Copolymers of poly(methylenephosphine)s : characterization and application in polymer-supported catalysis
department or school: Science, Faculty of
department or school: Chemistry, Department of
data provider: DSpace
degree campus: UBCV
creator: Suen, Jeffrey Jun-Yan
issued: 2021-12-20T22:56:23Z
issued: 2021
related degree: Master of Science - MSc
degree grantor: University of British Columbia
description: This thesis outlines the synthesis, characterization, and catalytic use of phosphorus containing copolymers. The incorporation of phosphorus imparts unique functionalities that allow for the use of polymeric ligands in catalysis. In Chapter 2, the gold metallated phosphorus containing copolymer (PMP-r-PS)-Au-Cl was used as a hydroamination catalyst for the intermolecular hydroamination of phenyl acetylene with aniline. At 5 mol% catalyst loading (5 mol% Au centres), the total product conversion was 99.6% at room temperature and 98.6% at 110°C. The (PMP-r-PS)-Au-Cl catalyst was also selective in producing only the Markovnikov product. In Chapter 3, the free radical copolymerization of PMP-r-PBA was investigated. The linkages between phosphaalkene (PA) and n-butyl acrylate (BA) residues were fully characterized by edHSQC NMR spectroscopy and GPC. The reactivity ratios between PA and BA monomers were determined using the Fineman-Ross linear method and the Mayo-Lewis graphical method. The reactivity ratios were rPA = 18.1, rBA = 0.670 and rPA = 22.7, rBA = 0.784 from both methods, respectively. The reactivity ratios suggested that a propagating PA• radical has a strong preference for homo-propagation and a propagating BA• radical has a slight preference for cross-propagation. To conclude, these instigations have opened the doors to new possibilities in the synthesis of PMP copolymers as well as their uses as catalyst supports in gold catalysis
aggregated CHO: https://circle.library.ubc.ca/rest/handle/2429/80485
note: COPOLYMERS OF POLY(METHYLENEPHOSPHINE)S: CHARACTERIZATION AND APPLICATION IN POLYMER-SUPPORTED CATALYSIS by Jeffrey Jun-Yan Suen B.Sc., McMaster University, 2016 A THESIS SUBMITTED IN PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR THE DEGREE OF MASTER OF SCIENCE in THE FACULTY OF GRADUATE AND POSTDOCTORAL STUDIES (Chemistry) THE UNIVERSITY OF BRITISH COLUMBIA (Vancouver) December 2021 © Jeffrey Jun-Yan Suen, 2021 ii The following individuals certify that they have read, and recommend to the Faculty of Graduate and Postdoctoral Studies for acceptance, a thesis entitled: Copolymers of Poly(methylenephosphine)s: Characterization and Application in Polymer-Supported Catalysis submitted by Jeffrey Jun-Yan Suen in partial fulfillment of the requirements for the degree of Master of Science in Chemistry Examining Committee: Dr. Derek P. Gates, Professor, Department of Chemistry, UBC Supervisor Dr. Zachary M. Hudson, Associate Professor, Department of Chemistry, UBC Supervisory Committee Member Dr. Eva M. Nichols, Assistant Professor, Department of Chemistry, UBC Supervisory Committee Member iii Abstract This thesis outlines the synthesis, characterization, and catalytic use of phosphorus containing copolymers. The incorporation of phosphorus imparts unique functionalities that allow for the use of polymeric ligands in catalysis. In Chapter 2, the gold metallated phosphorus containing copolymer (PMP-r-PS)-Au-Cl was used as a hydroamination catalyst for the intermolecular hydroamination of phenyl acetylene with aniline. At 5 mol% catalyst loading (5 mol% Au centres), the total product conversion was 99.6% at room temperature and 98.6% at 110°C. The (PMP-r-PS)-Au-Cl catalyst was also selective in producing only the Markovnikov product. In Chapter 3, the free radical copolymerization of PMP-r-PBA was investigated. The linkages between phosphaalkene (PA) and n-butyl acrylate (BA) residues were fully characterized by edHSQC NMR spectroscopy and GPC. The reactivity ratios between PA …
has type: Thesis/Dissertation
date issued: 2022-05
is shown at: 10.14288/1.0406100
language: eng
degree discipline: Chemistry
provider: Vancouver : University of British Columbia Library
publisher: University of British Columbia
rights: Attribution-NonCommercial-NoDerivatives 4.0 International
rights URI: http://creativecommons.org/licenses/by-nc-nd/4.0/
scholar level: Graduate
contributor: Gates, Derek P.
type: Text
identifier URI: http://hdl.handle.net/2429/80485