A comparative study of the SET-LRP of oligo(ethylene oxide) methyl ether acrylate in DMSO and in H2O

Nguyen, Nga H., Kulis, Jakov, Sun, Hao-Jan, Jia, Zhongfan, Van Beusekom, Bart, Levere, Martin E., Wilson, Daniela A., Monteiro, Michael J. and Percec, Virgil (2013) A comparative study of the SET-LRP of oligo(ethylene oxide) methyl ether acrylate in DMSO and in H2O. Polymer Chemistry, 4 1: 144-155. doi:10.1039/c2py20782f

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Author Nguyen, Nga H.
Kulis, Jakov
Sun, Hao-Jan
Jia, Zhongfan
Van Beusekom, Bart
Levere, Martin E.
Wilson, Daniela A.
Monteiro, Michael J.
Percec, Virgil
Title A comparative study of the SET-LRP of oligo(ethylene oxide) methyl ether acrylate in DMSO and in H2O
Journal name Polymer Chemistry   Check publisher's open access policy
ISSN 1759-9954
1759-9962
Publication date 2013-01-01
Year available 2012
Sub-type Article (original research)
DOI 10.1039/c2py20782f
Open Access Status Not Open Access
Volume 4
Issue 1
Start page 144
End page 155
Total pages 12
Place of publication Cambridge, United Kingdom
Publisher R S C
Language eng
Abstract A comparative analysis of the SET-LRP of oligo(ethylene oxide) methyl ether acrylate (OEOMEA) in DMSO and in H2O at 25 degrees C is reported. Both the catalysis with activated Cu(0) wire/Me-6-TREN and with mimics of "nascent" Cu(0) nanoparticles/Me-6-TREN resulted in a higher rate of polymerization in water than in DMSO. This result is consistent with the acceleration expected for SET-LRP by a more polar reaction solvent, and with the difference between the equilibrium constants of disproportionation of CuBr in DMSO (K-d = 1.4-4.4) and in water (K-d = 10(6) to 10(7)), both much higher in the presence of Me-6-TREN. The inefficient access of the Cu(0) catalyst to the hydrophobic reactive centers of the monomer and initiator assembled in micellar structures explains the induction time observed in the SET-LRP of OEOMEA in water. This induction period is longer for Cu(0) wire. The use of "nascent" Cu(0) nanoparticles prepared by the disproportionation of CuBr in DMSO, in combination with 5 mol% CuBr2, led to an extremely efficient SET-LRP of OEOMEA in water. This SET-LRP in water is fast and follows first order kinetics to complete monomer conversion with linear dependence of experimental M-n on conversion, and narrow molecular weight distribution. Under the polymerization conditions investigated in both water and DMSO, no reduction in the absorbance of CuBr2/Me-6-TREN was observed by online UV-vis spectroscopy. This excludes the formation of CuBr by reduction of CuBr2 by Cu(0) during the SET-LRP in DMSO and in water.
Formatted abstract
A comparative analysis of the SET-LRP of oligo(ethylene oxide) methyl ether acrylate (OEOMEA) in DMSO and in H2O at 25 °C is reported. Both the catalysis with activated Cu(0) wire/Me6-TREN and with mimics of “nascent” Cu(0) nanoparticles/Me6-TREN resulted in a higher rate of polymerization in water than in DMSO. This result is consistent with the acceleration expected for SET-LRP by a more polar reaction solvent, and with the difference between the equilibrium constants of disproportionation of CuBr in DMSO (Kd = 1.4–4.4) and in water (Kd = 106 to 107), both much higher in the presence of Me6-TREN. The inefficient access of the Cu(0) catalyst to the hydrophobic reactive centers of the monomer and initiator assembled in micellar structures explains the induction time observed in the SET-LRP of OEOMEA in water. This induction period is longer for Cu(0) wire. The use of “nascent” Cu(0) nanoparticles prepared by the disproportionation of CuBr in DMSO, in combination with 5 mol% CuBr2, led to an extremely efficient SET-LRP of OEOMEA in water. This SET-LRP in water is fast and follows first order kinetics to complete monomer conversion with linear dependence of experimental Mn on conversion, and narrow molecular weight distribution. Under the polymerization conditions investigated in both water and DMSO, no reduction in the absorbance of CuBr2/Me6-TREN was observed by online UV-vis spectroscopy. This excludes the formation of CuBr by reduction of CuBr2 by Cu(0) during the SET-LRP in DMSO and in water.
Keyword SET-LRP
OEOMEA
DMSO
Water
Nanoparticles
Monomer conversion
Q-Index Code C1
Q-Index Status Confirmed Code
Grant ID DMR-1120901
FP7/2007-20012/ERC-StG 307679
Institutional Status UQ
Additional Notes First published online: 8 October 2012.

 
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