Bong Shik Kim

Morphology and Rheology on the Blends of PLA/CMPS

The rheological behaviors and morphologies of polylactide (PLA) and chemically modified plasticized starch (CMPS) blends were investigated. For this study, oscillatory shear flow measurements of the PLA, CMPS and their blends were performed. A scanning electron microscope (SEM) study was also conducted on the extracted extrudates of the blends. The morphology of the blend changed in relation to the composition: sphere-shaped CMPS disperse/continuous PLA, rod-like deformed CMPS phase/continuous PLA, a co-continuous structure with bridged CMPS long rods and PLA dispersed/continuous CMPS. The composition of the phase inversion could be estimated and closely coincided from the observed morphology experimental results. The rheological behavior of the blends, from oscillatory measurements, was found to vary in relation to the composition, and reflected the morphologies of the blends. PLA showed Newtonian flow behavior, while CMPS showed strong shear thinning behavior. The relationships between the morphology and rheological properties were observed in detail.

Copolymerization of Ethylene and Norbornene via Polymethylene Bridged Dinuclear Constrained Geometry Catalysts

The dinuclear half-sandwich CGCs (constrained geometry catalyst) with a polymethylene bridge, [Ti(η5 :η1-indenyl)SiMe2NCMe3]2(CH2)n][n = 6 (1) and 12 (2)], have been employed in the copolymerization of ethylene and norbornene (NBE). To compare the mononuclear metallocene catalysts; Ti(η5:η1-2-hexylindenyl) SiMe2NCMe3 (3), (Cp* SiMe2NCMe3)Ti (Dow CGC) (4) andansa-Et(Ind)2ZrCl2 (5), were also studied for the copolymerization of ethylene and NBE. It was found that the activity increased in the order:1 <2 <3 <5 <4, indicating that the presence of the bridge between two the CGC units contributed to depressing the polymerization activity of the CGCs. This result strongly suggests that the implication of steric disturbance due to the presence of the bridge may play a significant role in slowing the activity. Dinuclear CGCs have been found to be very efficient for the incorporation of NBE onto the polyethylene backbone. The NBE contents in the copolymers formed ranged from 10 to 42%, depending on the polymerization conditions. Strong chemical shifts were observed at δ 42.0 and 47.8 of the isotactic alternating NBE sequences, NENEN, in the copolymers with high NBE contents. In addition, a resonance at 47.1 ppm for the sequences of the isolated NBE, EENEE, was observed in the13C-NMR spectra of the copolymers with low NBE contents. The absence of signals for isotactic dyad at 48.1 and 49.1 ppm illustrated there were no isotactic or microblock (NBE-NBE) sequences in the copolymers. This result indicated that the dinuclear CGCs were effective for making randomly distributed ethylene-NBE copolymers.