Study of copolymerization of ethylene with hex-1-ene on applied catalysts

Finogenova, L.T; Захаров, В. А.; Buniyat-Zade, A.A.; Букатов, Г. Д.; Plaksunov, T.K

doi:10.1016/0032-3950(80)90024-6

Cited by 28 publications

(15 citation statements)

References 4 publications

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“…1, curves 5 and 6). The increase in activity upon copolymerization on Ti‐based supported catalysts when compared with homopolymerization was noted earlier in numerous works 1, 6–10, 23, 24…”

Section: Resultssupporting

confidence: 69%

“…Rheological and physicomechanical properties of these polymers depend on their molecular‐weight characteristics, comonomer content, and short chain branching (SCB) distribution. Many publications1–12 were devoted to studying ethylene/α‐olefin copolymerization on supported Ziegler catalysts (titanium–magnesium catalysts [TMCs]) and molecular structure of the resulting copolymers. It was shown2, 6–8, 10–13 that the introduction of comonomer usually results in a decrease in molecular weight ( M w ) of the polymer.…”

Section: Introductionmentioning

confidence: 99%

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Copolymerization of ethylene with α‐olefins over supported titanium–magnesium catalysts. II. Comonomer as a chain transfer agent

Nikolaeva

Matsko

Mikenas

et al. 2012

J of Applied Polymer Sci

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The data on the effect of comonomer (propylene and 1‐hexene) on molecular weight (Mw), molecular weight distribution (MWD), and content of terminal double bonds were obtained for ethylene/α‐olefin copolymers produced over a supported titanium–magnesium catalyst (TMC) upon polymerization in the absence of hydrogen. The experimental data on the effect of comonomer concentration on Mw of polymers were used to calculate the ratios between the effective rate constants of chain transfer with monomer and the propagation rate constant. It was shown that the effective rate constant of chain transfer with monomers increases in the row of monomers: ethylene < 1‐hexene < propylene. Meanwhile, the data on the effect of copolymers on content of terminal double bonds of various types demonstrate that different reactions of chain transfer with comonomer may simultaneously occur during copolymerization. It results in simultaneous formation of terminal vinylidene and trans‐vinylene bonds. Therefore, the calculated rate constants of chain transfer with comonomer are complex values, which include the rate constants of chain transfer with comonomer occurring via different mechanisms. The data on MWD, short chain branching (SCB) and terminal double bonds content of different types were obtained by molecular weight fractionation of copolymers followed by the analysis of narrow fractions. The analysis of the data on MWDs of SCB and terminal double bonds shows that active sites of the TMC are considerably heterogeneous with respect to the rates of different chain transfer reactions with monomers. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012

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Section: Resultssupporting

confidence: 69%

Section: Introductionmentioning

confidence: 99%

Copolymerization of ethylene with α‐olefins over supported titanium–magnesium catalysts. II. Comonomer as a chain transfer agent

Nikolaeva

Matsko

Mikenas

et al. 2012

J of Applied Polymer Sci

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“…The comonomer causes the chain to fold more often and creates these thinner lamellas which show a lower melting point with a corresponding decrease in crystallinity. A drop in molecular weight is also seen while there is normally an increase in activity following an increase in comonomer incorporation 1–4. A bending of the density and melting point curves in a comonomer test polymerization series is also witnessed 5–8.…”

Section: Introductionmentioning

confidence: 92%

Chemical composition distribution study in ethylene/1‐hexene copolymerization to produce LLDPE material using MgCl₂‐TiCl₄‐based Ziegler‐Natta catalysts

Garoff

Mannonen

Väänänen

et al. 2009

J of Applied Polymer Sci

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The characteristic features of LLDPE polymerization with ZN catalyst are the time drift effect during polymerization and the bending effect when trying to decrease density of the copolymer by adding more comonomer to the polymerization. The time drift in LLDPE polymerization is revealed by a constant decrease of comonomer incorporation during polymerization time. The bending is revealed by difficulties in lowering the density of LLDPE material below the density of 920 kg/ m 3 . With increasing comonomer content during polymerization, the density does not decrease, but the soluble fraction increases. To try to observe if these phenomena are connected, two types of catalysts, SiO 2 supported and precipitated MgCl 2 ZN catalysts, were studied. A short time (10 min) and an extended time (60 min) copolymerization test series where the polymerizations were performed in the presence of a gradually increasing comonomer amount. Both catalysts show a strong bending when density is presented as a function of 1-hexene both in 10-and 60-min polymerization, indicating no connection between time drift and bending. The density, melting point, and crystallinity results all indicate that both catalysts are making similar copolymer material with identical chemical composition distribution.

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“…Beta-H elimination is thought to be more easily accomplished from the tertiary carbon of an incorporated branch (Scheme 11), rather than the secondary carbon of a linear chain [29][30][31]323]. Beta-H elimination is thought to be more easily accomplished from the tertiary carbon of an incorporated branch (Scheme 11), rather than the secondary carbon of a linear chain [29][30][31]323].…”

Section: Short Chain Branchingmentioning

confidence: 99%

Review of the Phillips Chromium Catalyst for Ethylene Polymerization

McDaniel

2008

Handbook of Heterogeneous Catalysis

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The year 2001 marked the 50th anniversary of the discovery of the Phillips chromium catalyst, from which today's worldwide high‐density polyethylene industry sprang. Appropriately, during that year the discoverers of this catalyst system, J. Paul Hogan and Robert L. Banks, were inducted into the National Inventors Hall of Fame, in Akron, OH, to join other distinguished inventors spanning two centuries who have shaped our world. This chapter reviews our understanding of the chemistry associated with that catalyst system, which is used globally to produce perhaps half of the world's high‐density polyethylene, and it provides examples of how that chemistry is exploited commercially.

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Study of copolymerization of ethylene with hex-1-ene on applied catalysts

Cited by 28 publications

References 4 publications

Copolymerization of ethylene with α‐olefins over supported titanium–magnesium catalysts. II. Comonomer as a chain transfer agent

Copolymerization of ethylene with α‐olefins over supported titanium–magnesium catalysts. II. Comonomer as a chain transfer agent

Chemical composition distribution study in ethylene/1‐hexene copolymerization to produce LLDPE material using MgCl₂‐TiCl₄‐based Ziegler‐Natta catalysts

Review of the Phillips Chromium Catalyst for Ethylene Polymerization

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Study of copolymerization of ethylene with hex-1-ene on applied catalysts

Cited by 28 publications

References 4 publications

Copolymerization of ethylene with α‐olefins over supported titanium–magnesium catalysts. II. Comonomer as a chain transfer agent

Copolymerization of ethylene with α‐olefins over supported titanium–magnesium catalysts. II. Comonomer as a chain transfer agent

Chemical composition distribution study in ethylene/1‐hexene copolymerization to produce LLDPE material using MgCl2‐TiCl4‐based Ziegler‐Natta catalysts

Review of the Phillips Chromium Catalyst for Ethylene Polymerization

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Chemical composition distribution study in ethylene/1‐hexene copolymerization to produce LLDPE material using MgCl₂‐TiCl₄‐based Ziegler‐Natta catalysts