Thesis (Ph. D.)--Technische Universiteit Eindhoven, 1993. / Includes bibliographical references.

Thesis (M.S.)--University of Texas at El Paso, 2008. / Title from title screen. Vita. CD-ROM. Includes bibliographical references. Also available online.

京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第19748号 / 工博第4203号 / 新制||工||1648(附属図書館) / 32784 / 京都大学大学院工学研究科高分子化学専攻 / (主査)教授 辻井 敬亘, 教授 山子 茂, 教授 渡辺 宏 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DFAM

Regardless of the simplicity in molecular structure, polyethylene is used in high-performance applications such as medical prostheses and ballistics. Recent advancements in homogeneous catalysis produced UHMWPE in the low-entangled or dis-entangled state that allowed solvent-free-solid-state processing to achieve ultimate mechanical properties ever achieved for a synthetic polymer. Although several homogeneous complexes are known to produce dis-UHMWPE, existing major challenges are uncontrolled nascent polymer morphology, as a consequence reactor fouling/wall sheeting. In such a scenario, a heterogeneous catalyst that can produce dis-UHWMPE to an extent that the characteristics and properties equivalent to that obtained in homogeneous condition, remains an open challenge. The thesis will discuss the know-how for the synthesis of dis-UHMWPE via heterogeneous route to facilitate industrial production by following fundamental understanding of polymerization catalysis, physics, processing, and testing. In this thesis, in-situ formed nano activator/support MgClx/EtnAly(2-ethyl-1-hexoxide)z is employed with a highly active bis[N-(3-tert-butylsalicylidene)pentafluoroanilinato] titanium (IV) dichloride (Cat. 1) for synthesis of dis-UHMWPE. In addition, the relatively easy formation of the MgClx/RnClmAly(OR’) activators/supports allows tailoring by the selection of different aluminum-alkyls and alcohols, giving access to a variety of co-catalysts. This investigation resulted in UHMWPE having Mw from 3 to an unprecedented 43 M g/mol and Ð from 3 to 38 with very high activities up to 2750 kgPE molcat.-1 bar-1 h-1. The adopted route resulted in nano-support that allows tailoring of the entangled state and control over the nascent morphology without reactor fouling, thus providing feasibility of pursuing the polymerization via a continuous process. The nascent polymer shows formation of single crystals of linear UHMWPE and is suggestive of the low-entangled state. The topological differences, with the commercial entangled sample, are identified solid-state NMR, DSC, and rheology. The disentangled crystals allowed desired chain orientation for securing unprecedented tensile modulus (>200 N/tex) and tensile strength (>4.0 N/tex) via solid-state processing. Additionally, the investigation of creep response in the uniaxial tapes has revealed strong influence of molecular weight and entanglement density. These unique characteristics and unprecedented mechanical properties are equivalent to that perceived using a homogeneous catalysis and are the first of their kind achieved for a polymer synthesized using a heterogeneous catalysis.