Silicones elastomers are widely used all over the world due to their unusual properties when compared to their carbon-based counterparts. Synthetic methods for their synthesis are still quite limited and the traditional silicone products are not able to completely meet the requirement for modern materials. Silicone elastomers with customized structures and with higher levels of sustainability will be the research focus for the development of next generation materials. The element sulfur and its functional groups are growing players in modern polymer and materials science, since sulfur reactions are exceptionally versatile. The incorporation of sulfur reactions into the design and preparation of silicone materials can lead to silicones with unique properties for various research interests. Initial exploration was focused on the creation of general and simple methods for 3D printing silicone elastomers using thiol-ene chemistry. However, silicone inks suitable for 3D printing are still quite limited. Photo-initiated thiol-ene chemistry was proposed to design a rapid cure silicone ink for extrusion 3D printing. Unlike other radical reactions, the relatively oxygen insensitive thiol-ene was able to provide the necessary rapid reaction rate and build up the necessary viscosity for practical printing in less than 2 seconds in the presence of air. Various customized silicone structures with different moduli were obtained with a relative fast printing speed. The use of thiol oxidation reactions in the synthesis of silicone elastomers is also demonstrated in this thesis. Reductive cleavage of the resulting disulfide bridge was successfully performed with the presence of hydrosilane and B(C6F5)3 catalyst. Herein, a synthetic method to reversible silicone elastomers based on the disulfide linkage is described. This method could be extended to cleave the disulfide and polysulfide linkage in used automotive rubber materials. Various kinds of sulfur-cured rubbers were successfully devulcanized to polymeric oil. This simple and efficient method could potentially offer a solution for the huge amount of tire waste produced every year. Finally, a new method for preparing thermoplastic silicone elastomers with ionic linkages is reported. A novel dicarboxylic acid-modified silicone was synthesized though thiol-Michael additions. The resulting ionic crosslinked networks were built though the neutralization between carboxylic and amino silicone. Thermoplastic silicone elastomers with unique viscoelastic behavior can be obtained. In summary, the thesis demonstrates that sulfur chemistry is an exceptional synthetic tool for the silicone chemist. / Thesis / Doctor of Philosophy (PhD)
| Identifer | oai:union.ndltd.org:mcmaster.ca/oai:macsphere.mcmaster.ca:11375/25834 |
| Date | January 2020 |
| Creators | Zheng, Sijia |
| Contributors | Brook, Michael A., Chemistry and Chemical Biology |
| Source Sets | McMaster University |
| Language | English |
| Detected Language | English |
| Type | Thesis |
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