Silicones are widely used polymeric materials due to their unique properties. The material properties of silicones may be altered by incorporating various organic groups. Traditional methods for linear silicone synthesis involve ring-opening polymerization, which leaves the growing chain susceptible to acid or base mediated chain redistribution and the formation of cyclic monomer byproducts. The Piers-Rubinsztajn (PR) reaction is an alternative siloxane synthetic route that avoids the use of tin- or platinum- based, or of Brønsted acid/base catalysts. Siloxane bond formation is catalyzed by tris(pentafluorophenyl)borane (B(C6F5)3) (R’3Si-H + RO-SiR”3 → R’3Si-O-SiR”3 + RH); alkoxysilanes can be replaced with silanols or alkoxybenzenes. The catalytic activity of B(C6F5)3 was shown to be hindered by trace water in solution; water acts as a Lewis base coordinating to B(C6F5)3. Since the hydrate-free form of B(C6F5)3 is required to initiate a PR reaction, water can act as an inhibitor. In a somewhat contradictory fashion, water was also shown to react with hydrosilanes via a B(C6F5)3 catalyzed hydrolysis reaction to give silanols, that themselves are reagents for the process. The reactivity of alkoxysilanes (or aryl ethers) in the PR reaction was found to be much quicker than water. This was exploited in the synthesis of Ax(AB)yAx triblock copolymers. The aryl rich AB core was first synthesized using the PR reaction. Excess silicone condensed via hydrolysis forming the A blocks. This method of exploiting relative reactivity to tune structure was applied to elastomers made using a single linker (eugenol) with multiple functional groups – elastomer morphology was controlled by changing order of addition. The development of aryl dense silicones is of interest for use in electronic devices. Phenylmethyl homopolymers and highly ordered phenyl pendant copolymers (Ph/Si ratio of 0.5-1.5) were synthesized from monomers to give polymers with high refractive indices (1.51-1.59) and Mw up to 170 kDa. Statistically relevant libraries of aryl functional silicones were developed using combinatorial chemistry in order to analyze their structure-property relationship. Incorporating aromatic groups into silicones worked to elevate thermal stability, refractive index and improve the mechanical strength of silicone rubbers. / Thesis / Doctor of Science (PhD) / Silicone fluids and elastomers possess numerous desirable characteristics which leads to their use in a wide range of applications in the automotive, electronics and biomedical fields, among others. Developing techniques to create well defined, ordered, modified silicones with improved optical properties, mechanical strength and thermal stability was the main focus of this thesis. These objectives were accomplished by incorporating aromatic groups into silicones using boron catalysis. Following the initial (intended) Piers-Rubinsztajn reaction, atmospheric moisture was utilized to promote further polymerization. Statistically relevant libraries of silicone elastomers were prepared using both standard and combinatorial chemistry techniques. This library of elastomers permitted the analysis of trends associated with small changes in elastomer formulation, which could not be accomplished using traditional one-by-one reaction methods in a timely fashion. The modified silicone materials exhibited high refractive indices (up to 1.59), elevated stiffness and improved thermal stability (maintain structure up to 500 °C) when compared to previously synthesized polymers.

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)