{"id":{"repo_id":"mit","oai_identifier":"oai:dspace.mit.edu:1721.1/158058"},"canonical_url":"https://search.dev.ndltd.org/etd/mit/oai:dspace.mit.edu:1721.1/158058","repository":{"repo_id":"mit","name":"MIT","base_url":"https://dspace.mit.edu/oai/request"},"display":{"title":"Designing Microporous Polymers for Separations","abstract":"In 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.","abstract_html":"In 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.","abstract_has_math":false,"creators":["Storme, Kayla R."],"institution":"Massachusetts Institute of Technology","degree_name":"Doctoral","degree_level":null,"degree_discipline":null,"degree_department":"Massachusetts Institute of Technology. Department of Chemistry","school":null,"contributors":[],"advisors":["Swager, Timothy M.","Smith, Zachary P."],"committee_chairs":[],"committee_members":[],"year":2024,"date_issued":"2024-02","date_published":"2024-02","updated_at":"2026-07-22T22:22:22Z","subjects":[],"languages":[],"rights":["In Copyright - Educational Use Permitted","Copyright retained by author(s)"],"rights_urls":["https://rightsstatements.org/page/InC-EDU/1.0/"],"identifier_entries":[]},"links":{"outbound_url":"https://hdl.handle.net/1721.1/158058","outbound_label":"Handle","outbound_source":"dc:identifier.uri"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor.advisor","label":"Advisor","values":["Swager, Timothy M.","Smith, Zachary P."]},{"key":"dc:contributor.department","label":"Department","values":["Massachusetts Institute of Technology. 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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."]},{"key":"dc:description.degree","label":"Dc Description Degree","values":["Ph.D."]},{"key":"dc:title","label":"Title","values":["Designing Microporous Polymers for Separations"]}]}],"canonical_facts":{"dc:contributor.advisor":["Swager, Timothy M.","Smith, Zachary P."],"dc:contributor.department":["Massachusetts Institute of Technology. Department of Chemistry"],"dc:creator":["Storme, Kayla R."],"dc:date.accessioned":["2025-01-23T17:20:19Z"],"dc:date.available":["2025-01-23T17:20:19Z"],"dc:date.issued":["2024-02"],"dc:description.abstract":["In 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:description.degree":["Ph.D."],"dc:identifier.uri":["https://hdl.handle.net/1721.1/158058"],"dc:publisher":["Massachusetts Institute of Technology"],"dc:rights":["In Copyright - Educational Use Permitted","Copyright retained by author(s)"],"dc:rights.uri":["https://rightsstatements.org/page/InC-EDU/1.0/"],"dc:title":["Designing Microporous Polymers for Separations"],"dc:type":["Thesis"],"thesis:degree_name":["Doctoral","Doctor of Philosophy"]},"updated_at":"2026-07-22T22:22:22Z"}