Heteroatom-containing Pi-ligand metallocene complex, preparation method thereof, catalyst system thereof and application of catalyst system

A metallocene complex and heteroatom technology, applied in the field of catalysts, can solve the problem of inability to achieve controllability of polyolefin materials

Active Publication Date: 2016-10-05
PETROCHINA CO LTD
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0011] The second object of the present invention is to provide a catalyst system with a heteroatom-containing π-ligand metallocene complex as the core component, to overcome the inability to achieve polyolefin material isotacticity at 50-90 in the prior art % Interval Controllable Defects

Method used

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  • Heteroatom-containing Pi-ligand metallocene complex, preparation method thereof, catalyst system thereof and application of catalyst system
  • Heteroatom-containing Pi-ligand metallocene complex, preparation method thereof, catalyst system thereof and application of catalyst system
  • Heteroatom-containing Pi-ligand metallocene complex, preparation method thereof, catalyst system thereof and application of catalyst system

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0188] Intermediate product a 1 Synthesis:

[0189]

[0190] The intermediate product a in the reaction formula 1 Synthesis:

[0191] Using phenylboronic acid as a substrate, the catalyst, tetrabutylammonium bromide (TBAB) and ethylene glycol are separated from the product by 3:1 PE / EA (petroleum ether / ethyl acetate), and reused (TBAB and ethylene glycol) Alcohol), the third reaction can obtain 82.2% separation yield.

[0192]

[0193] Intermediate product b 1 Synthesis:

[0194] Weigh the intermediate product a 1 Put 5mmol into a 100ml two-necked reaction flask, add 40ml of THF (tetrahydrofuran), put it in an ice-water bath to fully cool; add Red-Al dihydrobis(2-methoxyethoxy)sodium aluminate) dropwise, and use 15min After adding all the drops, react for 2 hours, warm up to room temperature, and react overnight at room temperature; prepare 10% HCl solution and add it dropwise to the reaction system, a white solid precipitates out, making the system acidic; filter ...

Embodiment 2

[0213] Z 2 The synthesis of is as follows, and other conditions are as in Example 1.

[0214]

[0215] product intermediate a 2 Synthesis:

[0216] Calculate the amount of raw materials according to the amount of 1mol product, and put it in a 2500ml two-necked reaction flask; stir for 20min under ice-water bath conditions; weigh dibromo-2-methylpropionyl bromide and anhydrous dichloromethane into the separatory funnel Slowly add dropwise in the reaction bottle; Weigh naphthalene and anhydrous dichloromethane and join in the separatory funnel, slowly dissolve in the reaction system after quickly dissolving, the color of the solution in the reaction bottle becomes yellow rapidly, and gradually becomes brownish red, Finally, add anhydrous dichloromethane to rinse the separating funnel; after reacting for 30min, take out the ice, and slowly warm the water bath to room temperature; The raw materials for the reaction, the organic phase is collected after liquid separation; the...

Embodiment 3- Embodiment 24

[0223] According to the conditions of Example 1, the structure and synthetic method of intermediate product a are as follows:

[0224]

[0225] Sequentially weigh 4-bromo-2-methyl-1-indanone (0.056g, 0.25mmol), phenylboronic acid Ar-B(OH) 2 (0.3mmol), potassium carbonate K 2 CO 3 (0.069g, 0.5mmol), PEG-400 (polyethylene glycol-400) (2g), tetrabutylammonium bromide TBAB (0.08g, 0.25mmol), plus catalyst palladium acetate Pd (OAc) 2 , heated and stirred at 110°C, the results obtained are shown in the following table.

[0226]

[0227]

[0228]

[0229]

[0230]

[0231] Synthesis of intermediate product b in the reaction formula:

[0232] Weigh 3mmol of the intermediate product a and put it into a 100ml two-necked reaction flask, add 40ml of tetrahydrofuran THF, and put it in an ice-water bath to cool fully; add red aluminum Red-Al dropwise, and add it all dropwise in 15min, react for 2h, warm up to room temperature, room temperature React overnight; prepare...

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Abstract

The invention relates to a heteroatom-containing Pi-ligand metallocene complex, a preparation method thereof, a catalyst system thereof and an application of the catalyst system. The metallocene complex has a chemical structure shown as a following chemical formula (I):, wherein, M is the third, fourth, fifth or sixth transition metal element in periodic table of elements, which comprises lanthanide and actinium series elements; X, equal to or different from each other, are selected from the group consisting of the hydrogen element, halogen, alkyl R, alkyloxy OR, mercapto SR, carboxyl OCOR, amidogen NR2, phosphino PR2, -OR.O- and OSO2CF3; n is an integer from 1 to 4, n is not equal to zero; the product of electrical numbers of n and X is equal to the charge number by reducing 2 of the central metal atom M; Q is divalent free radical; A is a Pi-ligand, and has a structure shown as the chemical formula (II):, and Z is the Pi-ligand, and Z is equal to A, or Z has the chemical structure shown as the following chemical formula.

Description

technical field [0001] The invention belongs to the field of catalysts, and in particular relates to a heteroatom-containing π-ligand metallocene complex, a catalyst system with the metallocene complex as the core component, a metallocene complex and a preparation process for the catalyst system , and the application of the catalyst system in the polymerization of α-olefins. Background technique [0002] Metal organic complexes (commonly known as metallocene complexes) formed by cyclopentadiene and its derivatives in the form of π-coordination, especially the metallocene complexes of transition metals of the third and fourth groups, when combined with When combined with appropriate activators, it has extremely high catalytic polymerization activity for olefins. A wide range of applications have been found in the catalytic polymerization of ethylene (H.G.Alte et al. Chemcal Reviews 2000, 100, 1205. Metallocene-Based Polyolefins. Preparation, Properties and Technology; Scheir...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07F7/10C07F7/00C07F7/08C08F10/00C08F4/6592C08F4/68C08F4/69C08F4/52
Inventor 辛世煊郎笑梅薛山李新乐胡泓梵孙鑫张雪芹周生远冉印李勃天朱博超贾军纪曲景平宋玉明谢亚梅母瀛高伟刘京龙
Owner PETROCHINA CO LTD
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