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Limited geometric configuration metallocene catalyst as well as preparation method and application thereof

A technology of metallocene catalysts and geometric configurations, applied in metallocenes, chemical instruments and methods, organic chemistry, etc., can solve the problems of no breakthrough in the performance of catalytic polymerization polymers, little difference in CGC structure, etc., and achieve industrial cost Effects of low cost, strong electron-withdrawing property, and high monomer insertion rate

Active Publication Date: 2021-03-26
PETROCHINA CO LTD
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

It has been nearly 30 years since the first CGC was synthesized. A series of CGCs have been synthesized, but most of the CGCs have little structural difference, and there has been no breakthrough in the performance of polymers that catalyze polymerization. Patent protection of constrained geometry catalysts, our country is subject to many restrictions in the production of polyolefin products such as low density polyethylene (LLDPE) and POE, so it is very meaningful to develop constrained geometry catalysts with novel structures

Method used

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  • Limited geometric configuration metallocene catalyst as well as preparation method and application thereof
  • Limited geometric configuration metallocene catalyst as well as preparation method and application thereof
  • Limited geometric configuration metallocene catalyst as well as preparation method and application thereof

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preparation example Construction

[0048] The present invention also provides a preparation method of a constrained geometry metallocene catalyst, the preparation method comprising the steps of:

[0049] Step 1, react formula II 2-pyrrole carboxaldehyde or its derivatives with indene to prepare formula III nitrogen-containing fulvene, R 1 , R 2 and R 3 independently selected from H, CH 3 -, saturated or double bond containing straight or branched chain C 2 -C 10 One of the hydrocarbon groups;

[0050] Step 2, reducing the nitrogen-containing fulvene of formula III to generate a ligand of formula IV containing pyrrole N heterocycle; and

[0051] Step 3, the ligand of formula IV containing pyrrole N heterocycle and Ti[N(R 4 ) 2 ] 4 A complex reaction occurs to generate a metallocene catalyst of formula Ⅰ, R 4 C is a straight or branched chain 1 -C 5 alkyl;

[0052]

[0053] Specifically, step 1 is: dissolving formula II 2-pyrrole carboxaldehyde or its derivatives and indene in an organic solvent in...

Embodiment 1

[0066] Complex 1 [(η 5 -C 9 h 6 )CH 2 (α-C 4 h 3 N)]Ti(NMe 2 ) 2 Synthesis

[0067] (1) fulvene (C 9 h 6 )CH(α-C 4 h 3 NH) preparation

[0068]

[0069]In a 200mL Schlenk bottle, 2-pyrrole carboxaldehyde (4g, 42mmol) and freshly distilled indene (12.3g, 106mmol) were dissolved in 40mL of methanol, and tetrahydropyrrole (6g, 84mmol) was slowly added dropwise under an ice-water bath. During the process, it can be seen that the solution gradually changes from light yellow to bright yellow, indicating that the reaction has started. After the dropwise addition, the solution was naturally raised to room temperature and stirred for 90 minutes. Add 50mL of distilled water to quench in an ice-water bath, add glacial acetic acid (5g, 84mmol) to adjust the pH to 7, add 20mL of diethyl ether, separate the liquid with a separatory funnel, take the upper organic phase, and extract the aqueous phase three times with diethyl ether (30mL× 3), combine the organic phases, then wa...

Embodiment 2

[0080] Complex 1 catalyzes the homogeneous polymerization of ethylene. Before the reaction, preheat the reactor in vacuum, set the temperature to 80°C, turn on the argon gas to rinse the reactor three times, then keep the temperature constant, and add materials to the glove box: Catalyst addition amount 10 μmol, toluene 100mL, MAO 6.7mL (i.e. the aluminum-titanium ratio is 1000); after feeding from the feeder, set the ethylene pressure to 0.6MPa, after 30 minutes of reaction, close the ethylene inlet valve, open the condensate to cool down, and open the reaction Take out the liner from the kettle and pour the product into a beaker, add hydrochloric acid-ethanol solution (V hydrochloric acid: V ethanol = 1:15) to terminate the reaction. The polymer was first rinsed repeatedly with hydrochloric acid-ethanol solution to dissolve the aluminum salt left over from the reaction, then washed three times with deionized water (100mL×3), and finally placed in a vacuum drying oven and drie...

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Abstract

The invention discloses a limited geometric configuration metallocene catalyst as well as a preparation method and application thereof. The preparation method comprises the steps of taking 2-pyrrole formaldehyde or a complex derivative thereof as a raw material, synthesizing fulvene with indene, preparing a ligand through lithium aluminum hydride reduction, and then obtaining a high-yield catalysttaking titanium as an active center by using an amine elimination method. The catalyst can catalyze olefin homopolymerization and copolymerization. Pyrrole N heterocycle replaces tert-butylamine to serve as an electron donor, the molecular structure of the catalyst is symmetrical, and the insertion rate of alpha-olefin in the polymer is increased. The catalyst disclosed by the invention is simplein synthetic route, easily available in raw materials and low in cost, the yield of the catalyst is greatly improved, and the catalyst has good olefin polymerization catalytic activity.

Description

technical field [0001] The invention relates to a pyrrolocene heterocyclic restricted geometry metallocene catalyst, a preparation method thereof, and a method for preparing polyolefins using the metallocene catalyst. Background technique [0002] When the bridging heteroatoms on the ligand and the metal atoms form a semi-sandwich structure bifunctional compound, they show a high ability to catalyze the polymerization of olefins under the action of MAO, which is called a constrained geometry catalyst (CGC ). Compared with other metallocene catalysts, constrained geometry catalysts are characterized by the introduction of constrained configuration substituent groups on the delocalized π-electron bonding group Cp*, so that the geometric configuration of the metal atoms in the complex is restricted, Cp*- Compared with similar complexes, the angle formed by the metal central atom-coordinating group connected to the bridging group is smaller. Therefore, the metal atom in the con...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C08F10/00C08F210/16C08F210/14C08F110/02C08F4/6592C07F17/00
CPCC08F10/00C08F210/16C08F110/02C07F17/00C08F4/6592C08F210/14
Inventor 王文燕米普科马丽许胜王立娟任鹤王婷兰孙彬彬董素琴牛娜邵炉杨琦和树立李瑞赵瑞达邹恩广王华宋磊杨国兴张丽洋
Owner PETROCHINA CO LTD
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