Polymerization of alkenes with a post‐metallocene catalyst containing a titanium complex with an oxyquinolinyl ligand

Rishina, L. A.; Kissin, Yury V.; Lalayan, S. S.; Гагиева, С. Ч.; Тuskaev, Vladislav А.; Крашенинников, В. Г.

doi:10.1002/pola.28549

Cited by 10 publications

(9 citation statements)

References 37 publications

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“…All its components are soluble in aliphatic and aromatic hydrocarbons, but their mixing generates solid products. Interaction between Al(C 2 H 5 ) 2 Cl and Mg(C 4 H 9 ) 2 produces highly dispersed MgCl 2 crystals with the Lewis‐acidic surface:

Mg {({normalC}_{4} {normalH}_{9})}_{2} + 2 Al {({normalC}_{2} {normalH}_{5})}_{2} Cl \to ([], {MgCl}_{2}) + 2 Al {({normalC}_{2} {normalH}_{5})}_{2} ((), C_{4} H_{9})

…”

Section: Discussionmentioning

confidence: 99%

“…Another reason for the high activity of the TiCl 4 –Al(C 2 H 5 ) 2 Cl/Mg(C 4 H 9 ) 2 system can be an interaction between Al(C 2 H 5 ) 2 Cl and Mg(C 4 H 9 ) 2 , which leads to the formation of ion pairs [Mg–C 4 H 9 ] + [ A ] − and [Mg–Cl] + [ A ] − , where [ A ] − = [Al(C 2 H 5 ) 2 (C 4 H 9 ) 2 ] − or [Al(C 2 H 5 ) 2 (C 4 H 9 )Cl … Al(C 2 H 5 ) 2 (C 4 H 9 ) 2 ] − . Such ion pairs can convert Cl 3 Ti IV – R and Cl 2 Ti III – R complexes into the second type of active centers containing the Ti + – R bond, for example:

{Cl}_{3} Ti - R + {[Mg ({normalC}_{4} {normalH}_{9})]}^{+} {[A]}^{-} \to ([], {Cl}_{2} {Ti}^{+} - R) {[A]}^{-} + Mg ((), C_{4} H_{9}) Cl

…”

Section: Discussionmentioning

confidence: 99%

“…It is currently generally accepted that the most probable structures of active centers in all Ti‐based Ziegler‐Natta catalysts include cationic species containing the catalytically active Ti + –C bond . Two reasons for high activity of the ternary TiCl 4 –Al(C 2 H 5 ) 2 Cl/Mg(C 4 H 9 ) 2 system in propylene polymerization reactions can be proposed by analogy with alkene polymerization reactions with various premetallocene and postmetallocene catalysts . First, the products of reactions between TiCl 4 and either AlR 3 and AlR 2 Cl (i.e., various Ti IV and Ti III complexes 423,24 ) are adsorbed on the Lewis‐acidic MgCl 2 surface [] and form cationic species containing the Ti + –C bond:

{Cl}_{3} Ti - normalR + ([], {MgCl}_{2}) \to {[{Cl}_{2} {Ti}^{+} - R]}_{adsorb} / {false[{MgCl}_{3} false]}^{-}

{Cl}_{2} Ti - normalR + ([], {MgCl}_{2}) \to {[{ClTi}^{bold+} - R]}_{adsorb} / {[{MgCl}_{3}]}^{-}

…”

Section: Discussionmentioning

confidence: 99%

“…The explanation for efficiency of AlR 2 Cl–MgR′ 2 combinations as cocatalysts represented by eqs. is universal for many transition metal catalysts, including catalysts based on various postmetallocene complexes …”

Section: Discussionmentioning

confidence: 99%

“…Earlier we discovered that combinations of Al(C 2 H 5 ) 2 Cl and organomagnesium compounds MgR 2 , when they are used at an [Al]/[Mg] molar ratio above 2, are universal cocatalysts for all types of transition‐metal polymerization catalysts, including common heterogeneous Ziegler‐Natta catalysts, Ti(OR) 4 compounds, metallocene complexes, and various post‐metallocene complexes . In particular, the Ziegler catalyst modified with Mg(C 4 H 9 ) 2 is a highly efficient catalyst for polymerization of ethylene and for ethylene/1‐alkene copolymerization reactions …”

