Author : Chi Zhang
Publisher :
Page : pages
File Size : 14,66 MB
Release : 2014
Category :
ISBN :
"Stimuli-responsive polymers have been touted as "smart" due to their fast and reversible responses to environmental changes. It is imperative for these polymers to have well-defined structures so that their performance can be consistent and predictable. In order to achieve this, nitroxide mediated polymerization (NMP) was employed as the synthesis technique for the microstructured polymers that form the core of the investigations presented in this thesis. As one of the main controlled radical polymerization techniques, NMP stands out for its simplicity in both required ingredients and purification procedures. Many known stimuli-responsive polymers are poly(methacrylates). However, homopolymerization of methacrylates has been challenging for NMP mainly due to the large equilibrium constant that resulted in high concentration of active radicals and thus excessive irreversible terminations. By using a small amount of "controlling co-monomer" such as styrene, copolymerizations with methacrylate-rich feeds can be controlled using the commercially available alkoxyamine initiator BlocBuilderTM via NMP, featuring linear increases in number average molecular weight versus conversion, and narrow molecular weight distribution.In this thesis, two methacrylates, namely 2-(dimethylamino)ethyl methacrylate (DMAEMA) and benzyl methacrylate (BzMA), whose homopolymers exhibit LCST-type phase separation behaviours in aqueous and ionic liquid (IL) solutions, respectively, were copolymerized with various controlling co-monomers by NMP to demonstrate the versatility of NMP in tuning thermo-responsive properties. For both methacrylates, styrene was initially used as the controlling co-monomer to obtain copolymers with relatively narrow molecular weight distribution and ability to extend chains to form block copolymers when reinitiated with a fresh batch of monomer. 2-Vinylpyridine (2VP) was then chosen to copolymerize with DMAEMA for its lower hydrophobicity compared to styrene and pH-sensitivity, where about 2 - 5 mol% 2VP was shown sufficient to obtain well-defined DMAEMA/2VP copolymers. The detailed phase behaviour characterization of these DMAEMA-rich copolymers in aqueous solutions revealed the effects of important factors such as pH, copolymer composition, solution concentration and polymer microstructure, on the tuning of transition temperatures.For BzMA, 9-(4-vinylbenzyl)-9H-carbazole (VBK) was used as an alternative controlling co-monomer. Controlled and pseudo-"living" copolymerizations were achieved with as little as 2 mol% VBK in the feed, demonstrating significant improvement compared to the BzMA/styrene system. The incorporation of fluorescent VBK resulted in 5-fold fluorescence enhancement during the phase separation of BzMA/VBK copolymers from IL [C2mim][NTf2]. The enhancement resulted from heightened efficiency of the fluorescence resonance energy transfer (FRET) between BzMA and VBK during aggregation. However, the solvatophobicity of VBK also significantly reduced the solubility of BzMA/VBK copolymers in the IL and rendered the phase separation irreversible. Further investigation on the effects of solvatophilicity and chain mobility on phase separation and reversibility in ILs was carried out by incorporating varying amounts of solvatophilic co-monomer, namely methyl methacrylate (MMA) and oligo(ethylene glycol) methacrylate (OEGMA), yielding BzMA/MMA/VBK and BzMA/OEGMA/VBK terpolymers. It was found that molecular weight, glass transition temperature, and solution concentration all played important roles on phase separation temperature but sufficiently high solvatophilicity (quantified by the concentration of solvatophilic group) was essential to facilitate the re-dissolution process after phase separation. " --