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Quantum Mechanical Calculations on Ring-opening Reactions of Hexachlorophosphazenes

XUE, YUAN
http://orcid.org/0000-0003-0484-8765
http://rave.ohiolink.edu/etdc/view?acc_num=akron1627595429444473

Abstract Details

2021, Doctor of Philosophy, University of Akron, Chemistry.
As the largest group of inorganic backbone polymers, phosphazenes are molecules with alternating phosphorus and nitrogen backbones. To date, the most popular method to prepare the parent, [PCl2N]n (n is used to denote polymer, m is used to denote oligomer, usually 3-20), has been through ring opening polymerization (ROP) of [PCl2N]3, though it has several major drawbacks including low reproducibility and high polydispersity index. To achieve better control over the polymerization process, different Lewis and Bronsted acids including MCl3 (M = B, Al, Ga), PCl5 and HCl have been added to the reaction. Because some experimental factors cannot be well explained using the previously proposed SN1-like mechanism, a deeper understanding of the ROP mechanism of oligomeric [PCl2N]m can be achieved by applying quantum mechanical density functional theory (DFT) calculations to investigate the inter- and intramolecular re-arrangements between two or more [PCl2N]3 molecules. These calculations also explore how different additives such as MCl3, PCl5 and HCl might act as initiators/catalysts in ROP, and how PCl5 might inhibit the chain propagation. Based on the analysis of the ROP potential energy surface, which describes the reactants, predicted reaction intermediates, and transition states of the reaction, this dissertation discusses a novel SN2-like reaction mechanism for the interaction between [PCl2N]3, which initiates the ROP in one concerted step.
Claire Tessier (Advisor)
Christopher Ziegler (Committee Chair)
Chrys Wesdemiotis (Committee Member)
Wiley Youngs (Committee Member)
Valentin Gogonea (Committee Member)
Susan Ramlo (Committee Member)
202 p.
Chemistry
Quantum mechanical calculations; DFT; ring-open polymerization; reaction mechanisms; phosphazenes

Recommended Citations

Citations

  • XUE, Y. (2021). Quantum Mechanical Calculations on Ring-opening Reactions of Hexachlorophosphazenes [Doctoral dissertation, University of Akron]. OhioLINK Electronic Theses and Dissertations Center. http://rave.ohiolink.edu/etdc/view?acc_num=akron1627595429444473

    APA Style (7th edition)

  • XUE, YUAN. Quantum Mechanical Calculations on Ring-opening Reactions of Hexachlorophosphazenes. 2021. University of Akron, Doctoral dissertation. OhioLINK Electronic Theses and Dissertations Center, http://rave.ohiolink.edu/etdc/view?acc_num=akron1627595429444473.

    MLA Style (8th edition)

  • XUE, YUAN. "Quantum Mechanical Calculations on Ring-opening Reactions of Hexachlorophosphazenes." Doctoral dissertation, University of Akron, 2021. http://rave.ohiolink.edu/etdc/view?acc_num=akron1627595429444473

    Chicago Manual of Style (17th edition)

akron1627595429444473
© 2021, all rights reserved.
This open access ETD is published by University of Akron and OhioLINK.