Free-radical propagation rate coefficients of dodecyl methacrylate deduced from electron spin resonance experiments

Buback, M., Kowollik, C., Kamachi, M., & Kajiwara, A. (1998) Free-radical propagation rate coefficients of dodecyl methacrylate deduced from electron spin resonance experiments. Macromolecules, 31(21).

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Propagation rate coefficients (kp) for the free-radical polymerization of dodecyl methacrylate (DMA) in solution in toluene have been measured via electron spin resonance (ESR) spectroscopy in the temperature range O to 50 °C. The polymerization is photochemically induced at different initiator concentrations of di-tert-butyl peroxide (DTBP). Free-radical concentration under steady-state conditions is deduced from double integration of the well-resolved ESR spectra, consisting of 13 lines in the initial period of the polymerization reaction and 9 lines at enhanced degrees of monomer conversion. The kp values from ESR analysis are in excellent agreement with the corresponding data from pulsed laser polymerization (PLP)/size-exclusion chromatography (SEC), the IUPAC-recommended procedure for reliable kp measurement. The activation energy associated with the ESR kp data, EA = 21.7 ± 2.0 kJ mol-1, is in full agreement with EA (kp) results from recent PLP-SEC studies.

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ID Code: 99036
Item Type: Journal Article
Refereed: Yes
Additional Information: Cited By :36 Export Date: 20 September 2016 CODEN: MAMOB Correspondence Address: Buback, M.; Inst. für Physikalische Chemie, Georg-August-Univ. Göttingen, Tammannstr. 6, D-37077 Göttingen, Germany References: Olaj, O.F., Bitai, I., Hinkelmann, F., (1987) Makromol. Chem., 188, p. 1689; 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; Beuermann, S., Buback, M., Davis, T.P., Gilbert, R.G., Hutchinson, R.A., Olaj, O.F., Russell, G.T., Van Herk, A.M., (1997) Macromol. Chem. Phys., 198, p. 1545; Beuermann, S., Buback, M., Russell, G.T., (1994) Macromol. Rapid Commun., 15, p. 351; Davis, P.T., 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; Kurz, C.H., (1995), Ph.D. Thesis, GöttingenLyons, 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, EindhovenKajiwara, A., Kamachi, M., (1996) Macromolecules, 29, p. 2378; Kajiwara, A., Kamachi, M., (1997) Macromol. Chem. Phys., 198, p. 787; Buback, M., Gracia-Rubio, L.H., Gilbert, R.G., Napper, D.H., Guillot, J., Hamielec, A.E., Hill, D., Winnik, M.A., (1988) J. Polym. Sci., Polym. Lett. Ed., 26, p. 293; Buback, M., Gilbert, R.G., Russell, G.T., Hill, D.J.T., Moad, G., O'Driscoll, K.F., Shen, J., Winnik, M.A., (1992) J. Polym. Sci., Polym. Chem. Ed., 30, p. 851; Aleksandrov, H.P., Genkin, V.N., Kital, M.S., Smirovna, J.M., Sokolov, V.V., (1977) Kvantovaya Elektron. (Moscow), 4, p. 976; Olaj, O.F., Bitai, I., (1987) Angew. Makromol. Chem., 155, p. 177; Davis, T.P., O'Driscoll, K.F., Pinton, M.C., Winnik, M.A., (1989) Macromolecules, 22, p. 2785; Tonge, M.P., Kajiwara, A., Kamachi, M., Gilbert, R.G., (1998) Polymer, 39, p. 2305; Hutchinson, R.A., Beuermann, S., Paquet Jr., D.A., McMinn, J.H., (1997) Macromolecules, 30, p. 3490; Kamachi, M., (1987) Adv. Polym. Sci., 82, p. 209; Van Herk, A.M., (1995) J. Chem. Educ., 72, p. 138; Beuermann, S., Buback, M., Russell, G.T., (1994) Macromol. Rapid. Commun., 15, p. 647; Matsumoto, A., Mizuta, K., (1994) Polym. Bull., 33, p. 141
Keywords: Activation energy, Electron spin resonance spectroscopy, Monomers, Photopolymerization, Pulsed laser applications, Solutions, Toluene, Diterbutyl peroxide, Dodecyl methacrylate, Free radical concentration, Propagation rate coefficient, Pulsed laser polymerization, Free radical polymerization
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: 22 Sep 2016 04:50

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