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Title: | Solvent Effects on Acrylate k(p) in Organic Media?-A Systematic PLP-SEC Study | Authors: | Haehnel, Alexander P. WENN, Benjamin Kockler, Katrin Bantle, Tobias Misske, Andrea M. Fleischhaker, Friederike JUNKERS, Tanja Barner-Kowollik, Christopher |
Issue Date: | 2014 | Publisher: | WILEY-V C H VERLAG GMBH | Source: | MACROMOLECULAR RAPID COMMUNICATIONS, 35 (23), p. 2029-2037 | Abstract: | The Arrhenius parameters of the propagation rate coefficient, k(p), are determined employing high-frequency pulsed laser polymerization-size exclusion chromatography (PLP-SEC) for the homologous series of five linear alkyl acrylates (i.e., methyl acrylate (MA), butyl acrylate (BA), dodecyl acrylate (DA), stearyl acrylate (SA), and behenyl acrylate (BeA)) in 1 M solution in butyl acetate (BuAc) as well as in toluene. The comparison of the obtained k(p) values with the literature known values for bulk demonstrates that no significant solvent influence neither in BuAc nor in toluene on the propagation reaction compared to bulk is detectable. Concomitantly, the k(p) values in toluene and in BuAc solution display a similar increase with increasing number of C-atoms in the ester side chain as was previously reported for the bulk systems. These findings are in clear contrast to earlier studies, which report a decrease of k(p) with increasing ester side chain length in toluene. The additional investigation of the longest and shortest ester side chain acrylate (i.e., BeA and MA) over the entire experimentally available concentration range at one temperature (i.e., 50 degrees C) does not reveal any general concentration dependence and all observed differences in the k(p) are within the experimental error. | Notes: | [Haehnel, Alexander P.; Kockler, Katrin; Bantle, Tobias; Barner-Kowollik, Christopher] Karlsruhe Inst Technol, Inst Tech Chem & Polymerchem, D-76128 Karlsruhe, Germany. [Haehnel, Alexander P.; Kockler, Katrin; Bantle, Tobias; Barner-Kowollik, Christopher] Karlsruhe Inst Technol, Inst Biol Grenzflachen, D-76344 Eggenstein Leopoldshafen, Germany. [Wenn, Benjamin; Junkers, Thomas] Univ Hasselt, Inst Mat Res IMO IMOMEC, B-3590 Diepenbeek, Belgium. [Misske, Andrea M.; Fleischhaker, Friederike] BASF SE, D-67056 Ludwigshafen, Germany. | Keywords: | arrhenius parameters; free radical polymerization; kinetics; PLP-SEC; solvent effects | Document URI: | http://hdl.handle.net/1942/18106 | ISSN: | 1022-1336 | e-ISSN: | 1521-3927 | DOI: | 10.1002/marc.201400479 | ISI #: | 000345977300008 | Rights: | © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim. | Category: | A1 | Type: | Journal Contribution | Validations: | ecoom 2016 |
Appears in Collections: | Research publications |
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