Reactivity of Tungsten-aryloxides with Hydrosilane Cocatalysts in Olefin Metathesis

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Determination of saturates, aromatics and ethanol in Brazilian commercial gasoline with low olefin content using 1 H NMR spectroscopy

In this work, a Hydrogen Nuclear Magnetic Resonance (1H NMR) method has been developed to determine aromatics and ethanol in Brazilian commercial gasoline with low olefin content. The proposed method involves subdividing an 1H NMR spectrum into regions, each of which is assumed to be associated with a specific type of structural group (OH, CH, CH2 and CH3). The method is based on the assignment of overlapping regions of 1H NMR spectra due to the signals of naphthene (N), iso and normal paraffins (P) and ethanol (E). Each 1H NMR spectrum was divided into 8 regions and the integration was correlated to the percentage of the substances to be determined. The results of the analysis by 1H NMR were compared with analysis of GC-FID obtained with the PONA system. The proposed technique of 1H NMR was shown to be an appropriate method for this sample type.

A comparative study of hydrosilane compounds as cocatalysts in the metathesis of 1-hexene

The selectivity of I-hexene metathesis using WCI6 as catalyst was evaluated with a series of hydrosilane-compounds as cocatalysts: Ph3SiH, Ph2SiH2, PhSiH3 and polymethylhydrosiloxane (PMHS). The metathesis reaction is favored by the addition of promoters. When in the presence of WCl4(OAr)(2), OAr = 2,6-dichlorophenoxide, 2,6-difluorophenoxide, olefin metathesis occurs with good selectivity without the use of promoters. (C) 1998 Elsevier B.V. B.V. All rights reserved.

Linear low density polyethylene (LLDPE) from ethylene using Tp(Ms)NiCl (Tp(Ms) = hydridotris(3-mesitylpyrazol-1-yl)) and CP2ZrCl2 as a tandem catalyst system

Linear low density polyethylene (LLDPE) with different branching contents were prepared from ethylene, without the addition of alpha-olefin comonomer, using a combination of catalyst precursors {Tp(Ms)}NiCl (1) (Tp(Ms) = hydridotris(3-mesitylpyrazol-1-yl)) and Cp2ZrCl2 (2) activated with MAO/TMA (1:1) in toluene at 0degreesC and by varying the nickel loading mole fraction (x(Ni)). The polymerization results showed that the turnover frequencies are strongly dependent on the x(Ni) varying from 6.6 x 10(3) to 32.1 x 10(3) mol[C2H4]/mol[Zr] h. The C-13 NMR spectra of the copolymers showed that the branch contents of the polymers increase as the x(Ni) increase in the medium promoting the production of polymers with a wide range of melting point (T-m) (C) 2004 Elsevier B.V. All rights reserved.