THE DESIGN AND SYNTHESIS OF SILOXANE PRECURSORS FOR CHIRAL PERIODIC MESOPOROUS ORGANOSILICA MATERIALS

The development of cost-effective and reliable methods for the synthesis and separation of asymmetric compounds is paramount in helping to meet society’s ever-growing demand for chiral small molecules. Of these methods, chiral heterogeneous supports are particularly appealing as they allow for the reuse of the chiral source. One such support, based on the synergy between chiral organic units and structurally stable inorganic silicon scaffolds are periodic mesoporous organosilicas (PMOs). In the work described herein, I examine some of the factors governing the transmission of chirality between chiral dopants and prochiral bulk phases in chiral PMO materials. In particular, the exploration of 1,1’-binaphthalene-bridged chiral dopants with a focus on the point of attachment into the materials. Moreover, the effects of ordering in the materials are examined and reveal that chirality transfer is more facile in materials with molecular-scale order then those containing amorphous walls. Secondly, the issues surrounding the synthesis and purification of aryl-triethoxysilanes as siloxane precursors are addressed. Both the introduction of a two-carbon linker and the direct attachment of allyl and mixed allyldiethoxysilane species are explored. This work demonstrates that allyldiethoxysilanes are ideal, in that they are stable enough to permit facile synthesis, while still being able to hydrolyze completely to produce well-ordered materials. Lastly, the production of new bulk phases for chiral PMO materials is examined by introducing new prochiral nitrogen-containing siloxane precursors. Biphenyldiamine and bipyridine-bridged siloxane precursors are readily synthesized on reasonable scales. Their use as the bulk siloxane precursor in the production of PMO materials however, is precluded by insufficient gelation and additional siloxane precursors are necessary for the production of ordered materials. In addition to the research detailed above that forms the body of this thesis, two short works are appended. The first details the production of polythiophene assemblies mediated through coordination nanospaces, while the second explores the production of N-heterocyclic carbene functionalized gold nanoparticles through ligand exchange.

Coagent Modified Polypropylene Prepared by Reactive Extrusion: A New Look Into the Structure-Property Relations of Injection Molded Parts

Peroxide-mediated reactive extrusion of linear isotactic polypropylene (L-PP) was conducted in the presence of trimethylolpropane trimethacrylate (TMPTMA) and triallyl trimesate (TAM) coagents, using a twin screw extruder. The resulting coagent-modified polypropylenes (CM-PP) had higher viscosities and elasticities, as well as increased crystallization temperature compared to PP reacted only with peroxide (DCP-PP). Additionally, deviations from terminal flow, and strain hardening were observed in PP modified with TAM, signifying the presence of long chain branching (LCB). The CM-PP formulations retained the modulus and tensile strength of the parent L-PP, in spite of their lower molar mass and viscosities, whereas their elongation at break and the impact strength were better. This was attributed to the finer spherulitic structure of these materials, and to the disappearance of the skin-core layer in the injection molded specimens.