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Title: Determination of Propagation Rate Coefficients for Methyl and 2-Ethylhexyl Acrylate via High Frequency PLP-SEC under Consideration of the Impact of Chain Branching
Authors: JUNKERS, Thomas
Schneider-Baumann, Maria
Koo, Sandy S. P.
Castignolles, Patrice
Barner-Kowollik, Christopher
Issue Date: 2010
Citation: MACROMOLECULES, 43(24). p. 10427-10434
Abstract: The radical propagation rate coefficients, k(p) 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/degrees 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(V-e) 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 x 10(-5) dL g(-1) alpha = 0 741) and (K = 9 85 x 10(-5) dL g(-1), alpha = 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 k(p) of EHA are beset with a larger error than those of MA The activation parameters in the temperature range between 20 and 80 degrees C read E-A(MA) = 18 5 (+0 8 to -0 9) kJ mol(-1) and A(MA) = 2 5 (+1 2 to -0 6) x 10(7) L mol(-1) s(-1), E-A(LIIA) = 15 8(+1 6 to -1 4) kJ mol(-1) and A(EHA) = 9 1 (+10 1 to -29) x 10(6) L mol(-1) s(-1)
Notes: [Junkers, Thomas; Schneider-Baumann, Maria; Koo, Sandy S. P.; Barner-Kowollik, Christopher] KIT, Inst Tech Chem & Polymerchem, D-76128 Karlsruhe, Germany. [Junkers, Thomas] Univ Hasselt, Inst Mat Res, B-3590 Diepenbeek, Belgium. [Castignolles, Patrice] Univ Western Sydney, Sch Nat Sci, Australian Ctr Res Separat Sci, Penrith, NSW 1797, Australia.
URI: http://hdl.handle.net/1942/11845
DOI: 10.1021/ma102130h
ISI #: 000285429400038
ISSN: 0024-9297
Category: A1
Type: Journal Contribution
Validation: ecoom, 2012
Appears in Collections: Research publications

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