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Racemo selective metallation process

A racemization and metallization technology, applied in organic chemistry methods, chemical instruments and methods, metallocenes, etc., can solve problems such as inconsistent effects

Inactive Publication Date: 2016-02-24
EXXONMOBIL CHEM PAT INC
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0005] Nifant'ev et al. used tert-butylamide as a directing agent for substituted bis-indenyl and indenyl (indacenyl) compounds, however the effect was inconsistent, especially for 2-methyl, 4-phenyl substitution For indene, see Nifant'ev, I.E. et al., OrganoMetallics, 2012, 31, 4340)

Method used

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  • Racemo selective metallation process
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Examples

Experimental program
Comparison scheme
Effect test

Embodiment approach

[0285] E1. A method comprising:

[0286] Contacting the deprotonated bridged bis(indenyl) compound with a racemic directing metallation reagent to form a product mixture enriched in the bridged bis(indenyl) relative to any formed meso isomer base) racemic isomers of metallocene transition metal compounds,

[0287] wherein said racemic-directing metallation reagent is represented by the following formula:

[0288] m d x e Y f Z g (preferably M * x 2 Y 2 Z 2 , where M * for Group 4 metals),

[0289] Wherein M, X, Y and Z are defined as follows, d is the coordination number of metal M and is 4, 5 or 6, e is 2, 3, 4 or 5, f is 1, 2, 3 or 4 and g is 0, 1 or 2, where e+f=d;

[0290] Wherein the bis(indenyl) metallocene transition metal compound is represented by the following formula:

[0291]

[0292] wherein M is a metal of group 4, 5 or 6 of the periodic table;

[0293] Where A is a divalent group, including C 1 -C 20 A hydrocarbyl group, a functional group com...

Embodiment 1

[0379] The deprotonated bridged bis(4- (o-tolyl)-2-methylindenyl) compound. At this point, the reaction mixture was cooled to -75°C. The deprotonated bridged bis(4-(o-tolyl)-2-methylindenyl) compound was then mixed with a stoichiometrically equivalent amount of ZrCl 2 (O-t-Bu) 2 (thf) 2 Contact (see Njua, E.Y. et al., ZrCl in Inorg.Chem., 2010,49,2163 2 (O-t-Bu) 2 (thf) 2 The preparation method of), ZrCl 2 (O-t-Bu) 2 (thf) 2 Introduced into the reaction mixture as a solid. The product mixture was warmed to room temperature (25°C) while stirring overnight. After concentration, filtration and drying, the crude product was obtained. The crude product was slurried in ether and the bridged bis(4-(o-tolyl)-2-methylindenyl)metallocene product was isolated as a yellow solid after filtration. The product, dimethylsilylbis[4-(o-methylphenyl)-2-methylindenyl]Zr(O-t-Bu) 2 , as the pure racemic isomer; by 1 HNMR did not observe the meso isomer.

Embodiment 2

[0383] Dimethylsilylbis[4-(phenyl)-2-methylindenyl]Zr(O-t-Bu) 2 The catalyst precursor is used to polymerize ethylene and hexene. This precursor was prepared according to the general procedure in Example 1 and approximately 3:1 rac, meso isomers were obtained. Afterwards, the precursor was purified by washing with ether and then recrystallized from a dichloromethane / pentane solvent mixture.

[0384] A 30 wt% solution of MAO in toluene (Albemarle; 0.7951 g; 4.112 mmol) was dissolved in 1.5 mL of toluene; the solution was stirred for 15 minutes. To this solution was added the catalyst precursor (29.9 mg; 0.0415 mmol) as a solid, and the residue was washed with 0.5 mL of toluene. The reaction mixture was stirred for 20 minutes. To the reaction mixture was added 1.0404 g of Silica-948 (Grace), which had been previously calcined at 600°C. The wet mixture was stirred with a spatula for 10 minutes, then dried under vacuum. 15 mL of hexene and 0.1 mL of tris(n-octyl)aluminum were...

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Abstract

This invention relates to racemic bridged bis(indenyl)metallocene transition metal compounds, rac-directing metallation reagents and a process to produce the racemic bridged bis(indenyl)metallocene transition metal compounds using the rac-directing metallation regents.

Description

[0001] Inventor: Glen E. Alliger [0002] Priority: This application claims priority and benefit from USSN 61 / 870,989 filed on August 28, 2013 and EP Application No.: 13196241.7 filed on December 9, 2013. field of invention [0003] The present invention relates to racemic bis(indenyl)metallocene transition metal compounds, their preparation and use. Background of the invention [0004] The synthesis of bridged bis(indenyl)metallocenes is challenging. Deprotonation of the pro-ligand followed by the introduction of a metal halide, typically the tetrachloride of a Group 4 metal, usually results in two isomers of the product, racemic (rac) and meso. The meso form is generally considered to be undesirable since its polymerization activity is significantly reduced relative to the racemic isomer. Furthermore, rac-dimethylsilyl-bridged bis(indenyl)metallocenes are particularly advantageous because of their ability to catalyze the formation of isotactic polypropylene. Therefore, ...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07F7/00C07F7/02C07B55/00C07F17/00
CPCC07F17/00C08F4/65912C08F4/65916C08F110/06C08F210/16C08F210/14C08F4/65927
Inventor G·E·阿里戈尔
Owner EXXONMOBIL CHEM PAT INC
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