Author: Di Liu (Ph. D.)

Publisher:

Published: 2016

Total Pages: 258

ISBN-13:

Post-polymerization modification of polymers is an important tool for accessing macromolecular materials with desired functional groups and tailored properties. Such strategy may become the only route to a target polymer when the availability or reactivity of the corresponding monomer is not suited for direct polymerization. Most post-polymerization modification processes are based on transforming functional groups that are pre-installed in the side chains or chain-ends of a polymer. Despite the excellent efficiency and versatility, they are limited to certain backbone structures and often require additional synthetic effort for the synthesis of the corresponding pre-functionalized monomers. More specifically, they are useful only when the pre-functionalized monomers can be readily prepared and incorporated to a polymer by direct polymerization. In contrast, direct functionalization of C-H bonds along the polymer backbone offers a markedly different strategy for the synthesis of functional polymers. Despite the inert nature, the ubiquity of the C-H bonds and their tunable reactivity make them ideal targets for selective chemical modification. In this dissertation, it is first demonstrated that poly(vinyl ester)s and poly(vinyl ether-co-vinyl ester) can be readily prepared via a ruthenium catalyzed C–H oxyfunctionalization of the corresponding poly(vinyl ether)s under mild conditions. The method can be further applied for the synthesis of high molecular weight poly(propenyl ester)s which cannot be obtained using other methods. In addition the method allows poly(isopropenyl ester) to be synthesized without the use of extremely high pressures. Using a similar strategy poly(ethylene glycol-co-glycolic acid) can be prepared by the ruthenium-catalyzed oxidation of poly(ethylene glycol) (PEG). A new process has been developed so that the transformation will cause little chain degradation. The presence of the hydrolytically labile ester groups in the PEG backbone renders the copolymer biodegradable, which may allow the PEG of higher molecular weight to be used in biomedical applications without the concerns of bioaccumulation of PEG into various organs. Lastly, it is demonstrated that azido-functionalized, isotactic polypropylene can be prepared via the direct C–H azidation of a commercially available polymer using a stable azidoiodinane. The azidated PP can further undergo copper-catalyzed azide-alkyne cycloaddition with alkyne terminated polymer to obtain PP-based graft copolymers. It is expected that the ability to incorporate versatile functional groups, such as azides, into common polyolefin feedstocks should expand their applications and potentially enable the realization of new classes of materials.