Self-Assembly of Stimulus-Responsive Water Soluble RAFT (Co)Polymers

In this thesis, homopolymers and well-defined AB diblock copolymers that are stimulus responsive were prepared via a combination of reversible-addition fragmentation chain transfer (RAFT) polymerization and post-polymerization modification. For the first part of the thesis, CO2-responsive (co)polymers containing an amidine and/or guanidine moiety were synthesized through the post-polymerization modification of pentafluorophenyl acrylate (PFPA) containing precursors. The use of CO2 as a gas trigger to tune the self-assembly of an amidine containing AB diblock copolymer was also successfully demonstrated. In the second and third part of the thesis, the ring opening reaction of 2-vinyl-4,4-dimethylazlactone (VDA) was highlighted. A range of novel pH and/or thermo-responsive (co)polymers were derived using RAFT synthesized (co)polymers containing the reactive 2-vinyl-4,4-dimethylazlactone (VDA) scaffold in the second part of the thesis and their aqueous solution behaviour were studied through the application of various temperature and/or pH stimuli. Finally, for the third part of the thesis, VDA homopolymers with different hydrophobic α end groups were post-modified using a range of different amines and their behaviour in aqueous media was studied. A comparison of their aqueous solution behaviour was made to determine the effects that different hydrophobic α end groups may have on the solution properties of the various homopolymers