Conventional free-radical miniemulsion polymerization has been well studied since early 1970s. Conventional free-radical miniemulsion polymerizations have inherent limitations associated with uncontrolled free-radical polymerization mechanism. The goal of this work is to develop a variety of unconventional miniemulsion polymerization techniques by applying new polymerization techniques (typically in solution or bulk) to miniemulsion systems to overcome their inherent limitations and extend the application of free-radical miniemulsion polymerization. This work focused on the exploration of kinetic and mechanistic aspects of unconventional miniemulsion polymerizations. First, enzyme initiated free-radical miniemulsion polymerization, in contrast with those conventional chemical initiated miniemulsion polymerization, is demonstrated for the first time as an answer to the challenges associated with using the hydrophobic of vinyl monomers in aqueous enzymatic reactions. A procedure for enzyme initiated free-radical miniemulsion polymerization was formulated and stable poly(styrene) latexes were successfully synthesized. The kinetics of enzyme initiated free-radical miniemulsion polymerization and the effect of reaction conditions on the polymerization was elucidated. Second, RAFT miniemulsion polymerization of hydrophobic monomers was performed in CSTR trains and the transient states, previously identified by others in our group, were elucidated. Next, RAFT miniemulsion polymerization of a partially water soluble monomer was studied. RAFT miniemulsion polymerizations of gamma-methyl-alpha-methylene-gamma-butyrolactone, a partially water soluble lactone monomer derived from renewable sources, was successfully formulated. Homogeneous nucleation was found to play an important role in the free-radical "miniemulsion" homopolymerization of MeMBL. By using styrene as a comonomer, the RAFT miniemulsion polymerizations of MeMBL and styrene were well controlled and narrowly distributed copolymers of MeMBL/styrene were produced. Following the study of the partially water monomer, RAFT inverse miniemulsion polymerization was proposed for the polymerization of hydrophilic monomers. The kinetics of RAFT inverse miniemulsion polymerization of acrylamide exhibited the typical behavior of controlled polymerizations up to high conversions. The effects of reaction parameters on the polymerization rate and particle size were investigated. The dominant locus of radical generation for particle nucleation and the fate of desorbed monomeric radicals in inverse miniemulsion polymerizations were evaluated. Finally in this work, conclusions and implications are presented and ideas for future work are suggested.

No abstract available.

Chitin is a natural polymer which is extracted from a number of biological sources. This polymer is deacetylated to form the related polymer chitosan. The design and preparation of chitosan derivatives has been investigated to tailor the physical and chemical properties towards specific applications. To this end, this thesis describes the synthesis and characterisation of a number of chitosan derivatives. The prepared polymers contained either naphthalimide groups, thiol groups, poly(methyl methacrylate) side chains or poly(oligoethylene glycol methyl ether methacrylate) side chains. Chitin was successfully extracted and purified from squid pens by literature methods to give polymers with DD values from 12 to 23%. The Kurita method was used to obtain chitosan samples with a range of DD values from 75 to 91%. The prepared polymers were characterised by microanalysis, IR, �H NMR and solid-state ��C NMR spectroscopy. The MW distributions of the chitosan samples were determined by GPC in 0.3 M AcOH/0.2 M AcONa(aq) solution with dextran standards. The N-(naphthalimide)-chitosan derivatives were fluorescent materials and were typically prepared from the reaction of 4-bromonaphthalic anhydride with chitosan. This reaction was thoroughly investigated to find the optimal reaction conditions. The bromo groups were subsequently displaced by one of four nucleophiles: dimethylamine, piperidine, methoxide or vinylferrocene. The polymers were characterised by microanalysis, GPC, IR, �H NMR, UV-vis and fluorescence spectroscopy. The excitation and emission wavelengths and Stokes shifts were dependent on the substituent present in the naphthalimide group. Chitin and chitosan were sequentially reacted with tosyl chloride, potassium thioacetate and sodium methoxide to form the thiolated derivatives. The success of the tosylation reaction was dependent on the synthetic route used and the DD of the polysaccharide. The thiolated chitin polymers were well defined although the samples were completely insoluble. The thiolated chitosan polymers were also characterised and were highly swollen in acetic acid solution. These thiolated polysaccharides were used as macroinitiators for the free-radical polymerisation of MMA. The products obtained from the reaction of 6-mercaptochitin in DMSO with MMA were typically prepared with low yields and low amounts of grafting. The products prepared from 6-mercaptochitosan under the same conditions contained larger amounts of the synthetic polymers although the products were highly variable. MMA was subsequently polymerised with 6-mercaptochitosan in acetic acid buffer to form highly grafted copolymers. Chitosan was reacted with the monomer OEGMA by ATRP to form chitosan-graft-poly(OEGMA) copolymers. Two synthetic routes were investigated. The "grafting-from" route involved. the formation of a chitosan macroinitiator and polymerisation of OEGMA with this polymer. The polymers contained a large amount of grafted side chains as estimated from the �H NMR spectra. However, the purification was not satisfactory as determined by the presence of two peaks in the GPC traces. The "grafting-to", route involved the formation of poly(OEGMA) by ATRP with activated initiators and subsequent attachment to chitosan. The prepared copolymers showed large differences in their appearance with even very low amounts of grafting. The purification of the polymers prepared by this method was successful with no detectable homopolymer as determined by GPC analysis.

