The work disclosed in this thesis is a discussion of the properties and implementation of glycerol-based materials with an emphasis on poly(acrylated glycerol). The first work discussed is the production and characterization of acrylated glycerol polymers. Because of the current abundance of glycerol, there is a large potential for materials and chemicals derived from glycerine. In this work we look at making and studying thermoplastic poly (glycerol-acrylate). In order to prevent these materials from rapidly producing thermosets, a type of polymerization chemistry known as reversible addition fragmentation chain transfer, or RAFT, is utilized. RAFT polymerization is a type of controlled radical polymerization that uses a small molecule called a chain transfer agent (CTA) to control the polymerization and to limit termination. As the CTA may not always be located at the end of the polymer chain it is of importance to know the stability of this molecule, especially when scale up is being considered.

This leads us to the second work in this thesis which is the study of the thermal stability of the CTA. This is important as many industrial processes use elevated temperatures in the processing of their materials. If these glycerine polymers are to be of industrial relevance the should ideally be compatible with existing polymer processing methods.

The third chapter of this thesis is the study of converting a living anionic polymer into a macro-chain transfer agent through a method known as atom transfer radical addition fragmentation reaction (ATRAF). The development of this method would open the door to efficiently producing glycerol, or other acrylics, that are block copolymers with styrenic or diene blocks. This work would give glycerol-acrylic polymers a strong competitive advantage against traditional petrochemical materials as it has properties that are difficult, or impossible, to obtain through petrochemical monomers, are abundant, and cost effective.

Finally I will detail two ongoing projects. The first ongoing work is the development of a more scalable way of converting living anionic polymers into macro-chain transfer agents. This is done first by converting the anion into a macro-monomer and then doing a single insertion RAFT step to yield the macro-cta. I will detail what synthesis and characterization has been completed and what work is yet to be done. The second is the production of glycerol-acetal/acetate-acrylate polymers. These materials have glass transitions that are higher than that of glycerol-acrylate polymers. In this work I detail the initial synthesis and characterization that has been completed and the work that we are intending to complete.