Photoinduced Atom Transfer Radical Polymerization with ppm-Level Cu Catalyst by Visible Light in Aqueous Media
Department of Chemistry, Carnegie Mellon University, 4400 Fifth Avenue, Pittsburgh, Pennsylvania 15213,United States
J. Am. Chem. Soc., Article ASAP
DOI: 10.1021/jacs.5b11599
Publication Date (Web): December 4, 2015
Copyright © 2015 American Chemical Society
Abstract
Photoinduced ATRP was successfully performed in aqueous media. Polymerization of oligo(ethylene oxide) methyl ether methacrylate (OEOMA) in the presence of CuBr2 catalyst and tris(2-pyridylmethyl)amine ligand when irradiated with visible light of 392 nm wavelength at 0.9 mW/cm2 intensity was well controlled. Linear semi-logarithmic kinetic plots and molecular weights increasing with conversion were observed. Polymers of OEOMA were synthesized with low dispersity (Mw/Mn = 1.12) using only 22 ppm of copper catalyst in the presence of excess bromide anions in highly diluted (90% v/v) aqueous media. The effects of copper concentration, salt, and targeted degrees of polymerization were investigated. The polymerization could be directly regulated by external stimulation, i.e., switching the irradiation on/off, with a good retention of chain-end functionality, as proved by clean chain extension of the OEOMA polymers. This new system could enable applications for controlled aqueous radical polymerization due to its low catalyst loading in the absence of any other chemicals.
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