Determination of propagation rate coefficients for methyl and 2-ethylhexyl acrylate via high frequency PLP-SEC under consideration of the impact of chain branching

Junkers, T., Schneider-Baumann, M., Koo, S. S. P., Castignolles, P., & Barner-Kowollik, C. (2010) Determination of propagation rate coefficients for methyl and 2-ethylhexyl acrylate via high frequency PLP-SEC under consideration of the impact of chain branching. Macromolecules, 43(24).

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The radical propagation rate coefficients, kp, of methyl acrylate (MA) and 2-ethylhexyl acrylate (EHA) have been determined in bulk via high frequency (500 Hz) pulsed laser polymerization coupled to size exclusion chromatography (PLP-SEC) up to elevated temperatures (20 ≤ T/°C ≤ 80). Prior to the analysis of the generated polymeric material, an investigation into the branching behavior of the generated polymers has been undertaken, employing the concept of local dispersity, D(Ve). In addition, the Mark-Houwkink-Kuhn-Sakurada parameters for both poly(MA) and polyEHA were determined at each studied reaction temperature. The temperature averaged values read (K = 10.2 × 10-5 dL g-1; α = 0.741) and (K = 9.85 × 10-5 dL g-1; α = 0.719) for poly(MA) and polyEHA, respectively. The local dispersity data indicate that branching in polyEHA may be considerably more prevalent than in poly(MA), as with increasing temperature polymer microinhomogeneities are observed. Consequently, the Arrhenius parameters for kp of EHA are beset with a larger error than those of MA. The activation parameters in the temperature range between 20 and 80 °C read: EA MA = 18.5 (+0.8 to -0.9) kJ•mol-1 and AMA = 2.5 (+1.2 to -0.6) × 107 L•mol-1•s-1; EA EHA = 15.8 (+1.6 to -1.4) kJ•mol-1 and A EHA = 9.1 (+10.1 to -2.9) × 106 L•mol -1•s-1. © 2010 American Chemical Society.

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ID Code: 99248
Item Type: Journal Article
Refereed: Yes
Additional Information: Cited By :23 Export Date: 5 September 2016 CODEN: MAMOB Correspondence Address: Junkers, T.; Preparative Macromolecular Chemistry, Karlsruhe Institute of Technology (KIT), Institut für Technische Chemie und Polymerchemie, Engesserstr. 18, 76128 Karlsruhe, Germany; email: References: Matyjaszewski, K., Xia, J., (2001) Chem. Rev., 101, p. 2921; Chiefari, J., Jeffery, J., Mayadunne, R.T.A., Moad, G., Rizzardo, E., Thang, S.H., (1999) Macromolecules, 32, pp. 7700-7704; Hawker, C.J., Bosman, A.W., Harth, E., (2001) Chem. Rev., 301, p. 3661; Beuermann, S., Buback, M., (2002) Prog. Polym. Sci., 27, pp. 191-254; Barner-Kowollik, C., Buback, M., Egorov, M., Fukuda, T., Goto, A., Russell, G.T., Vana, P., Zetterlund, P.B., (2005) Prog. Polym. Sci., 30, p. 605; Olaj, O.F., Bitai, I., Hinkelmann, F., (1987) Makromol. 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Keywords: 2-Ethyl hexyl acrylate, Activation parameter, Arrhenius parameters, Chain branching, Dispersity, Elevated temperature, High frequency, Methyl acrylates, Microinhomogeneities, Polymeric material, Propagation rate coefficient, Pulsed laser polymerization, Reaction temperature, Temperature range, Acrylic monomers, Size exclusion chromatography, Polymers
DOI: 10.1021/ma102130h
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: 07 Oct 2016 02:42

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