Polyhedral oligomeric silsesquioxanes (POSSs), with Si vertices interconnected by –O– linkages, form three-dimensional nanometer size cage structures with substituents attached to silicon atoms. These substituents may contain reactive groups, such as hydroxyl or isocyanate. A combination of a rigid inorganic nanocore with organic vertex groups makes POSS molecules useful hybrid building blocks that can be chemically incorporated in the polymer matrix by copolymerization, grafting or reactive blending, or physically mixed by solvent casting or polymer processing by using, for example, the extrusion technique [1]. The use of POSSs for making polymer composites has grown exponentially since the last few years of the 20th century. In comparison with the other most commonly used fillers, POSSs possess the advantage of being molecules. Thus, this allows us to combine their nano-sized cage structures, which have dimensions that are similar to those of most polymer segments and produce a particular and exclusive chemical composition. These characteristics linked with their hybrid (inorganic–organic) nature allow researchers to modify POSS according to particular needs or original ideas, before incorporating them into polymers [2]. Figure 1. Molecular structure of the prepared and investigated POSSs In this context, our research group at the University of Catania, in collaboration with eminent researchers in the field, tested the stabilization of different polymers, synthetics or naturals, such as polyethersulfone (PES), ethylene propylene diene monomer (EPDM), polyethylene oxide (PEO), and chitosan by the incorporation of polyhedral oligomeric silsesquioxanes (POSS) molecules [3-6]. Represented in their most common form by the symbol T8 and having a diameter usually falling in the range of 1.5–3 nm, POSS molecules comprise a silicon and oxygen cage completed by organic groups that are covalently bonded with silicon atoms. Novel architectures of POSS with various organic groups were synthesized by using corner capping reaction in order to verify their polimeryzability in the presence of monomer. In this work, after a spectroscopic investigation aiming at verify that the obtained molecules have the structure for which they were designed, their thermal behavior in terms of resistance to thermal degradation were evaluated by means of thermogravimetric analysis (TGA). The obtained temperatures at 5% mass loss (T5%) were compared with each other and with those of the POSSs previously designed and studied by us. Bibliography [1] Lichtenhan, J.D., Pielichowski, K., Blanco, I. POSS-Based Polymers. Polymers 2019, 11, 1727 [2] Blanco, I. The Rediscovery of POSS: A Molecule Rather than a Filler. Polymers 2018, 10, 904. [3] Cicala, G., Blanco, I., Latteri, A., Ognibene, G., Agatino Bottino, F., Fragalà, M.E. PES/POSS Soluble Veils as Advanced Modifiers for Multifunctional Fiber Reinforced Composites. Polymers 2017, 9, 281 [4] Zaharescu, T., Blanco, I., Bottino, F.A. Antioxidant activity assisted by modified particle surface in POSS/EPDM hybrids. Appl. Surf. Sci. 2020, 509, 144702 [5] Legnani, L.; Iannazzo, D.; Pistone, A.; Celesti, C.; Giofrè, S.; Romeo, R.; Di Pietro, A.; Visalli, G.; Fresta, M.; Bottino, P.; et al. Functionalized polyhedral oligosilsesquioxane (POSS) based composites for bone tissue engineering: Synthesis, computational and biological studies. RSC Adv. 2020, 10, 11325–11334 [6] Stipanelov Vrandečić, N., Erceg, M., Andričić, B., Blanco, I., Bottino, F.A. Characterization of poly(ethylene oxide) modified with different phenyl hepta isobutyl polyhedral oligomeric silsesquioxanes. J. Therm. Anal. Calorim. 2020, 142, 1863–1875

Design and Thermal and Spectroscopic Characterization of novel architecture’s POSS nanoparticles

Michelina Catauro
2021

Abstract

Polyhedral oligomeric silsesquioxanes (POSSs), with Si vertices interconnected by –O– linkages, form three-dimensional nanometer size cage structures with substituents attached to silicon atoms. These substituents may contain reactive groups, such as hydroxyl or isocyanate. A combination of a rigid inorganic nanocore with organic vertex groups makes POSS molecules useful hybrid building blocks that can be chemically incorporated in the polymer matrix by copolymerization, grafting or reactive blending, or physically mixed by solvent casting or polymer processing by using, for example, the extrusion technique [1]. The use of POSSs for making polymer composites has grown exponentially since the last few years of the 20th century. In comparison with the other most commonly used fillers, POSSs possess the advantage of being molecules. Thus, this allows us to combine their nano-sized cage structures, which have dimensions that are similar to those of most polymer segments and produce a particular and exclusive chemical composition. These characteristics linked with their hybrid (inorganic–organic) nature allow researchers to modify POSS according to particular needs or original ideas, before incorporating them into polymers [2]. Figure 1. Molecular structure of the prepared and investigated POSSs In this context, our research group at the University of Catania, in collaboration with eminent researchers in the field, tested the stabilization of different polymers, synthetics or naturals, such as polyethersulfone (PES), ethylene propylene diene monomer (EPDM), polyethylene oxide (PEO), and chitosan by the incorporation of polyhedral oligomeric silsesquioxanes (POSS) molecules [3-6]. Represented in their most common form by the symbol T8 and having a diameter usually falling in the range of 1.5–3 nm, POSS molecules comprise a silicon and oxygen cage completed by organic groups that are covalently bonded with silicon atoms. Novel architectures of POSS with various organic groups were synthesized by using corner capping reaction in order to verify their polimeryzability in the presence of monomer. In this work, after a spectroscopic investigation aiming at verify that the obtained molecules have the structure for which they were designed, their thermal behavior in terms of resistance to thermal degradation were evaluated by means of thermogravimetric analysis (TGA). The obtained temperatures at 5% mass loss (T5%) were compared with each other and with those of the POSSs previously designed and studied by us. Bibliography [1] Lichtenhan, J.D., Pielichowski, K., Blanco, I. POSS-Based Polymers. Polymers 2019, 11, 1727 [2] Blanco, I. The Rediscovery of POSS: A Molecule Rather than a Filler. Polymers 2018, 10, 904. [3] Cicala, G., Blanco, I., Latteri, A., Ognibene, G., Agatino Bottino, F., Fragalà, M.E. PES/POSS Soluble Veils as Advanced Modifiers for Multifunctional Fiber Reinforced Composites. Polymers 2017, 9, 281 [4] Zaharescu, T., Blanco, I., Bottino, F.A. Antioxidant activity assisted by modified particle surface in POSS/EPDM hybrids. Appl. Surf. Sci. 2020, 509, 144702 [5] Legnani, L.; Iannazzo, D.; Pistone, A.; Celesti, C.; Giofrè, S.; Romeo, R.; Di Pietro, A.; Visalli, G.; Fresta, M.; Bottino, P.; et al. Functionalized polyhedral oligosilsesquioxane (POSS) based composites for bone tissue engineering: Synthesis, computational and biological studies. RSC Adv. 2020, 10, 11325–11334 [6] Stipanelov Vrandečić, N., Erceg, M., Andričić, B., Blanco, I., Bottino, F.A. Characterization of poly(ethylene oxide) modified with different phenyl hepta isobutyl polyhedral oligomeric silsesquioxanes. J. Therm. Anal. Calorim. 2020, 142, 1863–1875
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11591/465938
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