Summary: In this study five xanthate (Reversible Addition‐Fragmentation chain Transfer (RAFT)/Macromolecular Design through Interchange of Xanthates (MADIX)) agents were synthesized, namely monofunctional, difunctional, trifunctional and tetrafunctional species of the form SC(O‐Z)‐S‐R, with different leaving groups and different activating moieties some of which are completely novel. Polyvinyl acetates (PVAc) in the form of linear, three armed and four armed star shaped polymers were then successfully synthesized in reactions mediated by these xanthate RAFT/MADIX agents.

ii Declaration I, the undersigned, hereby declare that the work contained in this thesis is my own original work and that I have not previously in its entirety or in part submitted it at any university for a degree. _____________________ Reda FleetSigned on the 27 th day of September 2006. Abstract iii AbstractCellulose, one of the most abundant organic substances on earth, is a linear polymer of D-glucose units joined through 1,4-β-linkages. Cellulose is however not easily processed without chemical modification. A number of techniques exist for the modification of cellulose, of which the viscose process is one of the most widely applied. Grafting of synthetic polymeric chains onto or from cellulosic materials is an useful technique that can be used to combine the strengths of synthetic and natural polymers dramatically, so changing the properties of cellulosic materials (pulp, regenerated cellulose, cellulose derivatives).In this study five model xanthate (Reversible Addition-Fragmentation chain Transfer

Glycopolymers (synthetic sugar-containing polymers) have become increasingly attractive to polymer chemists because of their role as biomimetic analogues and their potential for commercial applications. Glycopolymers of different structures confer high hydrophilicity and water solubility and can therefore be used for specialised applications, such as artificial materials for a number of biological, pharmaceutical and biomedical uses. The synthesis and characterisation of a series of novel glycopolymer brushes, namely poly(2-(2-and poly(4-vinylbenzyl chloride-alt-maleic anhydride)-g-poly(methyl 6-O-methacryloyl-a-Dglucoside) (P(S d -alt-MAnh)-g-P(6-O-MMAGIc)) are described in this paper. Reversible addition-fragmentation chain transfer (RAFT)-mediated polymerisation was used to synthesise four well-defined atom transfer radical polymerisation (ATRP) macroinitiators (the backbone of the glycopolymer brushes). These ATRP macroinitiators were subsequently used in the 'grafting from' approach (in which side chains are grown from the backbone) to prepare high molar mass and low polydispersity index glycopolymer brushes with different grafting densities along the backbone. The number average molar mass of the glycopolymer brushes was determined using size exclusion chromatography with a multi-angle laser light scattering detector and further structural characterisation was conducted using 1 H-nuclear magnetic resonance spectroscopy. The results confirmed that glycopolymer brushes were successfully synthesised via a combination of RAFT-mediated polymerisation and ATRP.

The synthesis and characterization of a series of glycopolymer brushes with P(methyl 6-O -methacryloyl-α -D -glucoside) (P(6-O -MMAGIc)) side chains (SCs) is reported. The formation of well-defi ned glycopolymer brushes is confi rmed by 1 H NMR spectroscopy and size exclusion chromatography (SEC) with a MALLS detector. Four multifunctional macroinitiators with different topologies and molar masses are prepared. The P(6-O -MMAGIc) SCs are cleaved from the backbone and analyzed by 1 H NMR and SEC-MALLS, which further confi rmed the synthesis of well-defi ned glycopolymer brushes. The grafting efficiency of P(6-O -MMAGIc) from the different macroinitiators are determined to be in the range 0.37 < f < 0.55.

Glycopolymers (synthetic sugar-containing polymers) have become increasingly attractive to polymer chemists because of their role as biomimetic analogues and their potential for commercial applications. Glycopolymers of different structures confer high hydrophilicity and water solubility and can therefore be used for specialised applications, such as artificial materials for a number of biological, pharmaceutical and biomedical uses. The synthesis and characterisation of a series of novel glycopolymer brushes, namely poly(2-(2bromoisobutyryloxy) ethyl methacrylate)-g-poly(methyl 6-O-methacryloyl-a-D-glucoside) (P(BIEM)-g-P(6-O-MMAGIc)), poly(2-(2-bromoisobutyryloxy) ethyl methacrylate-co-methyl methacrylate)-g-poly(methyl 6-O-methacryloyl-a-D-glucoside) P(BIEM-co-MMA)-g-P(6-O-MMAGIc), poly(2-(2-bromoisobutyryloxy) ethyl methacrylate-b-methyl methacrylate)g-poly(methyl 6-O-methacryloyl-a-D-glucoside) P(BIEM-b-MMA)-g-P(6-O-MMAGIc) and poly(4-vinylbenzyl chloride-alt-maleic anhydride)-g-poly(methyl 6-O-methacryloyl-a-Dglucoside) (P(S d -alt-MAnh)-g-P(6-O-MMAGIc)) are described in this paper. Reversible addition-fragmentation chain transfer (RAFT)-mediated polymerisation was used to synthesise four well-defined atom transfer radical polymerisation (ATRP) macroinitiators (the backbone of the glycopolymer brushes). These ATRP macroinitiators were subsequently used in the 'grafting from' approach (in which side chains are grown from the backbone) to prepare high molar mass and low polydispersity index glycopolymer brushes with different grafting densities along the backbone. The number average molar mass of the glycopolymer brushes was determined using size exclusion chromatography with a multi-angle laser light scattering detector and further structural characterisation was conducted using 1 H-nuclear magnetic resonance spectroscopy. The results confirmed that glycopolymer brushes were successfully synthesised via a combination of RAFT-mediated polymerisation and ATRP.