Skip to Main Content
 

Global Search Box

 
 
 
 

Files

File List


ReevesThesisFinal.pdf (6.97 MB)

ETD Abstract Container

Abstract Header

Photochemistry: Its Application to Reversible Deactivation Radical Polymerization, Degradation, and Post-polymerization Modification

Reeves, Jennifer Anne
http://orcid.org/0000-0002-5336-5447
http://rave.ohiolink.edu/etdc/view?acc_num=miami154297403540796

Abstract Details

2018, Doctor of Philosophy, Miami University, Chemistry and Biochemistry.
Polymers are a large part of daily life. As such, efficient ways to synthesize them are important. Techniques such as reversible addition-fragmentation chain transfer (RAFT) polymerization and atom transfer radical polymerization (ATRP) allow for the controlled growth of polymers through radical polymerization. Photochemistry gives access to high energy intermediates and both spatial and temporal control. Photochemistry has been applied to both RAFT and ATRP with great success. A specific subset of photoRAFT polymerization, Photoinduced electron/energy transfer (PET)-RAFT has received great attention in recent years. Understanding the factors that affect the rate of the polymerization to allow for statistical comparisons between different research groups is important. It was discovered that although reactor geometry, volume, and concentration have little effect upon the kinetics, chain transfer agent and photocatalyst concentration and photoreactor intensity greatly impact the rate. With polymers being consumed in high quantities, new ways to allow for easy degradation of polymeric materials is important to allow them to be removed from the environment. Poly(phenyl vinyl ketone) (poly(PVK)) is a known photodegradable polymer under ultraviolet (UV) irradiation. Due to phenyl vinyl ketone’s acetophenone subgroup, it can act as photoinitiator. Polymers of varying chain lengths were synthesized under self-initiated conditions under blue light irradiation and then degraded under UV irradiation. Although the PVK monomer absorbs significantly in the UV region and insignificantly in the blue region, irradiation with blue light is more efficient for polymerization. This phenomena led to a systematic study of self-initiated and photoredox initiated PET-RAFT polymerization of PVK under various wavelengths of light. This study showed that under self-initiated conditions, blue light was the most efficient energy source for promoting polymerization. Under photoredox PET-RAFT conditions with an Ir(III) complex, violet light was the most efficient. However, the difference in the efficiency between the two systems was not extreme. Considering economic factors, the self-initiated blue light irradiated system is the best system for polymerization. Beyond new photodegradation, other photomodification of polymers is important. Red light photochemistry is especially challenging because it is lower energy light. A norbornene functionalized methacrylate monomer was polymerized under photoATRP conditions with high control, allowing for selective activation of methacrylate double bond. This norbornene functionalized polymer was subjected to red light activated inverse electron demand hetero Diels-Alder reaction for post-polymerization modification, though with limited success.
Dominik Konkolewicz, PhD (Advisor)
Richard Taylor, PhD (Committee Chair)
C. Scott Hartley, PhD (Committee Member)
Richard Page, PhD (Committee Member)
Natosha Finley, PhD (Committee Member)
160 p.
Chemistry; Organic Chemistry; Polymer Chemistry; Polymers
Polymer, Photochemistry, Reversible-Deactivation Radical Polymerization, RAFT, ATRP, Kinetics

Recommended Citations

Citations

  • Reeves, J. A. (2018). Photochemistry: Its Application to Reversible Deactivation Radical Polymerization, Degradation, and Post-polymerization Modification [Doctoral dissertation, Miami University]. OhioLINK Electronic Theses and Dissertations Center. http://rave.ohiolink.edu/etdc/view?acc_num=miami154297403540796

    APA Style (7th edition)

  • Reeves, Jennifer. Photochemistry: Its Application to Reversible Deactivation Radical Polymerization, Degradation, and Post-polymerization Modification. 2018. Miami University, Doctoral dissertation. OhioLINK Electronic Theses and Dissertations Center, http://rave.ohiolink.edu/etdc/view?acc_num=miami154297403540796.

    MLA Style (8th edition)

  • Reeves, Jennifer. "Photochemistry: Its Application to Reversible Deactivation Radical Polymerization, Degradation, and Post-polymerization Modification." Doctoral dissertation, Miami University, 2018. http://rave.ohiolink.edu/etdc/view?acc_num=miami154297403540796

    Chicago Manual of Style (17th edition)

miami154297403540796
344
© 2018, all rights reserved.
This open access ETD is published by Miami University and OhioLINK.
Release 3.2.12