Living alpha-olefin polymerization by cationic zirconium and hafnium complexes containing chelating diamidopyridine ligands

Thesis (Ph. D.)--Massachusetts Institute of Technology, Dept. of Chemistry, 2002.Vita.Includes bibliographical references (leaves 196-199).This electronic version was submitted by the student author. The certified thesis is available in the Institute Archives and Special Collections.by Parisa Mehrkhodavandi.Ph.D

On the Mechanism of the Conversion of Methanol to 2,2,3-Trimethylbutane (Triptane) over Zinc Iodide

Methanol is converted to a mixture of hydrocarbons by reaction with zinc iodide at 200 °C with one highly branched alkane, 2,2,3-trimethylbutane (triptane), being obtained in surprisingly high selectivity. Mechanistic studies implicate a two-stage process, the first involving heterogeneously catalyzed formation of a carbon−carbon-bonded species, probably ethylene, that undergoes homogeneously catalyzed sequential cationic methylation to higher hydrocarbons. The first stage can be bypassed by addition of olefins, higher alcohols, or arenes, which act as initiators. Rationales for the particular activity of zinc iodide and for the selectivity to triptane are proposed

Solution and melt viscoelastic properties of controlled microstructure poly(lactide)

A series of controlled microstructure poly(lactide) (PLA) samples were synthesized using a novel chiral dinuclear indium catalyst capable of living polymerization of lactide. PLAs with different ratios of L- to D- monomer ratios of 100:0, 90:10, 75:25, 50:50, and 0:100 were investigated. The relationship between intrinsic viscosity and the absolute molar mass distribution of the samples obtained by light scattering gel permeation chromatography in tetrahydrofuran gives [η] = 0.014 + 0.75 Mw, a scaling law of typical coil dimensions of linear macromolecules in good solvent. The melt rheological study includes determination of zero-shear viscosity and its relationship with the molecular weight, the relaxation spectrum, and its relation with molecular weight characteristics, as well as plateau modulus and other important rheological parameters that are helpful in predicting the linear viscoelasticity of PLA. Emphasis is placed on the uniaxial melt behavior of these polymers. At low temperatures, significant strain hardening is observed, which gradually disappears with an increase in temperature and decrease of Hencky strain rate. The K-BKZ constitutive equation is used to model the experimental data. It is concluded that in spite of their linear structure, PLAs exhibit strain hardening which is not due to strain-induced crystallization, and it is solely due to the dynamics of molecular relaxation

Rheology and melt fracture of poly(lactides)

The wall slip and melt fracture behaviour of several commercial polylactides (PLAs) have been investigated. PLAs with molecular weights greater than a certain value were found to slip, with the slip velocity to increase with decrease of molecular weight. The onset of melt fracture for the high molecular weight PLAs was found to occur at around 0.2 to 0.3 MPa, depending on the geometrical characteristics of the dies. Addition of 0.5wt% of a poly(e-caprolactone) (PCL) into the PLA that exhibits melt fracture was found to be effective in eliminating and delaying the onset of melt fracture to higher shear rates