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Kate's dissertation-2.pdf (10.57 MB)

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RAFT Polymerization: Pushing the Limits and Gaining Control via Kinetic Analysis

Bradford, Kate Georgia Elizabeth
http://orcid.org/0000-0003-4403-5187
http://rave.ohiolink.edu/etdc/view?acc_num=miami1650637008842556

Abstract Details

2022, Doctor of Philosophy, Miami University, Chemistry and Biochemistry.
Polymers are everywhere and they are made up of a series of repeating units chained together. With increased demand for polymers with tailored applications, methods such as atom transfer radical polymerization (ATRP) and reversible addition-fragmentation chain transfer (RAFT) were created in order to gain control of the growing chains. These methods provide a way to synthesize chains with known molecular weights and low dispersity. This work was designed to explore polymerization methods at its core. The analysis of the reaction rates is based on retardation, reaction conditions, and chain transfer reagent composition in order to help better understand the RAFT reaction mechanism. Looking at quintessential RAFT, many assumptions have been made about every aspect of the reaction; from choosing a chain transfer reagent all the way to the solvent choice. Many of these preconceived notions have not been thoroughly tested in parallel to each other. Here, we analyzed reaction rate along with chain length and dispersity to see how the growing polymers responded to variations from the literature standard. Rate retardation is the decrease in reaction rate as the concentration of chain transfer reagent increases. In our study, we analyzed beyond traditional dithiobenzoate chain transfer reagents in order to understand the universality of rate retardation within RAFT. RAFT also allows for complex architecture with unique physical properties, such as star polymers, blocks, and gradients. Within this dissertation, these complex architectures are studied by looking at the unique physical properties as well as the kinetics and composition of the polymer. This was important when analyzing the folding of the ortho-phenylene core of a star polymer and understanding how R group affects the control of synthesizing gradient polymers by RAFT.
Dominik Konkolewicz (Advisor)
C. Scott Hartley (Advisor)
Suzanne Harper (Committee Member)
Richard Page (Committee Member)
David Tierney (Committee Chair)
240 p.
Chemistry
RAFT; Polymer; Kinetics; Rate Retardation; Gradients; Star Polymers;

Recommended Citations

Citations

  • Bradford, K. G. E. (2022). RAFT Polymerization: Pushing the Limits and Gaining Control via Kinetic Analysis [Doctoral dissertation, Miami University]. OhioLINK Electronic Theses and Dissertations Center. http://rave.ohiolink.edu/etdc/view?acc_num=miami1650637008842556

    APA Style (7th edition)

  • Bradford, Kate. RAFT Polymerization: Pushing the Limits and Gaining Control via Kinetic Analysis. 2022. Miami University, Doctoral dissertation. OhioLINK Electronic Theses and Dissertations Center, http://rave.ohiolink.edu/etdc/view?acc_num=miami1650637008842556.

    MLA Style (8th edition)

  • Bradford, Kate. "RAFT Polymerization: Pushing the Limits and Gaining Control via Kinetic Analysis." Doctoral dissertation, Miami University, 2022. http://rave.ohiolink.edu/etdc/view?acc_num=miami1650637008842556

    Chicago Manual of Style (17th edition)

miami1650637008842556
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© 2022, all rights reserved.
This open access ETD is published by Miami University and OhioLINK.