Termination kinetics of styrene free-radical polymerization studied by time-resolved pulsed laser experiments

Buback, M., Kowollik, C., Kurz, C., & Wahl, A. (2000) Termination kinetics of styrene free-radical polymerization studied by time-resolved pulsed laser experiments. Macromolecular Chemistry and Physics, 201(4).

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The single pulse (SP)-pulsed-laser polymerization (PLP) technique has been applied to measure kt/kp, the ratio of termination to propagation rate coefficients, for the free-radical bulk polymerization of styrene at temperatures from 60 to 100°C and pressures from 1800 to 2650 bar. kt/kp is obtained by fitting monomer concentration vs. time traces that are determined via time-resolved (μs) near infrared monitoring of monomer conversion induced by single excimer laser pulses of about 20 ns width. Styrene is a difficult candidate for this kind of measurements as conversion per pulse is small for this low kp and high kt monomer. Thus between 160 to 300 SP signals were co-added to yield a concentration vs. time trace of sufficient quality for deducing kt/kp with an accuracy of better than ±20 per cent. With kp being known from PLP-SEC experiments, chain-length averaged kt values are immediately obtained from kt/kp. At given pressure and temperature, kt is independent of the degree of overall monomer conversion, which, within the present study, has been as high as 20 %. The kt value, however, is found to slightly increase with the amount of free radicals produced by a single pulse in laser-induced decomposition of the photoinitiator DMPA (2,2-dimethoxy-2-phenyl acetophenone). This remarkable observation is explained by DMPA decomposition resulting in the formation of two free radicals which significantly differ in reactivity. Extrapolation of SP-PLP kt data from experiments at rather different DMPA levels and laser pulse energies toward low primary free-radical concentration, yields very satisfactory agreement of the extrapolated kt values with recent literature data from chemically and photochemically induced styrene polymerizations. © Wiley-VCH Verlag GmbH, 2000.

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ID Code: 99040
Item Type: Journal Article
Refereed: Yes
Additional Information: Cited By :62
Export Date: 20 September 2016
Correspondence Address: Buback, M.; Institut für Physikalische Chemie, Universität Göttingen, Tammannstraße 6, D-37077 Göttingen, Germany
References: Olaj, O.F., Schnöll-Bitai, I., (1989) Eur. Polym. J., 25, p. 635; Buback, M., Gilbert, R.G., Hutchinson, R.A., Klumperman, B., Kuchta, F.-D., Manders, B.G., O'Driscoll, K.F., Schweer, J., (1995) Macromol. Chem. Phys., 196, p. 3267; Buback, M., Kuchta, F.-D., (1995) Macromol. Chem. Phys., 196, p. 1887; Buback, M., Kurz, C.H., Schmaltz, C., (1998) Macromol. Chem. Phys., 199, p. 1721; Lyons, R.A., Hutovic, J., Piton, M.C., Christie, D.I., Clay, P.A., Manders, B.G., Cable, S.H., Gilbert, R.G., (1996) Macromolecules, 29, p. 1918; Beuermann, S., Paquet Jr., D.A., McMinn, J.H., Hutchinson, R.A., (1996) Macromolecules, 29, p. 4206; Manders, B.G., (1997), Ph.D. Thesis, EinhovenBeuermann, S., Buback, M., Russell, G.T., (1994) Macromol. Rapid Commun., 15, p. 351; Davis, T.P., O'Driscoll, K.F., Piton, M.C., Winnik, M.A., (1990) Macromolecules, 23, p. 2113; Hutchinson, R.A., Paquet Jr., D.A., McMinn, J.H., Beuermann, S., Fuller, R.E., Jackson, C., (1995) DECHEMA Monogr., 131, p. 467; Buback, M., Geers, U., Kurz, C.H., Heyne, J., (1997) Macromol. Chem. Phys., 198, p. 3451; Deibert, S., Bandermann, F., Schweer, J., Sarnecki, J., (1996) Macromol. Rapid Commun., 13, p. 351; Pascal, P., Winnik, M.A., Napper, D.H., Gilbert, R.G., (1993) Macromolecules, 26, p. 4572; Shipp, D.A., Smith, T.A., Solomon, D.H., Moad, G., (1995) Macromol. Rapid Commun., 16, p. 837; Van Herk, A.M., (1997) J. M. S. - Rev. Macromol. Chem. Phys., C37, p. 633; Buback, M., Hippler, H., Schweer, J., Vögele, H.-P., (1986) Makromol. Chem., Rapid Commun., 7, p. 261; Buback, M., (1990) Makromol. Chem., 191, p. 1575; Schweer, J., (1988), Ph.D. Thesis, GöttingenBuback, M., Schweer, J., (1988) Makromol. Chem., Rapid Commun., 9, p. 699; Buback, M., Schweer, J., (1989) Z. Phys. Chem. N. F., 161, p. 153; Kurz, C.H., (1995) Laserinduzierte Radikalische Polymerisation von Methylacrylat und Dodecylacrylat in Einem Weiten Zustandsbereich, , Graphikum Verlag, Göttingen; Beuermann, S., Buback, M., Schmaltz, C., (1999) Ind. Chem. Res., 38, p. 3338; Buback, M., Kowollik, C., (1999) Macromolecules, 32, p. 1445; Buback, M., Kowollik, C., (1999) Macromol. Chem. Phys., 200, p. 1764; Kowollik, C., (1999) Free-Radical Bulk Copolymerization Kinetics of Acrylate and Methacrylate Monomers Studied by Pulsed Laser Techniques, , Cuvillier Verlag, Göttingen; Buback, M., Kowollik, C., (1998) Macromolecules, 31, p. 3211; Buback, M., Kuchta, F.-D., (1997) Macromol. Chem. Phys., 198, p. 1455; Buback, M., Hinton, C., (1997) High-pressure Techniques in Chemistry and Physics, , W. B. Holzapfel, N. S. Isaacs, Eds., Oxford University Press, Oxford, England; Fischer, H., Baer, R., Hany, R., Verhoolen, I., Walbiner, M., (1990) J. Chem. Soc. Perkin Trans., 2, p. 787; Wulkow, M., (1996) Macromol. Theory Simul., 5, p. 393; Buback, M., Busch, M., Kowollik, C., Macromol. Theory Simul., , submitted
ISSN: 10221352
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: 22 Sep 2016 04:50

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