Section: Introductionmentioning

confidence: 99%

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Synthesis of atactic polypropylene: Propylene polymerization reactions with TiCl₄–Al(C₂H₅)₂Cl/Mg(C₄H₉)₂ catalyst

Rishina

Kissin

Lalayan

et al. 2019

J of Applied Polymer Sci

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The Ziegler catalyst, a combination of TiCl4 and Al(C2H5)2Cl, is a very poor catalyst for propylene polymerization. However, the addition of Mg(C4H9)2 to the Ziegler catalyst at a [Mg]:[Al] molar ratio < 0.5 leads to the formation of a potent catalyst system for homopolymerization of propylene. Polymers produced with the TiCl4–Al(C2H5)2Cl/Mg(C4H9)2 catalyst are mostly atactic and amorphous, their minor partially crystalline isotactic components constitute merely 5–10% of the combined polymer material. Principal advantages of the TiCl4–Al(C2H5)2Cl/Mg(C4H9)2 catalyst for the manufacture of atactic PP include high activity, low cost, and the ease of use: the catalyst is prepared in situ from three commercially available components. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019, 136, 47692.

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Mg {({normalC}_{4} {normalH}_{9})}_{2} + 2 Al {({normalC}_{2} {normalH}_{5})}_{2} Cl \to ([], {MgCl}_{2}) + 2 Al {({normalC}_{2} {normalH}_{5})}_{2} ((), C_{4} H_{9})

…”

Section: Discussionmentioning

confidence: 99%

{Cl}_{3} Ti - R + {[Mg ({normalC}_{4} {normalH}_{9})]}^{+} {[A]}^{-} \to ([], {Cl}_{2} {Ti}^{+} - R) {[A]}^{-} + Mg ((), C_{4} H_{9}) Cl

…”

Section: Discussionmentioning

confidence: 99%

{Cl}_{3} Ti - normalR + ([], {MgCl}_{2}) \to {[{Cl}_{2} {Ti}^{+} - R]}_{adsorb} / {false[{MgCl}_{3} false]}^{-}

{Cl}_{2} Ti - normalR + ([], {MgCl}_{2}) \to {[{ClTi}^{bold+} - R]}_{adsorb} / {[{MgCl}_{3}]}^{-}

…”

Section: Discussionmentioning

confidence: 99%

Section: Discussionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Synthesis of atactic polypropylene: Propylene polymerization reactions with TiCl₄–Al(C₂H₅)₂Cl/Mg(C₄H₉)₂ catalyst

Rishina

Kissin

Lalayan

et al. 2019

J of Applied Polymer Sci

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Catalyst Activation and Chain Transfer Agents in Metallocene Catalysts for Ethylene Polymerization: A Computational Investigation

Kumawat

Gupta

2021

Eur J Inorg Chem

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A density functional theory (DFT) study has been carried out to investigate the effect of various cocatalysts/chain transfer agents (such as Al(R) 3 , Mg(R) 2 , (R)Mg(Cl), Zn(R) 2 , (R)Zn(Cl), B(C 6 F 5 ) 3 , and Al(C 6 F 5 ) 3 , here, R = alkyl group) on catalyst activation and ethylene polymerization including chain transfer steps using (Cp R, R' ) 2 M(Cl) 2 (M = Zr, Hf and R, R' = alkyl group) metallocenes. Initially, the catalyst alkylation step (where one of the chlorine atoms of the catalyst is replaced by an alkyl group of the cocatalyst) has been studied using the Al(Me) 3 , Mg(Me) 2 , (Me)Mg(Cl), Zn(Me) 2 , and (Me)Zn(Cl) moieties, and it was observed that the AlMe 3 species is more effective for the alkylation step. Furthermore, a modification in the metallocene, such as (Cp R, R' ) 2 Zr(Cl) 2 , where R and R' = H, Me, Et, n-propyl, isopropyl, iso-butyl, tert-butyl, and different combinations of those, has been performed to evaluate the effect of different alkyl substituents on the alkylation process, whereby it was found that the mono-substituted metallocene favors the alkylation in comparison to bi-substituted metallocene. Moreover, a detailed fundamental understanding of the ion pair formation step was gained by incorporating various steric and electronic factors of different alkyl groups, including fluorinated alkyl group bound on the Cp ligand. These results suggest that only B(C 6 F 5 ) 3 and Al(C 6 F 5 ) 3 activators could form the ion pairs by abstracting a methyl group from the metallocene. Additionally, the ethylene polymerization has also been investigated using B(C 6 F 5 ) 3 or Al(C 6 F 5 ) 3 cocatalyst, where B(C 6 F 5 ) 3 was found to be more effective towards polymerization. Furthermore, the Al(Me) 3 , Mg(R) 2 , (Me)Mg(Cl), Zn(R) 2 , and (Me)Zn(Cl) species have been employed as chain transfer agent (CTA). It has been observed that the magnesium-and zinc-based species are more likely to behave as CTAs, and this process can be improved by changing the alkyl substituents on them. These chemical calculations shed light on catalyst alkylation and ethylene polymerization, including the chain transfer process, in metallocenes.

