Design, Synthesis and Applications of Versatile Porous Poly(arylene ether)s

Abstract

This thesis describes the synthesis of various porous poly(arylene ether)s for the applications in heterogeneous catalysis and gas separation.

In Chapter I, we offer an overview of the structure and properties of porous poly(arylene ether)s, and introduce the key challenges in heterogeneous catalysis and gas separation. In

Chapter II, we present the development of a solution-processable microporous organic polymer catalyst that displays high catalytic performance and size-selectivity in the heterogeneous SuzukiMiyaura coupling reaction. The catalyst can be used to create catalytic impellers that simplifies its use and recovery, thereby conforming to green chemistry principles.

In Chapter III, we demonstrate a tunable synthetic platform for the advent of eight representative microporous poly(arylene ether)s with tertiary-amine functional groups. We compare the competition enhancements in sorption affinity for H₂S and CO₂ to those of primary-amine functional membranes and provide explanation for the reason why the slight enhancements do not fully translate to enhanced separation performance.

In Chapter IV, we explore the potential of free volume manipulation in enhancing acid gas separation for microporous polymer membranes. By incorporating labile functional groups onto a microporous poly(arylene ether) and employing thermal treatment with oxygen, we improve the combined acid gas selectivity and increase membrane resistance to plasticization.

In Chapter V, we synthesize a series of ionic poly(arylene ethers), and evaluate their potential applications in propylene/propane separation, proton exchange and heterogenous catalysis. We study the separation performance of carboxylate-functionalized polymer, and the ion exchange capacity and efficiency as solid acid catalyst for sulfonated polymers to demonstrate their promise.