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Synthesis and Characterization of Molecular Bottlebrushes Prepared by Iron-Based ATRP

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Department of Chemistry, Center for Macromolecular Engineering, Carnegie Mellon University, 4400 Fifth Avenue, Pittsburgh, Pennsylvania 15213, United States
Department of Chemistry, University of North Carolina at Chapel Hill, Chapel Hill, North Carolina 27599-3290, United States
Cite this: Macromolecules 2012, 45, 23, 9243–9249
Publication Date (Web):November 19, 2012
https://doi.org/10.1021/ma3020867
Copyright © 2012 American Chemical Society
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Abstract

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Molecular bottlebrushes with hydrophobic poly(n-butyl acrylate) or polystyrene and hydrophilic poly(di(ethylene glycol) ethyl ether acrylate)) side chains were successfully synthesized by grafting from a poly(2-(2-bromoisobutyryloxy)ethyl methacrylate) macroinitiator using iron-based atom transfer radical polymerization (ATRP). Iron(II) bromide, iron(III) bromide, and tetrabutylammonium bromide catalyst was employed for an ATRP grafting-from reaction, resulting in brush macromolecules with a narrow molecular weight distribution (Mw/Mn = 1.18–1.28). Molecular weights measured by multiangle laser light scattering correlates well with the theoretical values for all bottlebrushes. Imaging of individual bottlebrushes by atomic force microscopy exhibited a wormlike conformation. Initiation efficiencies were calculated by cleaving the side chains by alcoholysis and then injecting to gel permeation chromatography. The initiation efficiencies were ca. 80–95%, showing relatively high values for a grafting from polymerization with an iron catalyst. These results indicate that iron-catalyzed ATRP allows well-controlled polymerization even when targeting dense grafting from procedures. The 0.1% (w/w) of water-soluble molecular bottlebrushes with poly(di(ethylene glycol) ethyl ether acrylate)) side chains displayed a lower critical solution temperature behavior in distilled water, and the average particle size started to increase above 8 °C due to intermolecular aggregation of the bottlebrushes. The slight decrease of the size in highly diluted solution (0.005% w/w) of the bottlebrush was observed as the temperature was increased, suggesting that intramolecular collapse of the individual molecules.

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