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dc.contributor.advisorSwager, Timothy M.
dc.contributor.advisorSmith, Zachary P.
dc.contributor.authorStorme, Kayla R.
dc.date.accessioned2025-01-23T17:20:19Z
dc.date.available2025-01-23T17:20:19Z
dc.date.issued2024-02
dc.date.submitted2024-12-23T19:44:10.358Z
dc.identifier.urihttps://hdl.handle.net/1721.1/158058
dc.description.abstractIn Chapter 1, we investigate the influence of side-chain length and dispersity in ring-opening metathesis polymerization (ROMP) polymers with pore-generating side chains. Macromonomers with four discrete monodispersities are separated and polymerized to produce bottlebrush polymers with monodisperse side chains. Each bottlebrush polymer is fabricated into a free-standing film. Pure-gas experiments are performed to explore the impact of dispersity and side chain length on gas separation performance. In Chapter 2, we evaluate the mixed-gas performance of a class of bottlebrush polymers described in Chapter 1. Gas sorption, diffusion, and CO₂-induced plasticization are reported. Competitive sorption effects are studied using 50:50 mixture of CO₂/CH₄. Separation performance at different compositions of CO₂/CH₄ is also explored. In Chapter 3, we incorporate nitrile functionality into the structure of a family of polymers with rigid, porogenic side chains described in Chapters 1 and 2. Statistical and block copolymers are synthesized to demonstrate the role of grafting density on separation performance and CO₂ plasticization resistance. Sorption experiments are performed to determine improvements to selectivity. In Chapter 4, we describe the optimized SN Ar synthesis of a poly(arylene ether) (PAE) that produces high molecular weight polymers. The synthesis of an analogous PAE with C-H functionality instead of C-F is also reported. Porosity and free volume are investigated in both PAEs. Separation performance is characterized and compared to other polymers with similar structural motifs.
dc.publisherMassachusetts Institute of Technology
dc.rightsIn Copyright - Educational Use Permitted
dc.rightsCopyright retained by author(s)
dc.rights.urihttps://rightsstatements.org/page/InC-EDU/1.0/
dc.titleDesigning Microporous Polymers for Separations
dc.typeThesis
dc.description.degreePh.D.
dc.contributor.departmentMassachusetts Institute of Technology. Department of Chemistry
mit.thesis.degreeDoctoral
thesis.degree.nameDoctor of Philosophy


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