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322. Zhang, W.; Fang, B.; Walther, A.; Müller, A.H.E.: Synthesis via RAFT Polymerization of Tadpole-Shaped Organic/Inorganic Hybrid Poly(acrylic acid) Containing Polyhedral Oligomeric Silsesquioxane (POSS) and Their Self-assembly in Water, Macromolecules 42(7), 2563 (2009) -- DOI: 10.1021/ma802803d -- PDF

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 pseudo-first-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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Related links:
  • Project: Alexander von Humboldt-Stiftung: Synthesis, self-assembly and properties of hybrid polymers based on polyhedral oligomeric silsesquioxane (POSS) molecules

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