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Please use this identifier to cite or link to this item: http://hdl.handle.net/1942/20611

Title: Improved Mechanistic Insights into Radical Sulfinyl Precursor MDMO-PPV Synthesis by Combining Microflow Technology and Computer Simulations
Authors: Zaquen, Neomy
Van Steenberge, Paul H. M.
D'hooge, Dagmar R.
Reyniers, Marie-Francoise
Marin, Guy B.
Vandenbergh, Joke
Lutsen, Laurence
Vanderzande, Dirk J. M.
Junkers, Thomas
Issue Date: 2015
Citation: MACROMOLECULES, 48 (22), p. 8294-8306
Abstract: A kinetic model using Predici is developed and applied to obtain an improved mechanistic understanding of the radical sulfinyl precursor polymerization route for poly(2-methoxy-5-(3'-7'-dimethyloctyloxy-4-((octylsulfinyl)methyl))-1,4-phenylenevinylene) (MDMO-PPV) synthesis. In this route, the premonomer-1-(chloromethyl)-5-((3,7-dimethyloctyl)-oxy)-2-methoxy-4-((octylsulfinyl)methyl)benzene (MDMO) is subjected to a base-induced elimination reaction using NatBuO as base and s-BuOH as solvent. Microreactors are used to ensure rapid mixing of reaction components and sharp quenching at precisely determined time points. Systematic kinetic data that follows the very fast precursor polymerizations with reaction time have in this way become available for the first time. Via the applied kinetic model, the presence of a chain transfer reaction is unambiguously confirmed and kinetic rate coefficients have been deduced, which fall within the typical expectations of radical chain reactions. Two models were further compared, one including chain reinitiation (noninhibition model) and one excluding reinitiation (inhibition model) of the by chain transfer-generated radical species. Investigation of trend lines suggest a preference of the reinitiation model, thereby implying that MDMO-PPV synthesis follows mostly a conventional free radical polymerization mechanism that only differs with respect to its initiation mode and the biradical nature of the propagation step.
Notes: [Zaquen, Neomy; Vandenbergh, Joke; Vanderzande, Dirk J. M.; Junkers, Thomas] Hasselt Univ, Inst Mat Res IMO IMOMEC, Polymer React Design Grp PRD, B-3590 Diepenbeek, Belgium. [Van Steenberge, Paul H. M.; D'hooge, Dagmar R.; Reyniers, Marie-Francoise; Marin, Guy B.] Univ Ghent, Chem Technol Lab, B-9052 Ghent, Belgium. [D'hooge, Dagmar R.] Univ Ghent, Dept Text, B-9052 Ghent, Belgium. [Lutsen, Laurence; Vanderzande, Dirk J. M.; Junkers, Thomas] IMEC Associated Lab IMOMEC, B-3590 Diepenbeek, Belgium.
URI: http://hdl.handle.net/1942/20611
DOI: 10.1021/acs.macromol.5b01884
ISI #: 000365463900024
ISSN: 0024-9297
Category: A1
Type: Journal Contribution
Validation: ecoom, 2016
Appears in Collections: Research publications

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