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Alkene polymerization reactions with catalysts based on acetylacetonate complexes of vanadium and titanium: effect of cocatalyst

Rishina

Kissin

Lalayan

et al. 2021

Polymer International

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Alkene polymerization reactions were studied with three catalyst systems containing complexes of vanadium and titanium with the acetylacetonate ligand (V(acac)3, VO(acac)2, Ti(acac)2Cl2) and a binary activator, a combination of Al(C2H5)2Cl and Mg(C4H9)2 at an [Al]:[Mg] molar ratio of ca 3. All three catalysts are highly active in ethylene homopolymerization reactions. They copolymerize ethylene and 1‐hexene to random, compositionally uniform products with 1‐hexene content of up to 20–25%. The Ti(acac)2Cl2–Al(C2H5)2Cl/Mg(C4H9)2 combination is also an effective catalyst for propylene polymerization to an essentially atactic product. Gel permeation chromatography analysis showed that all the studied M(acac)n–Al(C2H5)2Cl/Mg(C4H9)2 catalysts contain several types of active centers which differ in the average molecular weight of polymer material they produce. © 2021 Society of Industrial Chemistry.

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Polymerization of alkenes with a post‐metallocene catalyst containing a titanium complex with an oxyquinolinyl ligand

Cited by 10 publications

References 37 publications

Synthesis of atactic polypropylene: Propylene polymerization reactions with TiCl₄–Al(C₂H₅)₂Cl/Mg(C₄H₉)₂ catalyst

Synthesis of atactic polypropylene: Propylene polymerization reactions with TiCl₄–Al(C₂H₅)₂Cl/Mg(C₄H₉)₂ catalyst

Catalyst Activation and Chain Transfer Agents in Metallocene Catalysts for Ethylene Polymerization: A Computational Investigation

Alkene polymerization reactions with catalysts based on acetylacetonate complexes of vanadium and titanium: effect of cocatalyst

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Polymerization of alkenes with a post‐metallocene catalyst containing a titanium complex with an oxyquinolinyl ligand

Cited by 10 publications

References 37 publications

Synthesis of atactic polypropylene: Propylene polymerization reactions with TiCl4–Al(C2H5)2Cl/Mg(C4H9)2 catalyst

Synthesis of atactic polypropylene: Propylene polymerization reactions with TiCl4–Al(C2H5)2Cl/Mg(C4H9)2 catalyst

Catalyst Activation and Chain Transfer Agents in Metallocene Catalysts for Ethylene Polymerization: A Computational Investigation

Alkene polymerization reactions with catalysts based on acetylacetonate complexes of vanadium and titanium: effect of cocatalyst

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Synthesis of atactic polypropylene: Propylene polymerization reactions with TiCl₄–Al(C₂H₅)₂Cl/Mg(C₄H₉)₂ catalyst

Synthesis of atactic polypropylene: Propylene polymerization reactions with TiCl₄–Al(C₂H₅)₂Cl/Mg(C₄H₉)₂ catalyst