Improved Mechanistic Insights into Radical Sulfinyl Precursor MDMO-PPV Synthesis by Combining Microflow Technology and Computer Simulations

Neomy Zaquen, Paul H.M. Van Steenberge, Dagmar R. D'hooge, Marie Francoise Reyniers, Guy B. Marin, Joke Vandenbergh, Laurence Lutsen, Dirk J.M. Vanderzande, Thomas Junkers

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9 Citations (Scopus)

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.

Original languageEnglish
Pages (from-to)8294-8306
Number of pages13
JournalMacromolecules
Volume48
Issue number22
DOIs
Publication statusPublished - 2 Nov 2015
Externally publishedYes

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