University of Tasmania
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Polymer-inorganic hybrid nanoparticles via polymerization-induced self-assembly

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posted on 2023-05-28, 09:08 authored by Teo, GH
Silica nanoparticles are commonly integrated within polymeric matrices to form composite materials, due to their non-toxic nature, chemical resistance and physical properties. Polymer-silica colloidal nanocomposites are the most studied class of hybrid nanoparticles and their applications can be tailored based on synthetic approaches. The aims of this work were to prepare polymer-silica colloidal nanocomposites via a combination of reversible deactivation radical polymerization, self-assembly and sol-gel chemistry. This approach enabled the preparation of hybrid nanoparticles with controllable shape and size. The influences of compositional design (e.g. block copolymer architecture), solvent and initiating systems were also studied. Firstly, polymer nanoparticles were prepared by Polymerization-Induced Self-Assembly (PISA) in ethanol where the solvophilic block was an alkoxysilane-functional methacrylate. Spherical nanoparticles and polymeric vesicles were successfully prepared. A solid silica shell was successfully grown from the particle surface via subsequent hydrolysis and condensation of tetraethyl orthosilicate. Secondly, block copolymer self-assembly was studied where the alkoxysilane functionality was present in the core-forming block. This approach was not viable by aqueous PISA emulsion polymerization. A solvent-mediated self-assembly approach was thus adopted, yielding spherical nanoparticles in water, and a mixture of spheres and vesicles in n-hexane. Finally, the reactivity of alkoxysilane-functional methacrylates was exploited to prepare triblock copolymers as surfactants where the interfacial block could be crosslinked via hydrolysis and condensation. Triblock copolymers were either formed separately (and used to stabilize oil-in-water miniemulsions) or in-situ via the PISA method. The encapsulation of Nile Red in the particle core was achieved in parallel with self-assembly and the retention rate was improved through interfacial crosslinking.


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Copyright 2018 the author Chapters 2 and 3 contain content which is related to an article published as: Teo, G. H., Kuchel, R. P., Zetterlund, P. B., Thickett, S. C., 2016. Polymer-inorganic hybrid nanoparticles of various morphologies via polymerization-induced self-assembly and sol‚Äö-gel chemistry, Polymer chemistry, 2016, 7(43), 6575-6585 Chapter 4 appears to be, in part, the equivalent of the pre-peer reviewed version of the following article: Teo, G. H., Kuchel, R. P., Zetterlund, P. B., Thickett, S. C., 2018, Self‚ÄövÑv™assembly of block copolymers with an alkoxysilane‚ÄövÑv™based core‚ÄövÑv™forming block: A comparison of synthetic approaches, Journal of polymer science Part A: Polymer chemistry, 56(4), 420-429, This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Use of Self-Archived Versions

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