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Published June 9, 2009 | Supplemental Material
Journal Article Open

Efficient Synthesis of Narrowly Dispersed Brush Polymers via Living Ring-Opening Metathesis Polymerization of Macromonomers


Various macromonomers (MMs) were efficiently synthesized through the copper-catalyzed "click" coupling of a norbornene moiety to the chain end of poly(methylacrylate), poly(t-butylacrylate), and polystyrene that were prepared using atom transfer radical polymerization. Ring-opening metathesis polymerization (ROMP) of these MMs was carried out using the highly active, fast-initiating ruthenium catalyst (H_2IMes)(pyr)_2(Cl)_2RuCHPh in THF at room temperature. ROMP of MMs was found to be living with almost quantitative conversions (>90%) of MMs, producing brush polymers with very low polydispersity indices of 1.01−1.07 and high Mn's of 200−2600 kDa. The efficient ROMP of such MMs provides facile access to a variety of brush polymers and overcomes previous difficulties in the controlled polymerization of MMs. Atomic force microscopy of the brush polymer products revealed extended, wormlike shapes as a result of significant steric repulsion of densely grafted side chains.

Additional Information

© 2009 American Chemical Society. Received February 6, 2009; Revised Manuscript Received March 19, 2009. Publication Date (Web): April 20, 2009. This work was supported by the Department of Energy (DE-FG02-05ER46218) and the National Science Foundation (CHE-0410425). We gratefully acknowledge Dr. Bradley D. Olsen and Peigen Cao for helpful discussions about the AFM, and Professor James R. Heath for the use of the AFM. Supporting Information: Additional GPC traces of prepolymers, macromonomers, and brush polymers, 1H NMR spectra of brush polymers, and AFM cross-sectional analysis of brush polymer. This material is available free of charge via the Internet at http://pubs.acs.org.

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August 20, 2023
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