Novel bridged tetradentate fourth-subgroup metal complex, and preparation method and application thereof

A metal complex, the fourth technology, which can be applied to the compounds of Group 4/14 elements of the periodic table, titanium organic compounds, chemical instruments and methods, etc., and can solve the problems of low catalytic efficiency, limited industrial application, and deactivation.

Active Publication Date: 2020-09-29
山东京博中聚新材料有限公司
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Olefin polymerization catalyst determines the internal structure and morphology of polyolefin products. It is the core technology in the development of polyolefin industry. Its development generally goes through three stages: a). Ziegler-Natta catalyst, which is the earliest olefin polymerization catalyst , its appearance gave birth to the polyolefin industry, but this type of catalyst is heterogeneous, it is difficult to be fully activated by the co-catalyst, there are multiple active centers, the catalytic efficiency is very low, and the ash content in the product is very high, which increases the difficulty of post-processing ; b). Metallocene catalysts, such catalysts need to use a large amount of expensive cocatalysts (MAO or boron promoters) during use, and the active center is easily poisoned and deactivated, which limits its application in industrial production; c). Non-metallocene catalysts, this type of catalyst has a single active center, relatively high activity, and the central metal has strong tolerance to heteroatoms. It not only has the advantages of the previous two generations of catalysts, but also can catalyze a variety of homopolymerization and copolymerization reactions. Therefore, it has a very goo

Method used

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  • Novel bridged tetradentate fourth-subgroup metal complex, and preparation method and application thereof
  • Novel bridged tetradentate fourth-subgroup metal complex, and preparation method and application thereof
  • Novel bridged tetradentate fourth-subgroup metal complex, and preparation method and application thereof

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preparation example Construction

[0183] The present invention provides a method for preparing the novel bridged tetradentate fourth subgroup metal complex described in the above technical solution, comprising the following steps:

[0184] will have a ligand of formula b and MX 4 reaction to obtain a novel bridging tetradentate fourth subgroup metal complex with a structure of formula a;

[0185]

[0186] In the present invention, the ligand having formula b is preferably prepared according to the following method:

[0187] The compound of formula I is brominated to obtain the compound of formula II;

[0188] The compound of the formula II is mixed with KOH and chloromethyl methyl ether (CH 3 OCH 2 Cl) reaction, obtains the compound of formula III;

[0189] reacting the compound of formula III with n-butyllithium, and then reacting with the compound of formula IV to obtain the compound of formula V;

[0190] Reacting the compound of the formula V structure with a dibromo compound to obtain a ligand hav...

Embodiment 1

[0224](1). Synthesis of related compounds containing bridging group Y with rigid ring structure

[0225] ①Synthesis of 1,2-dibromomethylcyclohexane

[0226]

[0227] Under nitrogen atmosphere, will contain LiAlH 4 (300mmol) in tetrahydrofuran (200mL) was cooled to 0°C, and the tetrahydrofuran (150mL) solution containing 1,2-cyclohexanedicarboxylic acid (150mmol) was added dropwise into the above system. , then reflux for 12h, stop the reaction, cool to 0°C, carefully add ammonium chloride powder thereinto, stop when no gas is produced in the reaction flask, add 15% sodium sulfate solution (150mL), then add diethyl ether (150mL), The organic phase was separated and retained, and the aqueous phase was extracted three times with diethyl ether. The organic phases were combined, dried over anhydrous magnesium sulfate, filtered, and the solvent was removed by rotary evaporation. The obtained crude product was frozen and recrystallized in methanol (-40°C) to obtain 1, 2-Dihydrox...

Embodiment 2

[0251] On the basis of Example 1, the complexes of P1~P36 structures were further prepared:

[0252] P1:R 1 = methyl, R 2 = methyl, R 3 = Hydrogen, R 4 =phenyl, Y=carbon three straight chains, M=Zr, X=methyl;

[0253] P2:R 1 = tert-butyl, R 2 = tert-butyl, R 3 =hydrogen, R4=phenyl, Y=carbon three straight chains, M=Zr, X=methyl;

[0254] P3:R 1 =3,5-di-tert-butylphenyl, R 2 = tert-butyl, R 3 = Hydrogen, R 4 =phenyl, Y=carbon three straight chains, M=Zr, X=methyl;

[0255] P4:R 1 = 1-naphthyl, R 2 = tert-butyl, R 3 = Hydrogen, R 4 =phenyl, Y=carbon three straight chains, M=Zr, X=methyl;

[0256] P5:R 1 =9-anthracenyl, R 2 = tert-butyl, R 3 = Hydrogen, R 4 =phenyl, Y=carbon three straight chains, M=Zr, X=methyl;

[0257] P6:R 1 = carbazolyl, R 2 = tert-butyl, R 3 = Hydrogen, R 4 =phenyl, Y=carbon three straight chains, M=Zr, X=methyl;

[0258] P7:R 1 = cumyl, R 2 = tert-butyl, R 3 = Hydrogen, R 4 =phenyl, Y=carbon three straight chains, M=Zr, X=meth...

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Abstract

The invention provides a novel bridged tetradentate fourth-subgroup metal complex, and a preparation method and application thereof. The complex has a structure as shown in a formula a, has good temperature tolerance, can keep very high catalytic activity at 120 DEG C, and can be used as a main catalyst for catalyzing ethylene homopolymerization to obtain ultrahigh-molecular-weight polyethylene; the complex can catalyze a copolymerization reaction of ethylene with norbornene, 1-hexene and 1-octene and is high in activity, and a polymer product with a high co-monomer insertion rate is obtained;and the complex can catalyze propylene polymerization to obtain a polypropylene product with high isotacticity.

Description

technical field [0001] The invention belongs to the technical field of olefin polymerization catalysts, and in particular relates to a novel bridged tetradentate fourth subgroup metal complex and its preparation method and application. Background technique [0002] Polyolefin products have many advantages such as abundant raw materials, low price, convenient production and processing, and superior performance. They are the most popular resin materials at present. The polyolefin industry represents the development level of a country's petrochemical industry. An important part of the national defense strategy. Olefin polymerization catalyst determines the internal structure and morphology of polyolefin products. It is the core technology in the development of polyolefin industry. Its development generally goes through three stages: a). Ziegler-Natta catalyst, which is the earliest olefin polymerization catalyst , its appearance gave birth to the polyolefin industry, but this ...

Claims

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Application Information

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IPC IPC(8): C07F7/28C07F7/00C08F110/02C08F210/02C08F232/08C08F210/16C08F210/14C08F4/64C08F4/642
CPCC07F7/28C07F7/00C08F110/02C08F210/02C08F210/16C08F4/64193C08F4/6428C08F2500/01C08F232/08C08F210/14Y02P20/52
Inventor 李彪刘龙飞赵永臣刘振学任学斌栾波
Owner 山东京博中聚新材料有限公司
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