Solvent Choice Differentiates SET-LRP and Cu-Mediated Radical Polymerization with Non-First-Order Kinetics

G. Lligadas, B. Rosen, Monteiro, Michael J. and V. Percec (2008) Solvent Choice Differentiates SET-LRP and Cu-Mediated Radical Polymerization with Non-First-Order Kinetics. Macromolecules, 41 22: 8360-8364. doi:10.1021/ma801774d


Author G. Lligadas
B. Rosen
Monteiro, Michael J.
V. Percec
Title Solvent Choice Differentiates SET-LRP and Cu-Mediated Radical Polymerization with Non-First-Order Kinetics
Journal name Macromolecules   Check publisher's open access policy
ISSN 0024-9297
Publication date 2008-10-30
Year available 2008
Sub-type Article (original research)
DOI 10.1021/ma801774d
Open Access Status
Volume 41
Issue 22
Start page 8360
End page 8364
Total pages 5
Editor Timothy P. Lodge
Place of publication USA
Publisher ACS Publications
Language eng
Subject C1
030306 Synthesis of Materials
870303 Polymeric Materials (e.g. Paints)
Abstract In order to assess the role of the solvent mediating the disproportionation of Cu(I)X into Cu(0) and Cu(II)X2 during SET-LRP, a series of polymerizations of methyl acrylate initiated with methyl 2-bromopropionate and catalyzed by Cu(0)/Me6-TREN at 25 °C in DMSO, MeCN, and their mixtures were investigated. These polymerizations proceed in a dissimilar manner. SET-LRP of MA in DMSO, a solvent that mediates disproportionation, was exemplary of “ultrafast living radical polymerization” with complete conversion in 45 min following the expected first-order kinetics and providing perfect fidelity of the structure of the polymer chain ends. When the polymerization was performed in MeCN, a solvent in which Cu(I)X species do not disproportionate, it displayed nonlinear first-order kinetics with a poor retention of the bromine chain end functionality. The lack of first-order kinetics and decrease of chain end functionality with conversion indicate a nonliving polymerization in MeCN. Increasing the concentration of DMSO in DMSO/MeCN mixtures provided a continuous transition from a nonliving to a living polymerization. The incompatibility of MeCN with SET-LRP lends support that disproportionation of Cu(I)X/N ligand to Cu(0) and Cu(II)X2/N ligand is the key step in SET-LRP.
Keyword Polymer Science
Polymer Science
POLYMER SCIENCE
Q-Index Code C1
Q-Index Status Confirmed Code
Grant ID DMR-0548559
Institutional Status Non-UQ

Document type: Journal Article
Sub-type: Article (original research)
Collections: 2009 Higher Education Research Data Collection
Australian Institute for Bioengineering and Nanotechnology Publications
 
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Created: Tue, 07 Apr 2009, 23:31:43 EST by Mrs Jennifer Brown on behalf of Aust Institute for Bioengineering & Nanotechnology