New catalytic systems based on fluorine-containing titanium(iv) alkoxides for the synthesis of ultrahigh-molecular-weight polyethylene and olefin elastomers

The catalytic activity of the systems based on titanium(iv) alkoxides (Ti(OPrⁱ)₄, Ti(OPrⁱ)₂(OCH(CF₃)₂)₂, and Ti(OCH(CF₃)₂)₄) and mixtures of alkylaluminum chlorides (Et₂AlCl or Et₃Al₂Cl₃) with dibutylmagnesium in ethylene polymerization and ethylene copolymerization with propylene and 5-ethylidene-2-norbornene was studied. Ultrahigh-molecular-weight polyethylene with the molecular weight reaching 4.9 · 10⁶ Da was found to be formed in the homopolymerization reaction, whereas copolymerization gives ter-copolymers containing propylene (up to 35 mol.%) and 5-ethylidene-2-norbornene (4.3 mol.%) units.

     

Syntheses of chiral fused 4,5-diazafluorene–bis(nopinane) derivatives

1. Download : Download high-res image (122KB)
2. Download : Download full-size image

     

Cyclometallated 1,2,3-triazol-5-ylidene iridium(III) complexes: synthesis,structure, and photoluminescence properties

1. Download high-res image (67KB)
2. Download full-size image

     

α-Diphenylphosphino-N-(pyrazin-2-yl)glycine as a ligand in Ni-catalyzed ethylene oligomerization

1. Download : Download high-res image (40KB)
2. Download : Download full-size image

     

Binuclear copper(II) complex with 2-imidazolylbenzothiazole and bridged chloride ligands

1. Download : Download high-res image (81KB)
2. Download : Download full-size image

     

DFT B3LYP/6-311+G* calculation study of a new nonclassical mechanism of electrophilic functionalization of aromatic C–H bond via aryl cation formation

1. Download : Download high-res image (84KB)
2. Download : Download full-size image

     

Trimetallic NiCoM catalysts (M = Mn,Fe, Cu) for methane conversion into synthesis gas

1. Download high-res image (195KB)
2. Download full-size image

     

Highly porous polymeric sponges for oil sorption

1. Download high-res image (129KB)
2. Download full-size image

     

Predicting polycyclic aromatic hydrocarbon formation with an automatically generated mechanism for acetylene pyrolysis

Using Reaction Mechanism Generator (RMG), we have automatically constructed a detailed mechanism for acetylene pyrolysis, which predicts formation of polycyclic aromatic hydrocarbons (PAHs) up to pyrene. To improve the data available for formation pathways from naphthalene to pyrene, new high‐pressure limit reaction rate coefficients and species thermochemistry were calculated using a combination of electronic structure data from the literature and new quantum calculations. Pressure‐dependent kinetics for the CH potential energy surface calculated by Zádor et al. were incorporated to ensure accurate pathways for acetylene initiation reactions. After adding these new data into the RMG database, a pressure‐dependent mechanism was generated in a single RMG simulation which captures chemistry from C to C. In general, the RMG‐generated model accurately predicts major species profiles in comparison to plug‐flow reactor data from the literature. The primary shortcoming of the model is that formation of anthracene, phenanthrene, and pyrene are underpredicted, and PAHs beyond pyrene are not captured. Reaction path analysis was performed for the RMG model to identify key pathways. Notable conclusions include the importance of accounting for the acetone impurity in acetylene in accurately predicting formation of odd‐carbon species, the remarkably low contribution of acetylene dimerization to vinylacetylene or diacetylene, and the dominance of the hydrogen abstraction CH addition (HACA) mechanism in the formation pathways to all PAH species in the model. This work demonstrates the improved ability of RMG to model PAH formation, while highlighting the need for more kinetics data for elementary reaction pathways to larger PAHs.