Nitroxide-Mediated Radical Polymerization/Increase of Steric Demand in Nitroxides. How Much Is Too Much?
Publication type: Journal Article
Publication date: 2006-01-20
scimago Q1
wos Q1
SJR: 1.352
CiteScore: 9.0
Impact factor: 5.2
ISSN: 00249297, 15205835
Materials Chemistry
Organic Chemistry
Inorganic Chemistry
Polymers and Plastics
Abstract
The influence of increasing steric demand in the nitroxide moiety of cyclic alkoxyamines derived from side chain modified TEMPO (2,2,6,6-tetramethylpiperidine-N-oxyl) derivatives on nitroxide-mediated polymerization (NMP) of n-butyl acrylate and styrene is described. Polymerizations at low temperatures (as low as 70 °C) with good control over the molecular weight distribution (polydispersity index, PDI < 1.2) can be achieved using sterically highly demanding nitroxides. Polymerization efficiency increases with the size of the nitroxide substituents. It is shown that in these sterically highly hindered alkoxyamines it is not the rate of homolysis (kd) but the rate of recombination (kc) of the persistent nitroxide with the transient macroradical that is mainly responsible for the enhanced polymerization efficiency (lowering of the reaction time). However, for too bulky nitroxides, the trapping reaction of the nitroxide with the macroradical becomes too slow and uncontrolled NMP is obtained.
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60
Total citations:
60
Citations from 2024:
2
(3.33%)
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Siegenthaler K. O., Studer A. Nitroxide-Mediated Radical Polymerization/Increase of Steric Demand in Nitroxides. How Much Is Too Much? // Macromolecules. 2006. Vol. 39. No. 4. pp. 1347-1352.
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Siegenthaler K. O., Studer A. Nitroxide-Mediated Radical Polymerization/Increase of Steric Demand in Nitroxides. How Much Is Too Much? // Macromolecules. 2006. Vol. 39. No. 4. pp. 1347-1352.
Cite this
RIS
Copy
TY - JOUR
DO - 10.1021/ma0513463
UR - https://doi.org/10.1021/ma0513463
TI - Nitroxide-Mediated Radical Polymerization/Increase of Steric Demand in Nitroxides. How Much Is Too Much?
T2 - Macromolecules
AU - Siegenthaler, Kai Oliver
AU - Studer, Armido
PY - 2006
DA - 2006/01/20
PB - American Chemical Society (ACS)
SP - 1347-1352
IS - 4
VL - 39
SN - 0024-9297
SN - 1520-5835
ER -
Cite this
BibTex (up to 50 authors)
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@article{2006_Siegenthaler,
author = {Kai Oliver Siegenthaler and Armido Studer},
title = {Nitroxide-Mediated Radical Polymerization/Increase of Steric Demand in Nitroxides. How Much Is Too Much?},
journal = {Macromolecules},
year = {2006},
volume = {39},
publisher = {American Chemical Society (ACS)},
month = {jan},
url = {https://doi.org/10.1021/ma0513463},
number = {4},
pages = {1347--1352},
doi = {10.1021/ma0513463}
}
Cite this
MLA
Copy
Siegenthaler, Kai Oliver, and Armido Studer. “Nitroxide-Mediated Radical Polymerization/Increase of Steric Demand in Nitroxides. How Much Is Too Much?.” Macromolecules, vol. 39, no. 4, Jan. 2006, pp. 1347-1352. https://doi.org/10.1021/ma0513463.