investigations into the termination kinetics of n-butyl acrylate macromonomers

Barth, J., Buback, M., Barner-Kowollik, C., Junkers, T., & Russell, G. T. (2012) Single-pulse pulsed laser polymerization-electron paramagnetic resonance investigations into the termination kinetics of n-butyl acrylate macromonomers. Journal of Polymer Science, Part A: Polymer Chemistry, 50(22).

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Abstract

The termination of model mid-chain radicals (MCRs), which mimic radicals that occur in acrylate polymerization over a broad range of reaction conditions, has been studied by single-pulse pulsed laser polymerization (SP-PLP) in conjunction with electron paramagnetic resonance spectroscopy. The model radicals were generated by initiator-fragment addition to acrylic macromonomers that were preformed prior to the kinetic experiments, thus enabling separation of termination from the propagation reaction, for these model radicals propagate sparingly, if at all, on the timescale of SP-PLP experiments. Termination rate coefficients of the MCRs were determined in the temperature range of 0-60°C in acetonitrile and butyl propionate solution as well as in bulk macromonomer over the range of 0-100 °C. Termination rate coefficients slightly below those of the corresponding secondary radicals were deduced, demonstrating the relatively high termination activity of this species, even when undergoing MCR-MCR termination. For chain length of 10, a reduction by a factor of 6 is observed. Unusually high activation energies were found for the termination rate coefficient in these systems, with 35 kJ mol -1 being determined for bulk macromonomer. Copyright © 2012 Wiley Periodicals, Inc.

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ID Code: 99301
Item Type: Journal Article
Refereed: Yes
Additional Information: Cited By :8
Export Date: 5 September 2016
CODEN: JPACE
Correspondence Address: Russell, G.T.; Department of Chemistry, University of Canterbury, Christchurch, New Zealand; email: greg.russell@canterbury.ac.nz
References: Junkers, T., Barner-Kowollik, C., (2008) J. Polym. Sci. Part A: Polym. Chem., 46, pp. 7585-7605; 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; Nikitin, A.N., Hutchinson, R.A., (2005) Macromolecules, 38, pp. 1581-1590; Nikitin, A.N., Castignolles, P., Charleux, B., Vairon, J.P., (2003) Macromol. Rapid Commun., 24, pp. 778-782; Barth, J., Buback, M., (2010) Macromol. React. Eng., 4, pp. 288-301; Buback, M., Egorov, M., Junkers, T., Panchenko, E., (2004) Macromol. Rapid Commun., 25, pp. 1004-1009; Barner-Kowollik, C., Buback, M., Egorov, M., Fukuda, T., Goto, A., Olaj, O.F., Russell, G.T., Zetterlund, P.B., (2005) Prog. Polym. Sci., 30, pp. 605-643; Barth, J., Buback, M., Hesse, P., Sergeeva, T., (2009) Macromol. Rapid Commun., 30, pp. 1969-1974; Barth, J., Buback, M., Hesse, P., Sergeeva, T., (2010) Macromolecules, 43, pp. 4023-4031; Zorn, A.-M., Junkers, T., Barner-Kowollik, C., (2011) Macromolecules, 44, pp. 6691-6700; Junkers, T., unpublished workTanaka, K., Yamada, B., Fellows, C.M., Gilbert, R.G., Davis, T.P., Yee, L.H., Smith, G.B., Russell, G.T., (2001) J. Polym. Sci. Part A: Polym. Chem., 39, pp. 3902-3915; Buback, M., Junkers, T., Müller, M., (2009) Polymer, 50, pp. 3111-3118; Junkers, T., Bennet, F., Koo, S.P.S., Barner-Kowollik, C., (2008) J. Polym. Sci. Part A: Polym. Chem., 46, pp. 3433-3437; Koo, S.P.S., Junkers, T., Barner-Kowollik, C., (2009) Macromolecules, 42, pp. 62-69; Zorn, A.M., Junkers, T., Barner-Kowollik, C., (2009) Macromol. Rapid Commun., 30, pp. 2028-2035; Barth, J., Buback, M., Hesse, P., Sergeeva, T., (2009) Macromolecules, 42, pp. 481-488; Buback, M., Hippler, H., Schweer, J., Vogele, H.P., (1986) Makromol. Chem. Rapid Commun., 7, pp. 261-265; Barth, J., Buback, M., Russell, G.T., Smolne, S., (2011) Macromol. Chem. Phys., 212, pp. 1366-1378; Barth, J., Siegmann, R., Beuermann, S., Russell, G.T., Buback, M., (2012) Macromol. Chem. Phys., 213, pp. 19-28; Barner-Kowollik, C., Russell, G.T., (2009) Prog. Polym. Sci., 34, pp. 1211-1259; Junkers, T., Barner-Kowollik, C., (2010) Macromol. Theory Simul., 18, pp. 421-433; Smith, G.B., Russell, G.T.Z., (2005) Phys. Chem. (Munich), 219, pp. 295-323; Wulkow, M., (1996) Macromol. Theory Simul., 5, pp. 393-416; Smith, G.B., Russell, G.T., Heuts, J.P.A., (2003) Macromol. Theory Simul., 12, pp. 299-314; Fröhlich, M.G., Vana, P., Zifferer, G., (2007) J. Chem. Phys., 127, p. 164906; Buback, M., Egorov, M., Junkers, T., Panchenko, E., (2005) Macromol. Chem. Phys., 206, pp. 333-341; Vana, P., Yee, L.H., Barner-Kowollik, C., Heuts, J.P.A., Davis, T.P., (2002) Macromolecules, 35, pp. 1651-1657; Nikitin, A.N., Hutchinson, R.A., (2006) Macromol. Theory Simul., 15, pp. 128-136; Nikitin, A.N., Hutchinson, R.A., (2009) Macromol. Rapid Commun., 30, pp. 1981-1988; Nikitin, A.N., Hutchinson, R.A., Wang, W., Kalfas, G.A., Richards, J.R., Bruni, C., (2010) Macromol. React. Eng., 4, pp. 691-706
Keywords: ESR/EPR, kinetics (polym.), macromonomers (acrylate), mid-chain radicals, radical polymerization, termination, Kinetics(polym.), Macro-monomers, Acetonitrile, Acrylics, Activation energy, Electron spin resonance spectroscopy, Experiments, Free radical polymerization, Kinetics, Magnetic resonance, Paramagnetism, Pulsed lasers, Monomers
DOI: 10.1002/pola.26295
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: 04 Oct 2016 03:23

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