The research reported in this thesis has been divided into five separate categories - Synthesis of dialkali metal silanediolate and siloxanediolate salts, - Synthesis of siloxane copolymers using interfacial condensation polymerisation, - Synthesis of silicon-organic copolymers using interfacial condensation polymerisation, - Investigation into the analysis of polymers using size exclusion chromatography, and - Theoretical investigation into TMDSC analysis of polymers. / Thesis (PhDAppliedScience)--University of South Australia, 2000.

Thesis (PhDAppliedScience)--University of South Australia, 2003.

Thesis (PhDAppliedScience)--University of South Australia, 2003.

Chitin is a natural polymer which is extracted from a number of biological sources. This polymer is deacetylated to form the related polymer chitosan. The design and preparation of chitosan derivatives has been investigated to tailor the physical and chemical properties towards specific applications. To this end, this thesis describes the synthesis and characterisation of a number of chitosan derivatives. The prepared polymers contained either naphthalimide groups, thiol groups, poly(methyl methacrylate) side chains or poly(oligoethylene glycol methyl ether methacrylate) side chains. Chitin was successfully extracted and purified from squid pens by literature methods to give polymers with DD values from 12 to 23%. The Kurita method was used to obtain chitosan samples with a range of DD values from 75 to 91%. The prepared polymers were characterised by microanalysis, IR, �H NMR and solid-state ��C NMR spectroscopy. The MW distributions of the chitosan samples were determined by GPC in 0.3 M AcOH/0.2 M AcONa(aq) solution with dextran standards. The N-(naphthalimide)-chitosan derivatives were fluorescent materials and were typically prepared from the reaction of 4-bromonaphthalic anhydride with chitosan. This reaction was thoroughly investigated to find the optimal reaction conditions. The bromo groups were subsequently displaced by one of four nucleophiles: dimethylamine, piperidine, methoxide or vinylferrocene. The polymers were characterised by microanalysis, GPC, IR, �H NMR, UV-vis and fluorescence spectroscopy. The excitation and emission wavelengths and Stokes shifts were dependent on the substituent present in the naphthalimide group. Chitin and chitosan were sequentially reacted with tosyl chloride, potassium thioacetate and sodium methoxide to form the thiolated derivatives. The success of the tosylation reaction was dependent on the synthetic route used and the DD of the polysaccharide. The thiolated chitin polymers were well defined although the samples were completely insoluble. The thiolated chitosan polymers were also characterised and were highly swollen in acetic acid solution. These thiolated polysaccharides were used as macroinitiators for the free-radical polymerisation of MMA. The products obtained from the reaction of 6-mercaptochitin in DMSO with MMA were typically prepared with low yields and low amounts of grafting. The products prepared from 6-mercaptochitosan under the same conditions contained larger amounts of the synthetic polymers although the products were highly variable. MMA was subsequently polymerised with 6-mercaptochitosan in acetic acid buffer to form highly grafted copolymers. Chitosan was reacted with the monomer OEGMA by ATRP to form chitosan-graft-poly(OEGMA) copolymers. Two synthetic routes were investigated. The "grafting-from" route involved. the formation of a chitosan macroinitiator and polymerisation of OEGMA with this polymer. The polymers contained a large amount of grafted side chains as estimated from the �H NMR spectra. However, the purification was not satisfactory as determined by the presence of two peaks in the GPC traces. The "grafting-to", route involved the formation of poly(OEGMA) by ATRP with activated initiators and subsequent attachment to chitosan. The prepared copolymers showed large differences in their appearance with even very low amounts of grafting. The purification of the polymers prepared by this method was successful with no detectable homopolymer as determined by GPC analysis.

Thesis (Ph. D.)--University of Canterbury, 2008. / Typescript (photocopy). "First submitted June 2007. Final version January 2008." Includes bibliographical references. Also available via the World Wide Web.

Thesis (Ph.D.)--McMaster University, 2002. / Advisor: H.D.H. Stöver. Includes bibliographical references. Also available via World Wide Web.

Thesis (Ph.D.)--McMaster University, 2005. / Supervisor: Shiping Zhu. Includes bibliographical references.