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Please use this identifier to cite or link to this item: http://hdl.handle.net/1942/12362

Title: Discovery of an Anionic Polymerization Mechanism for High Molecular Weight PPV Derivatives via the Sulfinyl Precursor Route
Authors: COSEMANS, Inge
HONTIS, Lieve
VAN DEN BERGHE, David
PALMAERTS, Arne
WOUTERS, Jimmy
CLEIJ, Thomas
LUTSEN, Laurence
MAES, Wouter
JUNKERS, Thomas
VANDERZANDE, Dirk
Issue Date: 2011
Publisher: AMER CHEMICAL SOC
Citation: MACROMOLECULES, 44(19). p. 7610-7616
Abstract: The polymerization of PPV via the sulfinyl precursor route has been investigated with respect to its mechanism. When polymerized in sec-butanol, a purely radical polymerization mechanism is observed as in most precursor polymerization routes. Accordingly, an increase in the reaction temperature induced an increase in the overall yield alongside with a reduction of the average molecular weight of the polymer. Upon changing the monomer concentration in solution before addition of the base NatBuO, an increase in molecular weight is observed, signifying that the polymerization is faster than the mixing of the two reaction components. When changing the solvent to NMP, a competition of anionic and radical polymerization has been established while in THF an anionic polymerization mechanism occurs exclusively. To prevent termination reactions, LDA and LHMDS were introduced as base whereby LHMDS shows less propensity to initiate anionic chain growth due to higher steric hindrance. With polymerizations in presence of the radical quencher TEMPO, the anionic polymerization mechanism could unambiguously be proven.
Notes: Vanderzande, DJM (reprint author),[Cosemans, I; Hontis, L; Van Den Berghe, D; Palmaerts, A; Wouters, J; Cleij, TJ; Maes, W; Junkers, T; Vanderzande, DJM] Hasselt Univ, Inst Mat Res IMO, B-3590 Diepenbeek, Belgium. [Lutsen, L; Vanderzande, DJM] IMEC, Div IMOMEC, B-3590 Diepenbeek, Belgium. dirk.vanderzande@uhasselt.be
URI: http://hdl.handle.net/1942/12362
DOI: 10.1021/ma201453s
ISI #: 000295487600014
ISSN: 0024-9297
Category: A1
Type: Journal Contribution
Validation: ecoom, 2012
Appears in Collections: Research publications

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