Thermodynamics of Titanium and Vanadium Reduction in Non-Aqueous Environment Calculated at Various Levels of Theory

Reduction of titanium and vanadium compounds is a process accompanying the activation of coordinative olefin polymerization catalysts. Four density functional theory (DFT) functionals, coupled cluster with single, double, and perturbative triple excitations method CCSD­(T) as well as complete active-space second-order perturbation theory method CASPT2 with a complete active-space self-consistent field CASSCF reference wave function were applied to investigate the thermodynamics of titanium and vanadium reduction. The performance of these theoretical methods was assessed and compared with experimental values. The calculations indicate that vanadium­(IV) chloride is more easily reduced by trimethylaluminum than the corresponding titanium compound; the energies of reaction calculated at the CCSD­(T) level are equal −57.21 and −33.10 kcal/mol, respectively. The calculations deal with the redox reactions of metal chlorides in the gas phase, rather than solvated ions in the aqueous solution. This approach may be more appropriate for olefin polymerization, usually carried out in nonpolar solvents

Impact of Organoaluminum Compounds on Phenoxyimine Ligands in Coordinative Olefin Polymerization. A Theoretical Study

The reduction of the phenoxyimine moiety in three individual speciesnamely free ligand, aluminum complex, and titanium complexwith aluminum alkyls and aluminum hydride has been studied by means of DFT. It was demonstrated that the free phenoxyimine ligand in an equimolar mixture with trimethylaluminum does not undergo reduction. Instead, experimentally observed formation of the six-membered cyclic aluminum–phenoxyimine complex, useful in the ring-opening polymerization of lactones, takes place as the kinetically and thermodynamically favored process. However, it is anticipated that a 2-fold excess of the aluminum compound, especially aluminum hydride, acting on the resulting cyclic complex can convert the imine to the aluminum-subsituted amine functionality easily with an energetic barrier of approximately 10 kcal/mol. Finally, the propensity of the imine moiety in the titanium-based precursor of the coordinative olefin polymerization toward reduction with organoaluminum compounds is revealed and the mechanism of this reaction is also suggested

Activity and Thermal Stability of Cobalt(II)-Based Olefin Polymerization Catalysts Adorned with Sterically Hindered Dibenzocycloheptyl Groups

Five examples of unsymmetrical 2-(2,4-bis(dibenzocycloheptyl)-6-methylphenyl- imino)ethyl)-6-(1-(arylyimino)ethyl)pyridine derivatives (aryl = 2,6-Me2C6H3 in L1; 2,6-Et2C6H3 in L2; 2,6-i-Pr2C6H3 in L3; 2,4,6-Me3C6H2 in L4 and 2,6-Et2-4-MeC6H2 in L5) were prepared and characterized. Treatment with CoCl2 offered the corresponding cobalt precatalysts Co1−Co5, which were characterized by FT-IR and NMR spectroscopy as well as elemental analysis. The molecular structures of Co3 and Co4 determined by single crystal X-ray diffraction revealed distorted square pyramidal geometries with τ5 values of 0.052−0.215. Activated with either MAO or MMAO, the precatalysts displayed high activities in ethylene polymerization, where Co1 with the least bulky substituents exhibited a peak activity of 1.00 × 107 g PE mol−1 (Co) h−1 at 60 °C. With MAO as a cocatalyst, the activity was reduced only by one order of magnitude at 90 °C, which implies thermally stable active sites. The polymerization product was highly linear polyethylene with vinyl end groups. Co3 with the most sterically hindered active sites was capable of generating polyethylene of high molecular weight, reaching 6.46 × 105 g mol−1. Furthermore, high melting point and unimodal molecular weight distribution were observed in the resulting polyethylene. It must be stressed that the thermal stability of the catalyst and the molecular weight of the obtained polyethylene attain the highest values reported for the unsymmetrical 2,6-bis(imino)pyridylcobalt (II) chloride precatalysts

Characterization of a Double Metal Cyanide (DMC)-Type Catalyst in the Polyoxypropylation Process: Effects of Catalyst Concentration

The alkaline catalysts commonly applied to alkoxylation are characterized by a limited spectrum of activity caused by an irreversible termination of the polyether chains. The presented results show that double metal cyanide (DMC) catalysts reduce or eliminate the aforementioned adverse rearrangement of hydroxyl groups. Moreover, DMC catalysts indicate high activity at low concentrations (ppm range), as expressed by high polymerization rates. It was demonstrated that decreased concentrations of DMC catalyst irreversibly influence its reactivity and the dispersity of the obtained products, as exemplified by the production and determination of selected polyoxypropylenediols at different concentrations of the catalyst. Because of their unique advantages, the DMC catalysts are a very attractive alternative to conventional alkaline catalysts for the polyaddition of oxiranes. The phenomenon was discussed and explained by an alteration of reaction rate coefficients at subsequent polyaddition stages