Thesis (MSc)--University of Stellenbosch, 2007. / ENGLISH ABSTRACT: The main objective of this project was the controlled synthesis of graft copolymers via a
thiol-ene addition mechanism. The Reversible Addition-Fragmentation chain Transfer
(RAFT) process was used in all polymerization reactions with the aim to achieve a
certain degree of control over the molecular weight. Several synthetic steps were
required in order to obtain the final graft copolymer and each step was investigated in
detail.
Firstly, two RAFT agents (cyanovaleric acid dithiobenzoate and dodecyl isobutyric acid
trithiocarbonate) were synthesized to be used in the various polymerization reactions of
styrene and butyl acrylate. This was done successfully and the RAFT agents were used
to synthesize low molecular weight polystyrene branches of the graft copolymer.
Different molecular weights were targeted. It was found that some retardation
phenomena were present especially at high RAFT agent concentrations.
The polystyrene branches that were synthesized contained RAFT end-groups. Various
pathways were explored to modify these RAFT end-groups to form thiol end-groups to
be used in the thiol-ene addition reaction during the grafting process. The use of sodium
methoxide for this purpose proved most successful and no evidence of the formation of
disulfide bridges due to the initially formed thiols was detected.
Allyl methacrylate (AMA) was chosen as monomer to be used for the synthesis of the
polymer backbone because it has two double bonds with different reactivities. For the
first time, RAFT was used to polymerize AMA via the more reactive double bond to
obtain linear poly(allyl methacrylate) (PAMA) chains with pendant double bonds.
However, at higher conversions, gelation occurred and the molecular weight distributions
were uncontrolled. NMR was successfully used to study the tacticity parameters of the
final polymer.
Finally, the synthesis of the graft copolymer, PAMA-g-polystyrene, was carried out by
means of the “grafting onto” approach. The thiol-functionalized polystyrene branches
were covalently attached to the pendant double bonds of the PAMA polymer backbone
via a thiol-ene addition mechanism in the presence of a free radical initiator. A Multi-
Angle Laser Light Scattering (MALLS) detector was utilized in conjunction with Size-
Exclusion Chromatography (SEC) to obtain molecular weight data of the graft
copolymer. The percentage grafting, as determined by 1H-NMR, was low. / AFRIKAANSE OPSOMMING: Die hoofdoel van hierdie projek is die beheerde sintese van ‘n entkopolimeer via ‘n
merkaptaan-een addisiereaksie. Die sogenaamde “Reversible Addition-Fragmentation
chain Transfer” (RAFT) proses is in al die polimerisasiereaksies gebruik met die doel om
‘n mate van beheer oor die molekulêre massa van die polimere te verkry. Verskeie
stappe (waarvan elkeen ten volle ondersoek is) was nodig om die finale entkopolimeer te
verkry.
Eerstens is twee RAFT-agente (sianovaleriaansuur ditiobensoaat en dodekielisobottersuur
tritiokarbonaat) gesintetiseer vir gebruik in verskeie polimerisasiereaksies van stireen en
butielakrilaat. Hierdie stap was suksesvol en die RAFT-agente is toe gebruik vir die
sintese van lae molekulêre massa polistireensytakke vir die entkopolimeer. Die
molekulêre massas van die sytakke is gevarieer en daar is gevind dat vertragings in die
polimerisasiereaksies voorgekom het, veral by hoë konsentrasies van die RAFT-agente.
Die polistireensytakke wat gemaak is, besit almal ‘n RAFT-eindgroep. Verskeie roetes is
bestudeer ten einde die RAFT-eindgroepe tot merkaptaan-eindgroepe te modifiseer om
sodoende tydens ‘n merkaptaan-een addisiereaksie gebruik te word. Die gebruik van
natriummetoksied was hier die suksesvolste en daar was geen teken van die vorming van
disulfiedbrûe as gevolg van die oorspronklik gevormde merkaptane nie.
Allielmetakrilaat (AMA) is gekies as die monomeer wat gebruik sou word vir die sintese
van die polimeerruggraat omdat die monomeer twee dubbelbindings met verskillende
reaktiwiteite besit het. Vir die eerste keer is RAFT gebruik vir die polimerisasie van
AMA via die meer reaktiewe dubbelbinding om lineêre poli(allielmetakrilaat) (PAMA)
kettings met dubbelbindings in die sygroepe te verkry. Gelvorming en onbeheerde
molekulêre massaverspreiding het egter by hoër monomeeromsettings voorgekom. KMR
is susksekvol gebruik om die taktisiteitsparameters van die finale polimeer te bestudeer.
Ten slotte is die sintese van die entkopolimeer, PAMA-g-polistireen, uitgevoer deur die
aanhegting van voorafgevormde sytakke. Die polistireensytakke met die
merkaptaaneindgroepe is kovalent geheg aan die dubbelbindings in die sygroepe van die
PAMA-polimeerruggraat via ‘n merkaptaan-een addisiemeganisme in die
teenwoordigheid van ‘n vrye radikaalinisieerder. ‘n Kombinasie van
gelpermeasiechromatografie en multi-hoeklaserligverstrooiing is gebruik om die
molekulêre massa van die entkopolimeer te bepaal. Die persentasie sytakke soos bepaal
deur 1H-KMR was laag.
| Identifer | oai:union.ndltd.org:netd.ac.za/oai:union.ndltd.org:sun/oai:scholar.sun.ac.za:10019.1/18700 |
| Date | 12 1900 |
| Creators | Stegmann, Jacobus Christiaan |
| Contributors | Sanderson, R.D., Stellenbosch University. Faculty of Science. Dept. of Chemistry and Polymer Science. |
| Publisher | Stellenbosch : Stellenbosch University |
| Source Sets | South African National ETD Portal |
| Language | en_ZA |
| Detected Language | English |
| Type | Thesis |
| Format | 116 leaves |
| Rights | Stellenbosch University |
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