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From macrocycles to materials: exploring the potential of oxacalixarenes in polymer synthesis
Fruciano, Salvatore J.
Fruciano, Salvatore J.
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2025
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This dissertation explores the synthesis, functionalization, and integration of oxacalixarenes macrocycles into polymer architectures. The work begins with a review of calixarene and oxacalixarene chemistry, emphasizing synthetic approaches, functional group manipulation and placement, and host-guest chemistry. Building on this foundation, three dicarboxylic acid-functional oxacalix[2]arene[2]hetarenes were synthesized, characterized, and prepared with consideration for step-growth polymerizations. These macrocycles underwent polymerization via Higashi-Yamazaki phosphorylation, yielding polyaramides with film-forming properties. However, post-synthetic purification was required due to the formation of cyclic oligomers, whose occurrence was closely tied to the geometry of the oxacalixarene. Copolymerization significantly reduced oligomer formation, thereby enhancing the mechanical performance of solution cast films. Mechanical testing confirmed that the polyaramides exhibited properties comparable to other high-performance polyamides. Further investigations into the polymerization of oxacalixarene-derived polyesters were conducted using dicarboxylic acid and diacid chloride-functionalized macrocycles across bulk, interfacial, and solution polymerization methods. The results demonstrated that oxacalixarene geometry exerts a strong influence on polymerization behavior, with certain comonomer combinations yielding film-forming polyester. Additionally, an oxacalixarene was successfully monofunctionalized with a single carboxylic acid functional group via a fragment coupling approach, providing insights into the selective placement of functional groups. The work presented herein represents the first detailed examination of oxacalixarenes as functional monomers in the polymerization of linear structures, offering new pathways for the integration into high-performance materials.
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