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

(2013) ACS MACRO LETTERS. 2(8). p.651-654
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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).
Keywords
2-ETHYL-2-OXAZOLINE, POLYMERS, THERMOCHEMISTRY, PERSPECTIVE, OXAZOLINES, PRINCIPLE, POLY(2-OXAZOLINE)S, CHEMICAL-REACTIVITY, DENSITY-FUNCTIONAL-APPROACH, FRONTIER-ELECTRON THEORY

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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.
@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},
}

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