Designing Microporous Polymers for Separations

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.

Name thesis:degree_name

Doctoral

Department dc:contributor.department

Massachusetts Institute of Technology. Department of Chemistry

Grantor dc:publisher

Massachusetts Institute of Technology

Year dc:date.issued

2024

Author dc:creator

• Storme, Kayla R.

Advisors dc:contributor.advisor

• Swager, Timothy M.
• Smith, Zachary P.

Statement dc:rights

• In Copyright - Educational Use Permitted
• Copyright retained by author(s)

Licence dc:rights.uri

• https://rightsstatements.org/page/InC-EDU/1.0/

Handle dc:identifier.uri

https://hdl.handle.net/1721.1/158058

OAI identifier oai:identifier

oai:dspace.mit.edu:1721.1/158058