Poly (vinyl ether)-based graft polymers have been synthesized by the combination of living cationic polymerization of vinyl ethers with other living or controlled/ living polymerization techniques (anionic and ATRP). The process involves the synthesis of well-defined homopolymers (PnBVE) and co/terpolymers [PnBVE-b-PCEVE-b-PSiDEGVE (ABC type) and PSiDEGVE-b-PnBVE-b-PSiDEGVE (CAC type)] by sequential living cationic polymerization of n-butyl vinyl ether (nBVE), 2-chloroethyl vinyl ether (CEVE) and tert-butyldimethylsilyl ethylene glycol vinyl ether (SiDEGVE), using mono-functional {[n-butoxyethyl acetate (nBEA)], [1-(2-chloroethoxy) ethyl acetate (CEEA)], [1-(2-(2-(t-butyldimethylsilyloxy)ethoxy) ethoxy) ethyl acetate (SiDEGEA)]} or di-functional [1,4-cyclohexanedimethanol di(1-ethyl acetate) (cHMDEA), (VEMOA)] initiators. The living cationic polymerizations of those monomers were conducted in hexane at -20 0C using Et3Al2Cl3 (catalyst) in the presence of 1 M AcOEt base.[1] The PCEVE segments of the synthesized block terpolymers were then used to react with living macroanions (PS-DPE-Li; poly styrene diphenyl ethylene lithium) to afford graft polymers. The quantitative desilylation of PSiDEGVE segments by n-Bu4N+F- in THF at 0 °C led to graft co- and terpolymers in which the polyalcohol is the outer block. These co-/terpolymers were subsequently subjected to “grafting-from” reactions by atom transfer radical polymerization (ATRP) of styrene to afford more complex macromolecular architectures. The base assisted living cationic polymerization of vinyl ethers were also used to synthesize well-defined α-hydroxyl polyvinylether (PnBVE-OH). The resulting polymers were then modified into an ATRP macro-initiator for the synthesis of well-defined block copolymers (PnBVE-b-PS). Bifunctional PnBVE with terminal malonate groups was also synthesized and used as a precursor for more complex architectures such as H-shaped block copolymer by “grafting-from” or “grafting-onto” methodologies, which yielding in well-defined PVEs segments with control Mn(GPC) = [VE]/[initiator] and narrow MWDs.

京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第19744号 / 工博第4199号 / 新制||工||1648(附属図書館) / 32780 / 京都大学大学院工学研究科高分子化学専攻 / (主査)教授 中條 善樹, 教授 赤木 和夫, 教授 松原 誠二郎 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DGAM

No description available.

No description available.

No description available.

No description available.

High resolution solid state 1H NMR is used to investigate proton mobility of Nafion, Sulfonated Polyether Ether Ketones(S-PEEK) and their composites, which provides better understanding of their proton conductivities. Proton exchange between sulfonic acid groups and water was observed in these materials. The proton mobility is dependent on both the temperature and the water content. Variable temperature experiments were used to determine the activation energy for proton transportation which generally increases with decrease in hydration level. The preparation of Nafion/SiO2 composites can cause large difference in proton diffusion coefficients and proton conductivities in dried states. This indicates that the amount of dopants needs to be optimized to minimize the blocking of proton diffusion pathways by dopant particles. Detailed information on the control of surface hydroxyl groups in Nafion/SiO2 is obtained through the combination of 29Si and 1H NMR. Although hydrated Nafion/ZrP composites show reduced proton activation energy, they present lower proton conductivity at 35°C than unmodified Nafion. For composites dried at 160°C, both the conversion of monohydrogen phosphate into pyrophosphate and the protonation of monohydrogen phosphate have been observed, which could be one of reasons for the decreased proton conductivity after rehydration. Under high humidification, a single or multiple sulfonic acid proton environments was observed in S-PEEKs, which explains the small proton conductivity difference between some of S-PEEKs. However, the observed conductivity difference for S-PEEKs cast from different solvents was attributed to distinct mobilities of polymer chains. In the crosslinked S-PEEK, not all the crosslinkers of ethylene glycol are fully crosslinked. Proton exchange between residual sulfonic acid and hydroxyls of the crosslinker was observed, which is the primary reason that the crosslinked S-PEEK, with very low residual degree of sulfonation (13 %), still shows proton conductivity comparable to those of S-PEEKs. / Thesis / Doctor of Philosophy (PhD)

Due to the remote and dispersed nature of Alberta’s oil wells, it is not economical for the energy industry to capture all of the solution gas produced and as a result, the gas is being flared and vented in significant amounts. The objective of this research is to aid in the conversion of solution gas into dimethyl ether (DME) in a remote location by designing a distillation column that purifies DME and its reaction by-products, carbon dioxide, methanol and water. In order to develop an implementable solution, the distillation equipment must fit inside of a 40-foot shipping container to be transported to remote locations. Given the size constraint of the system, process intensification is the best strategy to efficiently separate the mixture. Several process intensification distillation techniques are explored, including semicontinuous distillation, the dividing wall column (DWC) and a novel semicontinuous dividing wall column (S-DWC). The traditional semicontinuous distillation column purifies DME to fuel grade purity, however the other components are not separated to a high enough grade given the height constrain of the system. The DWC and S-DWC both purify DME to its desired purity along with producing high purity waste streams. The S-DWC purifies the reaction intermediate methanol to a grade slightly higher than the DWC and is pure enough to recycle back to the reactor. An economic comparison is made between the three systems. While the DWC is a cheaper method of producing DME, the trade-off is the purity of the methanol produced. Overall, this research shows that it is possible to purify DME and its reaction by-products in a 40-foot distillation column at a cost that is competitive with Diesel. / Thesis / Master of Applied Science (MASc)

No description available.

No description available.