The control of polymer architecture and composition through kinetic studies

The architecture and composition of polymers greatly affects the material properties, ultimately determining the types of applications that the polymers can be used for. Thus, the development of new synthetic strategies for controlling the architecture and composition of polymers can open the doors for the design of next-generation materials. Chapter 1 gives an overview of the types of polymers that will be discussed in this dissertation, as well as an overview of each of the methods that will be used to control the architecture and composition of the synthesized polymers. Chapter 2 first introduces a new synthetic method for obtaining shaped bottlebrush polymers using a simultaneous graft-from and graft-through reaction via ring-opening metathesis polymerization (ROMP) or ring-opening polymerization (ROP). Chapter 3 then dives into examining a phenomenon we observed where the rate of macromonomer polymerization via ROMP depends on the polymeric chain more than the norbornene anchor group. Next, Chapter 4 describes a new method developed to synthesize Janus bottlebrush polymers via sequential graft-to reaction then graft-from ROP in a one-pot polymerization, using mostly commercially available reagents, that only require a simple two-step purification process. Lastly, Chapter 5 discusses kinetic studies that were performed for the copolymerization between two different di-epoxides with a diamine to gain a molecular insight into the compositional structure of the resulting copolymers. Throughout the chapters of this dissertation, kinetic studies were used to evaluate reaction progress, reaction compatibility, polymer architecture and polymer composition, showcasing how vital and extensive polymerization kinetics can be utilized, depending on the needs of the project.

Name thesis:degree_name

Ph.D.

Level thesis:degree_level

Dissertation

Discipline thesis:degree_discipline

Chemistry

Grantor

University of Illinois Urbana-Champaign

Year dc:date

2025

Author dc:creator

• McCleary-Petersen, Keelee Cathleen

Contributors dc:contributor

• Guironnet, Damien S
• Han, Hee-Sun
• Leal, Cecilia
• Moore, Jeff

• Polymer
• Bottlebrush
• Architecture
• Shape
• Composition
• Janus Bottlebrush
• Kinetic Studies

Statement dc:rights

• Copyright 2025 Keelee McCleary-Petersen

Language dc:language

en, eng

Handle dc:identifier

https://hdl.handle.net/2142/129537

OAI record oai:identifier

https://www.ideals.illinois.edu/oai-pmh?verb=GetRecord&metadataPrefix=etdms&identifier=oai%3Awww.ideals.illinois.edu%3A2142%2F129537