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Cationic ring-opening polymerization of 2-propyl-2-oxazolines: understanding structural effects on polymerization behavior based on molecular modeling

Hannelore Goossens, Saron Catak UGent, Mathias Glassner, Victor Retamero De La Rosa UGent, Bryn Monnery, Frank De Proft, Veronique Van Speybroeck UGent and Richard Hoogenboom UGent (2013) ACS MACRO LETTERS. 2(8). p.651-654
abstract
The surprising difference in the cationic ring-opening polymerization rate of 2-c-yclopropyl-2-oxazoline versus 2-n-propyl-2-oxazoline and 2-isopropyl-2-oxazoline was investigated both experimentally and theoretically. The polymerization kinetics of all three oxazolines were experimentally measured in acetonitrile at 140 degrees C, and the polymerization rate constant (k(p)) was found to decrease in the order c-PropO x > n-PropOx > i-PropOx. Theoretical free energy calculations confirmed the trend for k(p), and a set of DFT-based reactivity descriptors, electrostatics, and frontier molecular orbitals were studied to detect the factors controlling this peculiar behavior. Our results show that the observed reactivity is dictated by electrostatic effects. More in particular, the charge on the nitrogen atom of the monomer, used to measure its nucleophilicity, was the most negative for c-PropOx. Furthermore, the electrophilicity of the cations does not change substantially, and thus, the nudeophilicity of the monomers is the driving factor for k(p).
Please use this url to cite or link to this publication:
author
organization
year
type
journalArticle (original)
publication status
published
subject
keyword
2-ETHYL-2-OXAZOLINE, POLYMERS, THERMOCHEMISTRY, PERSPECTIVE, OXAZOLINES, PRINCIPLE, POLY(2-OXAZOLINE)S, CHEMICAL-REACTIVITY, DENSITY-FUNCTIONAL-APPROACH, FRONTIER-ELECTRON THEORY
journal title
ACS MACRO LETTERS
ACS Macro Lett.
volume
2
issue
8
pages
651 - 654
Web of Science type
Article
Web of Science id
000323472100004
JCR category
POLYMER SCIENCE
JCR impact factor
5.242 (2013)
JCR rank
6/82 (2013)
JCR quartile
1 (2013)
ISSN
2161-1653
DOI
10.1021/mz400293y
language
English
UGent publication?
yes
classification
A1
copyright statement
I have transferred the copyright for this publication to the publisher
id
4145588
handle
http://hdl.handle.net/1854/LU-4145588
date created
2013-09-26 14:35:41
date last changed
2016-12-19 15:43:03
@article{4145588,
  abstract     = {The surprising difference in the cationic ring-opening polymerization rate of 2-c-yclopropyl-2-oxazoline versus 2-n-propyl-2-oxazoline and 2-isopropyl-2-oxazoline was investigated both experimentally and theoretically. The polymerization kinetics of all three oxazolines were experimentally measured in acetonitrile at 140 degrees C, and the polymerization rate constant (k(p)) was found to decrease in the order c-PropO x {\textrangle} n-PropOx {\textrangle} i-PropOx. Theoretical free energy calculations confirmed the trend for k(p), and a set of DFT-based reactivity descriptors, electrostatics, and frontier molecular orbitals were studied to detect the factors controlling this peculiar behavior. Our results show that the observed reactivity is dictated by electrostatic effects. More in particular, the charge on the nitrogen atom of the monomer, used to measure its nucleophilicity, was the most negative for c-PropOx. Furthermore, the electrophilicity of the cations does not change substantially, and thus, the nudeophilicity of the monomers is the driving factor for k(p).},
  author       = {Goossens, Hannelore and Catak, Saron and Glassner, Mathias and Retamero De La Rosa, Victor and Monnery, Bryn and De Proft, Frank and Van Speybroeck, Veronique and Hoogenboom, Richard},
  issn         = {2161-1653},
  journal      = {ACS MACRO LETTERS},
  keyword      = {2-ETHYL-2-OXAZOLINE,POLYMERS,THERMOCHEMISTRY,PERSPECTIVE,OXAZOLINES,PRINCIPLE,POLY(2-OXAZOLINE)S,CHEMICAL-REACTIVITY,DENSITY-FUNCTIONAL-APPROACH,FRONTIER-ELECTRON THEORY},
  language     = {eng},
  number       = {8},
  pages        = {651--654},
  title        = {Cationic ring-opening polymerization of 2-propyl-2-oxazolines: understanding structural effects on polymerization behavior based on molecular modeling},
  url          = {http://dx.doi.org/10.1021/mz400293y},
  volume       = {2},
  year         = {2013},
}

Chicago
Goossens, Hannelore, Saron Catak, Mathias Glassner, Victor Retamero De La Rosa, Bryn Monnery, Frank De Proft, Veronique Van Speybroeck, and Richard Hoogenboom. 2013. “Cationic Ring-opening Polymerization of 2-propyl-2-oxazolines: Understanding Structural Effects on Polymerization Behavior Based on Molecular Modeling.” Acs Macro Letters 2 (8): 651–654.
APA
Goossens, Hannelore, Catak, S., Glassner, M., Retamero De La Rosa, V., Monnery, B., De Proft, F., Van Speybroeck, V., et al. (2013). Cationic ring-opening polymerization of 2-propyl-2-oxazolines: understanding structural effects on polymerization behavior based on molecular modeling. ACS MACRO LETTERS, 2(8), 651–654.
Vancouver
1.
Goossens H, Catak S, Glassner M, Retamero De La Rosa V, Monnery B, De Proft F, et al. Cationic ring-opening polymerization of 2-propyl-2-oxazolines: understanding structural effects on polymerization behavior based on molecular modeling. ACS MACRO LETTERS. 2013;2(8):651–4.
MLA
Goossens, Hannelore, Saron Catak, Mathias Glassner, et al. “Cationic Ring-opening Polymerization of 2-propyl-2-oxazolines: Understanding Structural Effects on Polymerization Behavior Based on Molecular Modeling.” ACS MACRO LETTERS 2.8 (2013): 651–654. Print.