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Improved mechanistic insights into radical sulfinyl precursor MDMO-PPV synthesis by combining microflow technology and computer simulations

Neomy Zaquen, Paul Van Steenberge UGent, Dagmar D'hooge UGent, Marie-Françoise Reyniers UGent, Guy Marin UGent, Joke Vandenbergh, Laurence Lutsen, Dirk JM Vanderzande and Thomas Junkers (2015) 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.
Please use this url to cite or link to this publication:
author
organization
year
type
journalArticle (original)
publication status
published
subject
keyword
KINETIC MONTE-CARLO, LIGHT-EMITTING-DIODES, POLY(P-PHENYLENE VINYLENE), CONJUGATED POLYMERS, MICROSTRUCTURED REACTORS, P-QUINODIMETHANE, LEAVING GROUP, GILCH ROUTE, POLYMERIZATION, DERIVATIVES
journal title
MACROMOLECULES
Macromolecules
volume
48
issue
22
pages
8294 - 8306
Web of Science type
Article
Web of Science id
000365463900024
JCR category
POLYMER SCIENCE
JCR impact factor
5.554 (2015)
JCR rank
7/85 (2015)
JCR quartile
1 (2015)
ISSN
0024-9297
DOI
10.1021/acs.macromol.5b01884
language
English
UGent publication?
yes
classification
A1
copyright statement
I have transferred the copyright for this publication to the publisher
id
7011570
handle
http://hdl.handle.net/1854/LU-7011570
date created
2015-12-16 11:51:33
date last changed
2017-03-09 12:52:08
@article{7011570,
  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.},
  author       = {Zaquen, Neomy and Van Steenberge, Paul and D'hooge, Dagmar and Reyniers, Marie-Fran\c{c}oise and Marin, Guy and Vandenbergh, Joke and Lutsen, Laurence and Vanderzande, Dirk JM and Junkers, Thomas},
  issn         = {0024-9297},
  journal      = {MACROMOLECULES},
  keyword      = {KINETIC MONTE-CARLO,LIGHT-EMITTING-DIODES,POLY(P-PHENYLENE VINYLENE),CONJUGATED POLYMERS,MICROSTRUCTURED REACTORS,P-QUINODIMETHANE,LEAVING GROUP,GILCH ROUTE,POLYMERIZATION,DERIVATIVES},
  language     = {eng},
  number       = {22},
  pages        = {8294--8306},
  title        = {Improved mechanistic insights into radical sulfinyl precursor MDMO-PPV synthesis by combining microflow technology and computer simulations},
  url          = {http://dx.doi.org/10.1021/acs.macromol.5b01884},
  volume       = {48},
  year         = {2015},
}

Chicago
Zaquen, Neomy, Paul Van Steenberge, Dagmar D’hooge, Marie-Françoise Reyniers, Guy Marin, Joke Vandenbergh, Laurence Lutsen, Dirk JM Vanderzande, and Thomas Junkers. 2015. “Improved Mechanistic Insights into Radical Sulfinyl Precursor MDMO-PPV Synthesis by Combining Microflow Technology and Computer Simulations.” Macromolecules 48 (22): 8294–8306.
APA
Zaquen, Neomy, Van Steenberge, P., D’hooge, D., Reyniers, M.-F., Marin, G., Vandenbergh, J., Lutsen, L., et al. (2015). Improved mechanistic insights into radical sulfinyl precursor MDMO-PPV synthesis by combining microflow technology and computer simulations. MACROMOLECULES, 48(22), 8294–8306.
Vancouver
1.
Zaquen N, Van Steenberge P, D’hooge D, Reyniers M-F, Marin G, Vandenbergh J, et al. Improved mechanistic insights into radical sulfinyl precursor MDMO-PPV synthesis by combining microflow technology and computer simulations. MACROMOLECULES. 2015;48(22):8294–306.
MLA
Zaquen, Neomy, Paul Van Steenberge, Dagmar D’hooge, et al. “Improved Mechanistic Insights into Radical Sulfinyl Precursor MDMO-PPV Synthesis by Combining Microflow Technology and Computer Simulations.” MACROMOLECULES 48.22 (2015): 8294–8306. Print.