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Reversible addition fragmentation chain transfer (RAFT) mediated polymerization of N-vinylpyrrolidone
Thesis (PhD (Chemistry and Polymer Science)--University of Stellenbosch, 2008.
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| Other Authors: | |
| Format: | Thesis |
| Language: | English |
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Stellenbosch : University of Stellenbosch
2008
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| _version_ | 1867613931623677952 |
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| access_status_str | Open Access |
| author | Pound, Gwenaelle |
| author2 | Klumperman, Bert |
| author_browse | Klumperman, Bert Pound, Gwenaelle |
| author_facet | Klumperman, Bert Pound, Gwenaelle |
| author_sort | Pound, Gwenaelle |
| collection | Thesis |
| dc_rights_str_mv | University of Stellenbosch |
| description | Thesis (PhD (Chemistry and Polymer Science)--University of Stellenbosch, 2008. |
| format | Thesis |
| id | oai:scholar.sun.ac.za:10019.1/1296 |
| institution | Stellenbosch University (South Africa) |
| language | English |
| last_indexed | 2026-06-10T12:43:59.464Z |
| license_str | Other — see source repository |
| provenance_str_mv | Harvested via OAI-PMH from SUNScholar — Stellenbosch University Repository |
| publishDate | 2008 |
| publishDateRange | 2008 |
| publishDateSort | 2008 |
| publisher | Stellenbosch : University of Stellenbosch |
| publisherStr | Stellenbosch : University of Stellenbosch |
| record_format | dspace |
| source_str | SUNScholar — Stellenbosch University Repository |
| spelling | oai:scholar.sun.ac.za:10019.1/1296 Reversible addition fragmentation chain transfer (RAFT) mediated polymerization of N-vinylpyrrolidone Pound, Gwenaelle Klumperman, Bert University of Stellenbosch. Faculty of Science. Dept. of Chemistry and Polymer Science. Living polymerization N-vinylpyrrolidone Raft Xanthtate Dissertations -- Polymer science Theses -- Polymer science Vinyl polymers Addition polymerization Thesis (PhD (Chemistry and Polymer Science)--University of Stellenbosch, 2008. Xanthate-mediated polymerization was investigated as a tool for the preparation of well-defined poly(N-vinylpyrrolidone) and copolymers of N-vinylpyrrolidone. Some results regarding the monomer vinyl acetate are included, mostly for comparison purposes. The structure of the leaving/reinitiating group of the xanthate mediating agent was tuned to match the monomer reactivity. This was achieved by studying the initialization behaviour of monomer-xanthate systems via in situ 1H-NMR spectroscopy. Additionally, the latter technique was valuable to identify side reactions affecting the monomer, xanthate and/or polymeric species. Subsequently, experimental conditions were defined, and used to optimize the level of control achieved during polymerization. Block copolymers were prepared from a xanthate end-functional poly(ethylene glycol) with both vinyl acetate and N-vinylpyrrolidone. Finally, the preparation of poly(N-vinylpyrrolidone) with a range of well-defined end groups was achieved via postpolymerization treatment of the xanthate end-functional polymerization product. 3 different routes were investigated, which lead to poly(N-vinylpyrrolidone) with 1) aldehyde or alcohol, 2) thiol or 3) unsaturated ω-chain-end functionality, in high yield, while the α-chain-end functionality is defined by the structure of the xanthate leaving group. The ω-aldehyde end-functional poly(N-vinylpyrrolidone) was successfully conjugated to the lysine residues of the model protein lysozyme via reductive amination. Particular attention was drawn to characterizing the polymerization products. NMR spectroscopy, liquid chromatographic and mass-spectroscopic techniques were used. The major achievements emerging from polymer analysis carried out in this study included the following: - a library of NMR chemical shifts for N-vinylpyrrolidone derivatives; - an estimation of the critical conditions for poly(N-vinylpyrrolidone) relevant for separation according to the polymer chain-ends; - conditions for the separation of block-copolymers comprising a poly(ethylene glycol) segment and a poly(N-vinylpyrrolidone) or poly(vinyl acetate) segment via liquid chromatography; - valuable results on matrix-assisted laser ionization-desorption time-of-flight mass spectroscopy (MALDI-ToF-MS) of poly(N-vinylpyrrolidone). Doctoral 2008-06-23T08:14:20Z 2010-06-01T08:17:54Z 2008-06-23T08:14:20Z 2010-06-01T08:17:54Z 2008-03 Thesis http://hdl.handle.net/10019.1/1296 en University of Stellenbosch application/pdf Stellenbosch : University of Stellenbosch |
| spellingShingle | Living polymerization N-vinylpyrrolidone Raft Xanthtate Dissertations -- Polymer science Theses -- Polymer science Vinyl polymers Addition polymerization Pound, Gwenaelle Reversible addition fragmentation chain transfer (RAFT) mediated polymerization of N-vinylpyrrolidone |
| title | Reversible addition fragmentation chain transfer (RAFT) mediated polymerization of N-vinylpyrrolidone |
| title_full | Reversible addition fragmentation chain transfer (RAFT) mediated polymerization of N-vinylpyrrolidone |
| title_fullStr | Reversible addition fragmentation chain transfer (RAFT) mediated polymerization of N-vinylpyrrolidone |
| title_full_unstemmed | Reversible addition fragmentation chain transfer (RAFT) mediated polymerization of N-vinylpyrrolidone |
| title_short | Reversible addition fragmentation chain transfer (RAFT) mediated polymerization of N-vinylpyrrolidone |
| title_sort | reversible addition fragmentation chain transfer raft mediated polymerization of n vinylpyrrolidone |
| topic | Living polymerization N-vinylpyrrolidone Raft Xanthtate Dissertations -- Polymer science Theses -- Polymer science Vinyl polymers Addition polymerization |
| url | http://hdl.handle.net/10019.1/1296 |
| work_keys_str_mv | AT poundgwenaelle reversibleadditionfragmentationchaintransferraftmediatedpolymerizationofnvinylpyrrolidone |