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, Tanja 
VANDERZANDE, Dirk 
Issue Date: 2011
Publisher: AMER CHEMICAL SOC
Source: 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
Document URI: http://hdl.handle.net/1942/12362
ISSN: 0024-9297
e-ISSN: 1520-5835
DOI: 10.1021/ma201453s
ISI #: 000295487600014
Category: A1
Type: Journal Contribution
Validations: ecoom 2012
Appears in Collections:Research publications

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