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Modification of Silica Nanoparticles with Miktoarm Polymer Brushes via ATRP

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Abstract

Silica nanoparticles were successfully modified with miktoarm brushes via atom transfer radical polymerization (ATRP) using three different approaches. In the first approach: “graft onto and from”, a poly(tert-butyl acrylate) (PtBA) macroinitiator was grafted onto the surface of a monomer-modified silica nanoparticle. Then, polystyrene (PSt) brush was grafted from the surface-tethered reactive chain end. In the second approach: “two-step reverse ATRP”, the PtBA and poly(n-butyl acrylate) (PBA) brushes were consecutively grafted from initiator-modified silica particles via ATRP. The polymerization was initiated from the silica surface via a two-step controlled thermal decomposition of surface-tethered diazo initiator moieties. In the third method: “diblock first”, a diblock copolymer of poly(tert-butyl acrylate) and poly(glycidyl methacrylate) (PtBA-b-PGMA) was grafted onto amine-modified silica particles. The diblock copolymer was covalently attached to the silica surface via interaction between surface-tethered amine groups and the short reactive block containing glycidyl groups. Next, the polystyrene brushes were grafted from surface-tethered reactive chain end. The materials prepared by three different approaches were characterized using gel permeation chromatography (GPC) and thermogravimetric analysis (TGA). The PtBA brushes were hydrolyzed under acidic conditions to form poly(acrylic acid) (PAA) brushes. The resulting materials were imaged using atomic force microscopy (AFM) and transmission electron microscopy (TEM).

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Acknowledgments

Financial support from NSF (DMR 1501324), BSF (2012074), DoE (EE0006702), Polish Ministry of Science and Higher Education (“Mobilnosc Plus” Grant No. 1055/MOB/2013/0) and Polish National Science Center (grant 2014/14/A/ST5/00204) is gratefully acknowledged.

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Authors and Affiliations

  1. Department of Chemistry, Carnegie Mellon University, 4400 Fifth Ave, Pittsburgh, PA, 15213, USA

    Amir Khabibullin, Maciej Kopeć & Krzysztof Matyjaszewski

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  1. Amir Khabibullin
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  2. Maciej Kopeć
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  3. Krzysztof Matyjaszewski
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Correspondence to Krzysztof Matyjaszewski.

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Khabibullin, A., Kopeć, M. & Matyjaszewski, K. Modification of Silica Nanoparticles with Miktoarm Polymer Brushes via ATRP. J Inorg Organomet Polym 26, 1292–1300 (2016). https://doi.org/10.1007/s10904-016-0427-2

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  • DOI: https://doi.org/10.1007/s10904-016-0427-2

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