SET-LRP of NIPAM in water via in situ reduction of Cu(II) to Cu(0) with NaBH4

Gavrilov, Mikhail, Zerk, Timothy J., Bernhardt, Paul V., Percec, Virgil and Monteiro, Michael J. (2016) SET-LRP of NIPAM in water via in situ reduction of Cu(II) to Cu(0) with NaBH4. Polymer Chemistry, 7 4: 933-939. doi:10.1039/c5py01855b


Author Gavrilov, Mikhail
Zerk, Timothy J.
Bernhardt, Paul V.
Percec, Virgil
Monteiro, Michael J.
Title SET-LRP of NIPAM in water via in situ reduction of Cu(II) to Cu(0) with NaBH4
Formatted title
SET-LRP of NIPAM in water via in situ reduction of Cu(II) to Cu(0) with NaBH4
Journal name Polymer Chemistry   Check publisher's open access policy
ISSN 1759-9954
1759-9962
Publication date 2016-01-28
Year available 2016
Sub-type Article (original research)
DOI 10.1039/c5py01855b
Open Access Status Not Open Access
Volume 7
Issue 4
Start page 933
End page 939
Total pages 7
Place of publication Cambridge, United Kingdom
Publisher Royal Society of Chemistry
Language eng
Abstract The direct and quantitative reduction of the air-stable Cu(II) Br-2/Me6TREN to Cu(0) by NaBH4 represents a new method for the aqueous single electron transfer-living radical polymerization (SET-LRP) of water soluble polymers. By changing the stoichiometry of NaBH4 to Cu(II)Br-2, any desired ratio of Cu(II)Br-2 to Cu(0) could be obtained with no evidence of Cu(I) species. This quantitative reduction to Cu(0) in combination with rapid disproportionation of Cu(I) Br/Me6TREN in water resulted in activation by Cu(0) initially and during the polymerization. Polymerizations of NIPAM produced polymer within minutes and with controlled and narrow molecular weight distributions in agreement with ideal 'living' radical behavior. The direct in situ thio-bromo 'click' reaction produce polymers with stable chain-end functionality, eliminating the concern of hydrolysis of the halide end-group (i.e. Br). It was found that the end-group functionality was greater than 95%, and for the very rapid polymerizations close to 100%.
Formatted abstract
The direct and quantitative reduction of the air-stable Cu(II)Br2/Me6TREN to Cu(0) by NaBH4 represents a new method for the aqueous single electron transfer-living radical polymerization (SET-LRP) of water soluble polymers. By changing the stoichiometry of NaBH4 to Cu(II)Br2, any desired ratio of Cu(II)Br2 to Cu(0) could be obtained with no evidence of Cu(I) species. This quantitative reduction to Cu(0) in combination with rapid disproportionation of Cu(I)Br/Me6TREN in water resulted in activation by Cu(0) initially and during the polymerization. Polymerizations of NIPAM produced polymer within minutes and with controlled and narrow molecular weight distributions in agreement with ideal ‘living’ radical behavior. The direct in situ thio-bromo ‘click’ reaction produce polymers with stable chain-end functionality, eliminating the concern of hydrolysis of the halide end-group (i.e. Br). It was found that the end-group functionality was greater than 95%, and for the very rapid polymerizations close to 100%.
Keyword Polymer Science
Polymer Science
Q-Index Code C1
Q-Index Status Provisional Code
Institutional Status UQ

 
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Created: Fri, 19 Feb 2016, 20:52:40 EST by Mrs Louise Nimwegen on behalf of Aust Institute for Bioengineering & Nanotechnology