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Suen, Jeffrey Jun-Yan

University of British Columbia

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

Text

2021-12-20

Attribution-NonCommercial-NoDerivatives 4.0 International

http://hdl.handle.net/2429/80485

Chemistry

University of British Columbia

UBCV

http://creativecommons.org/licenses/by-nc-nd/4.0/