Bottlebrush polymers are interesting topologies that have become increasingly relevant in various applications including rheology modifiers, super-soft elastomers, photonic crystals, anti-fouling coatings, the in vivo delivery of therapeutic agents, and as promising substrates in lithographic printing. These macromolecules are comprised of numerous polymeric side-chains densely grafted to a polymer backbone. The densely grafted nature of bottlebrush polymers results in steric repulsion between neighboring polymer chains, forcing these macromolecules to adopt a chain-extended conformation. Although these remarkable macromolecules have a many different applications, the transformative potential of the bottlebrush polymer topology has not been realized because the synthesis of high molecular weight bottlebrush polymers is challenging. This dissertation focusses on improving the synthesis of these large macromolecules using the grafting-through strategy in the first section and the transfer-to strategy in the second section. For the first time the effect of anchor group chemistry—the configuration of atoms linking the polymer to a polymerizable norbornene—was studied on the kinetics of ring-opening metathesis polymerization (ROMP) of macromonomers (MMs) initiated by Grubbs 3rd generation catalyst. A variance in the rate of propagation of >4-fold between similar MMs with different anchor groups was observed. This phenomenon was conserved across all MMs tested, regardless of solvent, molecular weight (MW), or repeat unit identity. Experimental and computational studies indicated that the rate differences likely resulted from a combination of varying steric demands and electronic structure among the different anchor groups. This new insight will allow others to achieve high MM conversion and prepare pure, high MW bottlebrush polymers by ROMP grafting-through. The second section of this dissertation deals with a little studied bottlebrush synthesis technique called the transfer-to method. This method is a hybrid of the grafting-from and grafting-to approaches in which the growing polymer side chains detach from the backbone, propagate freely in solution, and then reattach to the backbone in a chain transfer step. Several parameters were investigated to determine optimal conditions for this process. This study provides for the first time a guide to use the transfer-to method to produce high purity bottlebrush polymers with controllable backbone and side chain length. / Ph. D. / Bottlebrush polymers are interesting topologies that have become increasingly relevant in various applications including super-soft elastomers and drug delivery agents. These macromolecules are comprised of numerous polymeric side-chains densely grafted to a polymer backbone. The densely grafted nature of bottlebrush polymers results in steric repulsion between neighboring polymer chains, forcing these macromolecules to adopt a chain-extended or worm like conformation. Although these remarkable macromolecules have a many different applications, the transformative potential of the bottlebrush polymer topology has not been realized because the synthesis of large bottlebrush polymers is challenging. This dissertation focusses on improving the synthesis of these big macromolecules using the grafting-through strategy in the first section and the transfer-to strategy in the second section. For the first time the effect of anchor group chemistry—the configuration of atoms linking the polymer to a polymerizable norbornene—was studied on bottlebrush synthesis. A variance in how fast the polymerization took between similar MMs with different anchor groups was observed. Experimental and computational studies indicated that the differences likely resulted from a combination of varying steric demands and electronic structure among the different anchor groups. This new insight will allow others to achieve high MM conversion and prepare pure, high MW bottlebrush polymers by ROMP grafting-through. The second section of this dissertation deals with a little studied bottlebrush synthesis technique called the transfer-to method. This method is a hybrid of two well-known methods, grafting-from and grafting-to approaches, in which the growing polymer side chains detach from the backbone, polymerize freely in solution, and then reattach to the backbone in a chain transfer step. Several parameters were investigated to determine optimal conditions for this process. This study provides for the first time a guide to use the transfer-to method to produce high purity bottlebrush polymers with controllable sizes.

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