Sustainable Polymers Through Creative Design

Plastics have changed the world of materials due to their high durability, low price, low density, and ease of processing. Unfortunately, the majority of plastic goods produced are discarded instead of recycled, leading to a massive accumulation of plastic waste in landfills and natural habitats. To decrease the impact of plastic waste, sustainable materials and synthetic methods are needed. This dissertation focuses on new strategies for developing renewable and degradable polymers with minimal energy input as well as new methods to blend legacy polyolefins with renewable polymers. The first half of the dissertation focuses on synthesizing polymers using light while the second section focuses on combining traditional polyolefins with renewable polymers. Photo-mediated polymerizations are an attractive alternative to traditional thermal polymerizations due to their ease of setup and the spatiotemporal control afforded by light. Using LED lights also affords a synthetic technique that requires little energy input, thus decreasing the overall environmental impact of the material. In this work, coupling LEDs with a trithiocarbonate allowed for the synthesis of many different polymers and topologies. Bottlebrush polymers synthesized with light afforded molar masses in excess of 11 million Da without the oligomerization of the bottlebrush polymers. These bottlebrush polymers were then used to make reversibly crosslinkable adhesives, allowing for a new example of recyclable adhesives. The second half of the dissertation focuses on developing sustainable polymers using ring-opening metathesis polymerization (ROMP) to combine the properties of polyolefins with renewable polymers. First, polyketones synthesized by ROMP were developed for their potential use as photodegradable polymers. This initial study probed the synthesis of different polyketone monomers and the properties of their respective polymers. Next, a photodegradable and biodegradable thermoplastic elastomer (TPE) was synthesized that incorporated a ketone containing polybutadiene (PB) flanked by polylactide (PLA). The thermomechanical properties were controlled based on the relative length of each block while the rate of photodegradation was controlled by the mol% of ketone incorporated into the PB block. Finally, ABA triblock copolymers of cellulose derivatives and polyolefins were developed for their uses as compatibilizers for blends. With the addition of as little as 1 wt% of the ABA triblock copolymer, the respective blends showed large imp