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).
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.
Impact and interest:
Citation counts are sourced monthly from and 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 theindexing service can be viewed at the linked Google Scholar™ search.
|Item Type:||Journal Article|
|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
|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|
Repository Staff Only: item control page