Polymerization of olefins catalyzed by a dichloride complex of titanium with a dioxolane dicarbonate ligand: The promoting effect of LiCl and MgCl2

Rishina, L. A.; Galashina, N. M.; Гагиева, С. Ч.; Тuskaev, Vladislav А.; Kissin, Yury V.

doi:10.1134/s1560090411020072

Cited by 17 publications

(26 citation statements)

References 17 publications

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“…As we discussed earlier, efficiency of AlR 2 Cl/MgBu 2 combinations as cocatalysts for Ti(O R ) 4 most probably depends on two factors. First, AlEt 2 Cl and MgBu 2 rapidly interact with the generation of highly dispersed MgCl 2 with the Lewis‐acidic surface:

{MgBu}_{2} + {2 AlEt}_{2} Cl \to true[{MgCl}_{2} true] + {2 AlEt}_{2} Bu

…”

Section: Resultsmentioning

confidence: 99%

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A new route to atactic polypropylene: The second life of premetallocene homogeneous polymerization catalyst

Kissin

Rishina

Lalayan

et al. 2015

J. Polym. Sci. Part A: Polym. Chem.

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Amorphous atactic polypropylene (PP) with an average molecular weight of 50,000-100,000 is produced by polymerizing propylene with a ternary Ti(Oiso-Pr) 4 -AlEt 2 Cl/MgBu 2 catalyst at 30-50. Main advantages of this catalyst compared with other catalysts capable of nearly exclusively producing atactic PP (such as some heterogeneous Ziegler-Natta, metallocene and postmetallocene catalysts) are high activity, low cost and the ease of use: the catalyst is prepared in situ from three commercially available compounds readily soluble in aliphatic and aromatic hydrocarbons.

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{MgBu}_{2} + {2 AlEt}_{2} Cl \to true[{MgCl}_{2} true] + {2 AlEt}_{2} Bu

…”

Section: Resultsmentioning

confidence: 99%

“…The reaction conditions are given in Table . Experimental details of the polymerization reactions were described earlier . The catalyst components were added to the reactor in a sequence: AlEt 2 Cl (or Al i ‐Bu 2 Cl), MgBu 2 , Ti(O iso ‐Pr) 4 .…”

Section: Methodsmentioning

confidence: 99%

A new route to atactic polypropylene: The second life of premetallocene homogeneous polymerization catalyst

Kissin

Rishina

Lalayan

et al. 2015

J. Polym. Sci. Part A: Polym. Chem.

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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%

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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“…Propylene polymerization was conducted via complete filling of the reactor with a liquid monomer as described in [9].…”

Section: Polymerizationmentioning

confidence: 99%

A novel efficient Ti(O-iso-C3H7)4-based olefin polymerization catalyst system

et al. 2016

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The polymerization of ethylene and propylene and the copolymerization of ethylene and hexene-1 with a Ti(O-iso-Pr) 4 -AlR 2 Cl/MgBu 2 catalyst system have been studied. The advantages of this system over metallocene and postmetallocene catalysts are high activity, low cost, and ease of synthesis. The resulting polymers and copolymers are characterized by a broad molecular-mass distribution, which reflects the heterogeneity of the active sites with respect to kinetic parameters. As a consequence, the ethylene/hexene-1 copolymers exhibit compositional heterogeneity. The active sites of the system produce copolymers with a pronounced tendency toward alternation of monomer units. The propylene polymerization product is mostly amorphous atactic polypropylene.

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Polymerization of olefins catalyzed by a dichloride complex of titanium with a dioxolane dicarbonate ligand: The promoting effect of LiCl and MgCl2

Cited by 17 publications

References 17 publications

A new route to atactic polypropylene: The second life of premetallocene homogeneous polymerization catalyst

A new route to atactic polypropylene: The second life of premetallocene homogeneous polymerization catalyst

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

A novel efficient Ti(O-iso-C3H7)4-based olefin polymerization catalyst system

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Polymerization of olefins catalyzed by a dichloride complex of titanium with a dioxolane dicarbonate ligand: The promoting effect of LiCl and MgCl2

Cited by 17 publications

References 17 publications

A new route to atactic polypropylene: The second life of premetallocene homogeneous polymerization catalyst

A new route to atactic polypropylene: The second life of premetallocene homogeneous polymerization catalyst

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

A novel efficient Ti(O-iso-C3H7)4-based olefin polymerization catalyst system

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