Polymerization of linear higher α-olefins with a modified Ziegler catalyst

Rishina, L. A.; Lalayan, S. S.; Galashina, N. M.; Perepelitsina, E. O.; Medintseva, T. I.; Kissin, Yury V.

doi:10.1134/s1560090414010096

Cited by 10 publications

(7 citation statements)

References 10 publications

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“…This finding showed that monomer length had significant effect on the polymer tacticity until the certain amount of C 8 ; after that by more increase in monomer size, tacticity would decrease, evidently. This trend had also been obtained by Kissin et al They have reported a tacticity amount of 73%, 76%, and 64%, for PH, PO, and PD polymers, respectively.…”

Section: Resultssupporting

confidence: 82%

Effects of monomer length on α‐olefins polymerization using a conventional Ziegler–Natta catalyst

et al. 2018

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α-Olefin monomers with different lengths from C 4 to C 10 were polymerized via a conventional Ziegler-Natta catalyst. It was found that activity of the catalyst decreases with increase in the monomer length as well as introduction of external donor. GPC results exhibited a steady decrease in molecular weight from poly1butene to poly1-decene; however, PDI did not show a clear trend. Based on differential scanning calorimetry and X-ray diffraction analyses, poly1-butene and poly1-decene represented crystalline structure with one and two melting points, respectively, while poly1-hexene and poly1-octene showed amorphous nature. The content of isotactic pentads increased from poly1-butene to poly1-octene, with maximum value of mmmm = 76%, but decreased again in poly1-decene. Calculated ΔE re-si values showed a peak by increasing monomer length which was in line with the experimental results for isotactic content. K E Y W O R D S

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Section: Resultssupporting

confidence: 82%

Effects of monomer length on α‐olefins polymerization using a conventional Ziegler–Natta catalyst

et al. 2018

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“…Polymerization of higher alpha olefins (1‐hexene and 1‐octene) over supported titanium–magnesium catalysts (TMC) is of significant fundamental and practical interest . We previously studied the effects of cocatalyst composition and various polymerization conditions on activity, molecular weight, and molecular weight distribution (MWD) of resulting polyhexene (PH) for 1‐hexene polymerization over a titanium–magnesium catalyst of composition TiCl 4 /D 1 /MgCl 2 ‐AlR 3 /D 2 (where D 1 is dibutyl phthalate (DBP), D 2 is propyltrimethoxysilane (PTMS), and AlR 3 is an organoaluminum cocatalyst) characterized by high specificity and activity) .…”

Section: Introductionmentioning

confidence: 99%

1‐Hexene Polymerization over Supported Titanium–Magnesium Catalyst: The Effect of Composition of the Catalytic System and Polymerization Conditions on Temperature Dependence of the Polymerization Rate

Echevskaya

Захаров

Matsko

et al. 2017

Macro Reaction Engineering

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The effect of temperature on the rate of 1‐hexene polymerization over supported titanium–magnesium catalyst of composition TiCl4/D1/MgCl2 + AlR3/D2 (D1 is dibutyl phthalate, D2 is propyltrimethoxysilane, and AlR3 is an organoaluminum cocatalyst) is studied. The unusual data that the polymer rate decreases when temperature is increased from 30 to 70 °C are obtained. The 1‐hexene polymerization rate and the pattern of changes in polymerization rate with temperature depend on a combination of factors such as cocatalyst (AlEt3 or Al(i‐Bu)3) and presence/absence of hydrogen and an external donor in the reaction mixture. These factors differ in their effects on catalytic activity at different polymerization temperatures, so the temperature coefficient (Eeff) values calculated using the Arrhenius dependence of the polymerization rate on polymerization temperature vary greatly. The “normal” Arrhenius plot where polymerization rate increases with temperature is observed only for polymerization with the Al(i‐Bu)3 cocatalyst in the presence of hydrogen and without an external donor. Formation of high‐molecular‐weight polyhexene at low polymerization temperatures results in catalyst particle fragmentation, which may additionally contribute to the increase in polymerization rate as polymerization temperature is reduced.

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“…Catalysts of different compositions can be employed to produce polyhexene; among them are traditional Ziegler-Natta type catalysts, supported titanium-magnesium catalysts (TMC) [ 3 , 4 , 5 , 6 , 7 , 8 , 9 , 10 , 11 , 12 , 13 , 14 , 15 , 16 ], and homogeneous metallocomplex catalysts [ 17 , 18 , 19 , 20 ]. Kinetics of hexene-1 polymerization over Ziegler-Natta catalysts with different composition and data on the effect of catalysts’ composition, and polymerization conditions on the molecular weight and molecular weight distribution of polyhexene are presented and discussed in refs.…”

Section: Introductionmentioning

confidence: 99%

Polymerization of Hexene-1 and Propylene over Supported Titanium–Magnesium Catalyst: Comparative Data on the Polymerization Kinetics and Molecular Weight Characteristics of Polymers

2022

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Data are presented on the great differences of the kinetics of hexene-1 and propylene polymerization over the same supported titanium–magnesium catalyst, as well as molecular weight and molecular weight distribution of the polymers produced. It is found that the composition of cocatalysts (AlEt3 or Al(i-Bu)3 greatly affects the kinetics of hexene-1 polymerization and molecular weight distribution of polyhexene, contrary to data obtained at propylene polymerization. The presence of hydrogen at hexene-1 polymerization leads to a much higher increase of activity in comparison with propylene polymerization. Possible reasons for these differences are discussed on the basis of experimental results.

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Polymerization of linear higher α-olefins with a modified Ziegler catalyst

Cited by 10 publications

References 10 publications

Effects of monomer length on α‐olefins polymerization using a conventional Ziegler–Natta catalyst

Effects of monomer length on α‐olefins polymerization using a conventional Ziegler–Natta catalyst

1‐Hexene Polymerization over Supported Titanium–Magnesium Catalyst: The Effect of Composition of the Catalytic System and Polymerization Conditions on Temperature Dependence of the Polymerization Rate

Polymerization of Hexene-1 and Propylene over Supported Titanium–Magnesium Catalyst: Comparative Data on the Polymerization Kinetics and Molecular Weight Characteristics of Polymers

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