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Synthesis via RAFT Polymerization of Tadpole-Shaped Organic/Inorganic Hybrid Poly(acrylic acid) Containing Polyhedral Oligomeric Silsesquioxane (POSS) and Their Self-assembly in Water

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Makromolekulare Chemie II, Universität Bayreuth, D-95440 Bayreuth, Germany, and Laboratory for Advanced Materials, Department of Chemistry, East China University of Science and Technology, 130 Meilong Road, Shanghai 200237, P. R. China
* Corresponding author. E-mail: [email protected]
†Makromolekulare Chemie II, Universität Bayreuth.
‡Laboratory for Advanced Materials, Department of Chemistry, East China University of Science and Technology.
Cite this: Macromolecules 2009, 42, 7, 2563–2569
Publication Date (Web):March 10, 2009
Copyright © 2009 American Chemical Society

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    Tadpole-shaped inorganic/organic hybrid poly(tert-butyl acrylate) was prepared by RAFT polymerization of tert-butyl acrylate (tBA) using a POSS-containing chain transfer agent (CTA). The polymerization kinetics showed a pseudofirst-order behavior with a short induction period; the number-average molecular weights linearly increase with conversion. In conjunction with low polydispersity (PDI < 1.3), this confirms a controlled polymerization. POSS-PtBA was further hydrolyzed into amphiphilic, tadpole-shaped poly(acrylic acid) (POSS-PAA). The self-assembly behavior of POSS-PAA in aqueous solution at pH = 8.5 was investigated by transmission electron microscopy (TEM) as well as static and dynamic light scattering (SLS and DLS). The results show that POSS-PAA self-assembles in water into rather large aggregates where the POSS moieties are dispersed in the particle. The size (average radius ≈ 60 nm by DLS) is nearly independent of the chain length of PAA. The aggregates are pH-responsive, contracting when decreasing pH from 8.5 to 4.

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    Figures showing FTIR, 1H, 13C NMR and 29Si NMR spectra of POSS-PtBA and POSS-PAA and MALDI−TOF mass spectrum of POSS-PAA. This material is available free of charge via the Internet at

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