Browsing by Author "Lee, Bin"
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- Synthesis and characterization of high performance polytetrahydrofuran based polyurethane-urea and ionene elastomersLee, Bin (Virginia Polytechnic Institute and State University, 1987)In this thesis, the effect of interphase bonding on the cohesiveness of domain structure was addressed. The interchain attractive forces between rigid segments and the phase separation between hard and soft segments have been improved by introducing either urea groups or ionic units. The urea linkages have the possibility of extensive hydrogen bonding while ionic units interact with each other by coulombic interactions, which provide even stronger interchain associations than the hydrogen bonding effects. This thesis addressed the preparation and characterization of polytetrahydrofuran based segmented polyurethane-urea and ionene elastomers. The urea linkages were effectively introduced to the polyurethane elastomers through an unconventional route which was based on carbamate-isocyanate interactions. The carbamates were generated principally from isocyanate functional prepolymers and tertiary alcohols. The carbamates were rearranged thermally and/or catalytically to produce amines which were rapidly converted to ureas. The effects of varying the size of the rigid and flexible segments in polyurethane elastomers on physical behavior were investigated. The importance of hydrogen bonding interactions in promoting phase separation of hard and soft segments and the cohesiveness of hard segment domain structure was demonstrated. Living, difunctional polytetrahydrofuran dioxonium ions were prepared via triflic anhydride initiation. The direct coupling of these "living" polytetrahydrofuran dioxonium ions with a ditertiary amine was used to produce a novel segmented ionene elastomer. The ionenes thus synthesized displayed interesting solution behavior and could be molded, or cast to produce good physical properties. Photochromic as well as thermochromic phenomena were also noticed in these systems.
- Synthesis and characterization of polydimethylsiloxane-polyamide segmented copolymersLee, Bin (Virginia Polytechnic Institute and State University, 1985)The polyamide poly(ε-caprolactam) or "nylon 6" is a very important fiber forming polymer which finds many applications in the carpet industry and elsewhere due to the very high strength of this fiber. However, a major drawback is its hydrophilicity. This feature influences both the surface and bulk mechanical behavior. Siloxane based macromolecules are hydrophobic, thermally stable and exhibit dimensional stability over a wide temperature range. Unlike the polyamide nylon 6, these hydrophobic materials display relatively low surface free energy. Thus, they can be used for the surface modification of nylon 6, provided a suitable adhesion or "anchoring" method is feasible. Polyamide-polydimethylsiloxane segmented or block copolymers were found to be suitable "interfacial" agents. They were synthesized by reacting aminopropyl-terminated polydimethylsiloxane (PDMS) oligomers with sebacyl chloride via an interfacial polymerization in which methylene chloride was used as the solvent or organic phase. A second diamine "chain extender" was also utilized, if desired. By varying the mole ratio of soft segment to the chain extender p-aminocyclohexylmethane (PACM-20), copolymers with various percentages of hard segments can be synthesized. Weight fractions of 2, 5, or 10% of the polyamide-poly-dimethylsiloxane block copolymers were physically melt mixed with nylon 6 in an extruder. The presence of polydimethylsiloxane on the surface of the blend was detected by determining the critical surface tensions of wetting using water as the contact angle test liquid. Such modified polyamides were successfully melt spun into fibers which displayed good mechanical properties and enhanced soil resistance. Fibers spun from these modified nylon 6 blends showed surface hydrophobicity. These modified polyamides or related materials may become technologically important in carpeting applications. Additional studies involving attempts at directly polymerizing ε-caprolactam via hydrolytic ring opening polymerization from functional polysiloxanes are also reported. In general, the structural integrity of these copolymers is less well defined. Certain procedures utilizing the aminopropyl polydimethylsiloxane initiated lactam oligomerization, followed by adipic acid chain extension produced interesting materials and should be further examined.