Precise Synthesis, Characterization, and Applications of Nonlinear Polymers with Varied Architectures
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Choi, Woosung
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Abstract
The precise synthesis of non-linear polymers with desired architectures is important in polymer science due to their unique properties compared to the linear counterparts, including superior rheological properties, abundant terminal groups, and potential for novel applications. Controlled radical polymerization (CRP) offers significant advantages in the synthesis of non-linear polymers owing to the versatility in monomer selection, end-group functionality, and precise structural control. However, there are still challenges and complexity in precisely synthesizing non-linear polymers via CRP techniques, including inter-/intramolecular radical coupling, non-uniform chain growth, and difficulty in accurate characterization. This thesis aims to carefully design and craft non-linear polymers with varied architectures, thoroughly characterize and understand their properties, and explore their unique functionalities for their potential use in small molecule detection, sustainable materials development, and stimuli-responsive recyclable emulsifiers.
First, we demonstrated how carefully designed non-linear polymers can be advantageous towards their linear counterparts by crafting nanometer-scale Janus star polymers without the need for self-assembly. The importance and difficulties in characterization were discussed. Then, we explored in what manner non-linear polymers with precisely controlled architectures can serve as unimolecular templates to grow stable plasmonic nanocrystals with intriguing morphology by utilizing carefully designed bottlebrush-like diblock copolymers to render polymer-ligated gold nanostars. We showed that our polymer-ligated gold nanostars exhibited improved colloidal and morphological stability. Finally, a novel strategy to render degradable yet mechanically robust polymer films was developed by leveraging the multifunctionality of star polymers. We showed that such degradable and crosslinkable star polymers could find their potential applications in advanced packaging materials with further optimization.
Therefore, the goal of this thesis is to address the importance and challenges in the precise synthesis of non-linear polymers by demonstrating their unique functionalities and applications originating from their distinct and well-controlled architectures. This work advances polymer engineering through careful design and understanding of various non-linear polymers while exploring their novel applications to address contemporary challenges in materials science and technology.
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2024-12-05
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Dissertation