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Use of the RAFT technique as an efficient method to synthesise well defined polymer-clay nanocomposites with improved properties

Thesis (PhD (Chemistry and Polymer Science))--University of Stellenbosch, 2009.

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Main Author: Samakande, Austin
Other Authors: Sanderson, R. D.
Format: Thesis
Language:en_ZA
Published: Stellenbosch : University of Stellenbosch 2009
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access_status_str Open Access
author Samakande, Austin
author2 Sanderson, R. D.
author_browse Samakande, Austin
Sanderson, R. D.
author_facet Sanderson, R. D.
Samakande, Austin
author_sort Samakande, Austin
collection Thesis
dc_rights_str_mv University of Stellenbosch
description Thesis (PhD (Chemistry and Polymer Science))--University of Stellenbosch, 2009.
format Thesis
id oai:scholar.sun.ac.za:10019.1/1242
institution Stellenbosch University (South Africa)
language en_ZA
last_indexed 2026-06-10T12:44:50.018Z
license_str Other — see source repository
provenance_str_mv Harvested via OAI-PMH from SUNScholar — Stellenbosch University Repository
publishDate 2009
publishDateRange 2009
publishDateSort 2009
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:10019.1/1242 Use of the RAFT technique as an efficient method to synthesise well defined polymer-clay nanocomposites with improved properties Samakande, Austin Sanderson, R. D. Hartmann, P. C. University of Stellenbosch. Faculty of Science. Dept. of Chemistry and Polymer Science. Dissertations -- Chemistry Theses -- Chemistry Addition polymerization Nanostructured materials Polymer clay Polymeric composites Thesis (PhD (Chemistry and Polymer Science))--University of Stellenbosch, 2009. Synthesis and structural characterization of two novel cationic and three new neutral reversible addition–fragmentation chain transfer (RAFT) agents is described. The cationic RAFT agents bear a quaternary ammonium group: N,N-dimethyl-N-(4- (((phenylcarbonothionyl)thio)methyl)benzyl)ethanammonium bromide (PCDBAB) and N-(4-((((dodecylthio)carbonothioyl)thio)methyl)benzyl)-N,N-dimethylethanammonium bromide (DCTBAB). The three neutral RAFT agents synthesized are 1,4- phenylenebis(methylene)dibenzene carbodithioate (PCDBDCP), didodecyl-1,4- phenylenebis(methyllene)bistrithiocarbonate (DCTBTCD) and 11-(((benzylthio)carbonothioyl) thio)undecanoic acid (BCTUA). The self-assembly behaviour in diluted aqueous solutions of the cationic RAFT agents, PCDBAB and DCTBAB, is described. The self-assembly behaviour was promoted by the presence of the thiocarbonyl- thio group on the RAFT agents, in addition to the overall chemical structure of the surfactant that also influence self-assembly. The RAFT agents were used for the bulk or miniemulsion RAFT-mediated controlled free-radical polymerization in the presence of clay to yield polymer–clay nanocomposites (PCNs). Bulk polymerization resulted in PCNs with better control of molar mass and polydispersity index (PDI) values when compared to PCNs prepared by miniemulsion polymerization. In both bulk and miniemulsion polymerizations the molar masses and PDI values were dependent on the amount of clay and RAFT agent present in the system. Free-radical bulk neutral RAFT agent-mediated polymerization resulted in PCNs with predominantly intercalated morphology. This was attributed to radical–radical coupling of the initiator anchored onto the clay galleries on which polymerization took place. On the other hand, when the cationic RAFT agent anchored onto clay, i.e. RAFT-modified clay was used, bulk polymerization resulted in predominantly exfoliated PCNs. However, miniemulsion polymerization carried out in the presence of the RAFT-modified clays resulted in PCNs with a morphology that ranged from partially exfoliated to intercalated morphology, as the clay loading was increased. The changing morphology for miniemulsion-based PCNs was attributed to the decreasing molar mass as the clay loading was increased. The PCNs obtained had enhanced thermo-mechanical properties as a result of the presence of clay. The thermo-mechanical properties depended on the molar mass, PDI, clay loading, and the morphology of the PCNs. Doctoral 2009-02-10T13:02:06Z 2010-06-01T08:16:19Z 2009-02-10T13:02:06Z 2010-06-01T08:16:19Z 2009-03 Thesis http://hdl.handle.net/10019.1/1242 en_ZA University of Stellenbosch application/pdf Stellenbosch : University of Stellenbosch
spellingShingle Dissertations -- Chemistry
Theses -- Chemistry
Addition polymerization
Nanostructured materials
Polymer clay
Polymeric composites
Samakande, Austin
Use of the RAFT technique as an efficient method to synthesise well defined polymer-clay nanocomposites with improved properties
title Use of the RAFT technique as an efficient method to synthesise well defined polymer-clay nanocomposites with improved properties
title_full Use of the RAFT technique as an efficient method to synthesise well defined polymer-clay nanocomposites with improved properties
title_fullStr Use of the RAFT technique as an efficient method to synthesise well defined polymer-clay nanocomposites with improved properties
title_full_unstemmed Use of the RAFT technique as an efficient method to synthesise well defined polymer-clay nanocomposites with improved properties
title_short Use of the RAFT technique as an efficient method to synthesise well defined polymer-clay nanocomposites with improved properties
title_sort use of the raft technique as an efficient method to synthesise well defined polymer clay nanocomposites with improved properties
topic Dissertations -- Chemistry
Theses -- Chemistry
Addition polymerization
Nanostructured materials
Polymer clay
Polymeric composites
url http://hdl.handle.net/10019.1/1242
work_keys_str_mv AT samakandeaustin useoftherafttechniqueasanefficientmethodtosynthesisewelldefinedpolymerclaynanocompositeswithimprovedproperties