CATALYTIC CONVERSION OF ETHYLENE ON SYSTEMS BASED ON THRICHLOROTRIS-(TETRAHYDROFURANATE)CHROMIUM(III) WITH SOS-TYPE LIGANDS IN COMBINATION WITH VARIOUS ORGANOALUMINUM COCATALYSTS

This work presents the results of studying the behavior of catalytic systems formed on the basis of trichlorotris-(tetrahydrofuranate)chromium(III) in the presence of sulfur-containing tridentate SOS-type ligands and activated by various organoaluminum compounds. In the formation of catalytic systems, the following compounds were used: SOS-type ligands - bis-(2-methylthioethyl) ether, bis-(2-ethylthioethyl) ether and bis-(2-phenylthioethyl) ether, organoaluminum compounds - triethylaluminum, triisobutylaluminum, tributylaluminum and methylaluminoxane. In the course of test experiments aimed at choosing an activator at a temperature of 40 °C and an ethylene pressure of 2 MPa, the best results were obtained for triethylaluminum. Therefore, further experiments on the catalytic conversion of ethylene were carried out only with this activator. To study the effect of the reaction temperature and ethylene pressure in the reaction zone, catalytic systems of the trichlorotris-(tetrahydrofuranate)chromium(III)/ligand/triethylaluminum composition were studied in the temperature range from 40 to 80 °C and an ethylene pressure of 2 - 3 MPa with a molar ratio of components Cr : L : AlEt3 = 1 : 1 : 20. As a result of studies, it was shown that in all cases when using tridentate ligands of the SOS type, the catalytic systems formed by us showed a tendency not only to polymerization, but also to oligomerization of ethylene. The best results in the field of ethylene oligomerization into hexenes were shown by the system of the composition trichlorotris-(tetrahydrofuranate)chromium(III) / bis-(2-methylthioethyl) ether/triethylaluminum, in which the content of the hexene fraction is 54 - 55 wt.%, while the selectivity to hexene-1 reaches 88 - 89%.

Preparation of ultrahigh molecular weight ethylene/1-octene block copolymers using ethylene pressure pulse feeding policies

Ultrahigh molecular weight ethylene/1-octene block copolymers were prepared from ethylene pressure pulse feeding policies in living coordination polymerization.

Ethylene Oligomerization by Ni(II) Complex Based on Peptide

A kind of peptide based Ni (II) complexes (general formula [ZN=C(An)-C(An)=NZ](NiBr2)2, Z=(4-NHR-3,5-C6H2(CH3)2)2CH(4-C6H5), R=dipeptide, An=acenaphthenequinone) has been synthesized. Ethylene oligomerizations were carried out by using those complexes in combination with ethyl aluminium sesquichloride (EAS) and produced olefin . The effects of important parameters such as temperature and EAS concentration. on the catalytic activity and the distribution of resulting oligomer were investigated. under the conditions of employing toluene as solvent, a reaction temperature of 50°C and an ethylene pressure of 1.0 MPa..

Correlation of Polymerization Conditions with Thermal and Mechanical Properties of Polyethylenes Made with Ziegler-Natta Catalysts

In this study, the synthesis of polyethylenes has been carried out with titanium-magnesium supported Ziegler-Natta catalysts in laboratory-scale reactors. A correlation of different polymerization conditions with thermal and mechanical properties of polyethylenes has been established. It is seen that there is lowering of molecular weight (Mw), polymer yield, and catalyst activity at high hydrogen pressure and high temperature. The Mw, polymer yield, and catalyst activity are improved with the increase in ethylene pressure. Dynamic mechanical analysis (DMA) results show that the increase in temperature and hydrogen pressure decreases storage modulus. The samples with higher Mw showed high activation energy. The melting point decreases with the increase in hydrogen pressure but increases slightly with the increase in ethylene pressure. It is seen that the increase in reaction temperature, ethylene pressure, and hydrogen pressure leads to an increase in crystallinity. The tensile modulus increases with the increase in hydrogen pressure and can be correlated with the crystallinity of polymer. The Mw has a major influence on the flow activation energy and tensile strength. But the other mechanical and thermal properties depend on Mw as well as other parameters.

Effect of Polymerization Conditions on Thermal and Mechanical Properties of Ethylene/1-Butene Copolymer Made with Ziegler-Natta Catalysts

The effect of polymerization conditions on thermal and mechanical properties of ethylene/1-butene copolymers synthesized through titanium-magnesium-supported Ziegler-Natta catalysts was studied. The increase in hydrogen pressure leads to a decrease in molecular weight (MW), storage modulus, and melting temperature. However, it yields an increase in molecular weight distribution (MWD),tan⁡δ, % crystallinity, tensile modulus, yield stress, and strain at break. The effects of ethylene pressure and polymerization temperature on the copolymer MW, MWD and thermal and mechanical properties have been investigated. However, the impacts of ethylene pressure and polymerization temperature on copolymer modulus, tensile strength, % crystallinity, crystallization peak temperature, yield stress, strain at break, and yield strain are marginal. The hydrogen pressure plays a major role in controlling the copolymer properties because it acts as an efficient chain transfer agent during polymerization reaction. The MW is the key parameter that influences flow activation energy. However, the other mechanical, dynamic mechanical, and thermal properties not only depend on MW but are also influenced by other parameters.

Copolymerization of Ethylene/Diene with Different Metallocene Catalysts

Copolymerizations of ethylene and 1,7-octadiene were carried out employing homogeneous catalysts Cp2ZrCl2, Ph2C(Flu,Cp)ZrCl2 and Et(Ind)2ZrCl2, and methylaluminoxane as cocatalyst. The polymerization characteristics, such as catalytic activity, polymerization rate, copolymer composition, and thermal properties were examined in relation to the catalyst type. Different comonomer concentrations were employed, and the reaction time was varied, ranging from 1 h up to 4 h, at 90°C and at 0.5 bar ethylene pressure. The results showed that the catalyst Cp2ZrCl2 was more efficient than Et(Ind)2ZrCl2 in the preparation of high diene content ethylene/1,7-octadiene copolymers. On the other hand, Et(Ind)2ZrCl2 and Ph2C(Flu,Cp)2ZrCl2 catalysts produced low insaturation content but possibly formed cyclic structures and crosslinking.