Homo-polymerization of α-Olefins and Co-polymerization of Higher α-Olefins with Ethylene in the Presence of

Abstract: Cyclopentadienyl-titanium complexes containing –OC6H4X ligands (X = Cl, CH3) activated with methylaluminoxane (MAO) were used in the homo-polymerization of ethylene, propylene, 1-butene, 1-pentene, 1-butene, and 1-hexene, and also in copolymerization of ethylene with the α-olefins mentioned. The-X substituents exhibit different electron donor-acceptor properties, which is described by Hammett’s factor (σ). The chlorine atom is electron acceptor, while the methyl group is electron donor. These catalysts allow the preparation of polyethylene in a good yield. Propylene in the presence of the catalysts mentioned dimerizes and oligomerizes to trimers and tetramers at 25 o C under normal pressure. If the propylene pressure was increased to 7 atmospheres, CpTiCl2(OC6H4CH3)/MAO catalyst at 25 o C gave mixtures with different contents of propylene dimers, trimers and tetramers. At 70 o C we obtained only propylene trimer. Using the catalysts with a-OC6H4Cl ligand we obtained atactic polymers with Mw 182,000 g/mol (at 25 o C) and 100,000 g/mol (at 70 o C). The superior activity of the CpTiCl2(OC6H4Cl)/MAO catalyst used in polymerization of propylene prompted us to check its activity in polymerization of higher α-olefins (1-butene, 1-pentene, 1-hexene

Use of fluidized bed reactor in 2,6-dimethylphenol synthesis

Prace badawcze dotyczyły otrzymywania i przetestowania katalizatorów do syntezy 2,6-dimetylofenolu, które mogłyby pracować jako złoże fluidalne. Zsyntezowano tlenek krzemu, na który nanoszono w różnych wariantach tlenki: żelaza(III), magnezu(II), chromu(III) i miedzi(II). Ponadto przebadano katalizator TZC-3/1 produkowany przez Grupę Azoty S.A. Tlenek krzemu z naniesionym na powierzchnię tlenkiem magnezu umożliwił prawie 100% przereagowanie fenolu w temp. 733K, przy selektywności w stosunku do 2,6-dimetylofenolu bliskiej 60%. Podobny stopień przereagowania fenolu otrzymano dla katalizatora przemysłowego TZC-3/1, ale jego selektywność względem 2,6-dimetylofenolu wynosi 90%. Wyniki eksperymentów wskazują, że najlepszym spośród badanych katalizatorów jest przemysłowy katalizator TZC-3/1 pozwalający otrzymać najlepsze wyniki w najniższej temperaturze.Research works were focused on obtaining and testing of catalysts for 2,6-dimethylphenol synthesis that could be used as fluidized bed. Silicon oxide was synthesized, on which subsequently various variants of iron (III), magnesium (II), chrome (III) and copper (II) oxides were deposited. Moreover, catalyst TZC-3/1 produced by Grupa Azoty SA was tested. Silicon oxide with deposited magnesium oxide allowed almost 100% conversion of phenol at 733K with selectivity towards 2,6-dimethylphenol equal to 60%. Similar degree of conversion for phenol was obtained for industrial catalyst TZC-3/1, but its selectivity towards 2,6-dimethylphenol was equal to 90%. Experimental results indicate that the best one among examined catalyst is the industrial catalyst TZC-3/1 that allows obtaining best results at lowest temperature

Homo-polymerization of α-Olefins and Co-polymerization of Higher α-Olefins with Ethylene in the Presence of CpTiCl2(OC6H4X-p)/MAO Catalysts (X = CH3, Cl)

Cyclopentadienyl-titanium complexes containing –OC6H4X ligands (X = Cl,CH3) activated with methylaluminoxane (MAO) were used in the homo-polymerizationof ethylene, propylene, 1-butene, 1-pentene, 1-butene, and 1-hexene, and also in co-polymerization of ethylene with the α-olefins mentioned. The -X substituents exhibitdifferent electron donor-acceptor properties, which is described by Hammett’s factor (Ã).The chlorine atom is electron acceptor, while the methyl group is electron donor. Thesecatalysts allow the preparation of polyethylene in a good yield. Propylene in the presenceof the catalysts mentioned dimerizes and oligomerizes to trimers and tetramers at 25oCunder normal pressure. If the propylene pressure was increased to 7 atmospheres,CpTiCl2(OC6H4CH3)/MAO catalyst at 25oC gave mixtures with different contents ofpropylene dimers, trimers and tetramers. At 70oC we obtained only propylene trimer.Using the catalysts with a -OC6H4Cl ligand we obtained atactic polymers with Mw182,000 g/mol (at 25oC) and 100,000 g/mol (at 70oC). The superior activity of theCpTiCl2(OC6H4Cl)/MAO catalyst used in polymerization of propylene prompted us tocheck its activity in polymerization of higher α-olefins (1-butene, 1-pentene, 1-hexene)and in co-polymerization of these olefins with ethylene. However, when homo-polymerization was carried out in the presence of this catalyst no polymers wereobtained. Gas chromatography analysis revealed the presence of dimers. The activity ofthe CpTiCl2(OC6H4Cl)/MAO catalyst in the co-polymerization of ethylene with higher α-olefins is limited by the length of the co-monomer carbon chain. Hence, the highest catalyst activities were observed in co-polymerization of ethylene with propylene (here a lower pressure of the reagents and shorter reaction time were applied to obtain catalytic activity similar to that for other co-monomers). For other co-monomers the activity of the catalyst decreases as follows: propylene >1-butene > 1-pentene >> 1-hexene. In the case of co-polymerization of ethylene with propylene, besides an increase in catalytic activity, an increase in the average molecular weight Mw of the polymer was observed. Other co- monomers used in this study caused a decrease of molecular weight. A significant increase in molecular weight distribution (Mw/Mn) evidences a great variety of polymer chains formed during the reaction