2026-09-19T08:07:19Zhttps://dspace.mit.edu/server/oai/requestoai:dspace.mit.edu:1721.1/1580582025-04-07T08:29:43Zcom_1721.1_7582com_1721.1_7581col_1721.1_131022
Swager, Timothy M.
Smith, Zachary P.
Storme, Kayla R.
Massachusetts Institute of Technology. Department of Chemistry
2025-01-23T17:20:19Z
2025-01-23T17:20:19Z
2024-02
2024-12-23T19:44:10.358Z
https://hdl.handle.net/1721.1/158058
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.
Ph.D.
Massachusetts Institute of Technology
In Copyright - Educational Use Permitted
Copyright retained by author(s)
https://rightsstatements.org/page/InC-EDU/1.0/
Designing Microporous Polymers for Separations
Thesis
application/pdf
Doctoral
Doctor of Philosophy
Publication
unknown
unknown
<Publication xmlns="https://www.openaire.eu/cerif-profile/1.1/" id="e78dd539-8464-4710-a846-fc3e0b4b685c">
<Type xmlns="https://www.openaire.eu/cerif-profile/vocab/COAR_Publication_Types">http://purl.org/coar/resource_type/c_1843</Type>
<Title>Designing Microporous Polymers for Separations</Title>
<PublishedIn>
<Publication>
</Publication>
</PublishedIn>
<PublicationDate>2024-02</PublicationDate>
<Authors>
<Author>
<DisplayName>Storme, Kayla R.</DisplayName>
<Affiliation>
<OrgUnit>
</OrgUnit>
</Affiliation>
</Author>
</Authors>
<Editors>
</Editors>
<Publishers>
<Publisher>
<DisplayName>Massachusetts Institute of Technology</DisplayName>
<OrgUnit />
</Publisher>
</Publishers>
<License>https://rightsstatements.org/page/InC-EDU/1.0/</License>
<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>
<Access xmlns="http://purl.org/coar/access_right"
>
</Access>
</Publication>