Syntezy i nanotechnologie funkcjonalizowanych oktasilseskwioksanów
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2011-06-22T11:20:08Z
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Syntheses and Nanotechnologies of Functionalized Octasilsesquioxanes
Abstract
Tematem niniejszej pracy jest synteza funkcjonalizowanych oktasilseskwioksanów (POSS) i zagadnienia związane z ich wykorzystaniem w technologiach wytwarzania nanokompozytów i materiałów hybrydowych. Jej główne cele to opracowanie metod otrzymywania nowych pochodnych i optymalizacja metod syntezy znanych POSS a także wykazanie ich przydatności jako modyfikatorów w syntezie nowych materiałów bazujących na komercyjnych polimerach. Badania dotyczące syntezy POSS prowadzono w oparciu o procesy hydrolitycznej polikondensacji, hydrosililowania oraz substytucji nukleofilowej, zaś jako komercyjnych polimerów do badań użyto preparatów Gumosil AD-2, Polastosil M-2000 i Sarsil H-50 oraz Nafion DE-2020. W wyniku realizacji tematyki pracy opracowano nową, efektywną metodę syntezy oktakis(3-chloropropylo)oktasilseskwioksanu na drodze polikondensacji hydrolitycznej a następnie wykorzystując wspomniany związek otrzymano na drodze substytucji nukleofilowej 4 nowe pochodne POSS. Opracowano także szereg syntez funkcjonalizowanych POSS w oparciu procesy hydrosililowania katalizowane kompleksami rodu w tym syntezy nowych pochodnych POSS z mieszanymi grupami funkcyjnymi. Wykorzystując reaktywność pochodnych epoksydowych POSS otrzymano nowe związki z grupami nitrowymi i azydkowymi. Modyfikując komercyjne polimery odpowiednimi POSS uzyskano nanokompozyty o poprawionych właściwościach fizykochemicznych.
The subject of this work is a synthesis of the functionalized octasilsesquioxanes (POSS) and issues related to their use in the nanocomposites and hybrid materials manufacture. Its main objectives are to develop methods for obtaining new POSS compounds, optimizing methods of synthesis of known ones and demonstration of their suitability as modifiers in synthesis of new materials based on well known polymers. Studies on the POSS compounds synthesis were based on the hydrolytic polycondensation, hydrosilylation and nucleophilic substitution processes while Gumosil AD-2, Polastosil M-2000, Sarsil H-50 and Nafion DE-2020 as commercial polymers were used. As a result of the research programme implementation a new, effective method of synthesis of octakis(3-chloropropyl) octasilsesquioxane via hydrolytic polycondensation has been developed. In the next step 4 new POSS derivatives have been obtained via nucleophilic substitution reaction of chlorine atoms in the mentioned compound. A number of POSS derivatives has been obtained via rhodium complex catalyzed hydrosilylation including those new with mixed functional groups. Using the reactivity of epoxy POSS derivatives new compounds bearing nitro and azido groups have been obtained. By modifying above mentioned polymers with relevant POSS derivatives nanocomposites of improved physicochemical properties have been also obtained.
The subject of this work is a synthesis of the functionalized octasilsesquioxanes (POSS) and issues related to their use in the nanocomposites and hybrid materials manufacture. Its main objectives are to develop methods for obtaining new POSS compounds, optimizing methods of synthesis of known ones and demonstration of their suitability as modifiers in synthesis of new materials based on well known polymers. Studies on the POSS compounds synthesis were based on the hydrolytic polycondensation, hydrosilylation and nucleophilic substitution processes while Gumosil AD-2, Polastosil M-2000, Sarsil H-50 and Nafion DE-2020 as commercial polymers were used. As a result of the research programme implementation a new, effective method of synthesis of octakis(3-chloropropyl) octasilsesquioxane via hydrolytic polycondensation has been developed. In the next step 4 new POSS derivatives have been obtained via nucleophilic substitution reaction of chlorine atoms in the mentioned compound. A number of POSS derivatives has been obtained via rhodium complex catalyzed hydrosilylation including those new with mixed functional groups. Using the reactivity of epoxy POSS derivatives new compounds bearing nitro and azido groups have been obtained. By modifying above mentioned polymers with relevant POSS derivatives nanocomposites of improved physicochemical properties have been also obtained.
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Wydział Chemii: Zakład Chemii Metaloorganicznej
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Keywords
Silseskwioksany, Silsesquioxanes, Hydrosililowanie, Hydrosilylation, Substytucja nukleofilowa, Nucleophilic substitution, Nanomateriały, Nanomaterials