[NNNN] tetradentate ligand fourth subgroup metal complex and application thereof

A technology of metal complexes and tetradentate ligands, which can be applied to compounds of Group 4/14 elements of the periodic table, organic compounds of Group 4/14 without C-metal bonds, and titanium organic compounds, etc., which can solve the problem of low molecular weight. , the synthesis steps are cumbersome, the copolymerization ability is poor, etc., to achieve the effect of long catalytic life, high catalytic activity and good thermal stability

Active Publication Date: 2021-08-31
SHANDONG JINGBO PETROCHEM
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  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Terunori Fujita et al. reported that a type of Fujita catalyst can catalyze ethylene polymerization with high activity, but this kind of catalyst has poor thermal stability and low insertion rate for catalyzing the copolymerization of ethylene and α-olefin (Organometallics.,2011,20,4793-4799)
Jun Okuda's subject combined a series of [ONNO]-type IV main group metal complexes that can produce linear low-density polyethylene with high activity, but its molecular weight is not high, which limits its industrial application (Organometallics.,2009,28,5159 -5165)
Mu Ying's research group reported that a series of [ONNO] tetradentate zirconium complexes can catalyze ethylene polymerization with high activity to obtain high molecular weight polyethylene, but the copolymerization ability is poor
Symyx Company and Dow Company applied for a series of bridged tetraoxo fourth subgroup non-metallocene catalyst patents (US2004010103A1; WO03091262A1; US20120108770A1; WO2013090396Al) with high catalytic activity and good thermal stability, but a large amount of noble metal palladium catalyst should be used in the synthesis process. The synthesis steps are cumbersome and the synthesis cost is very high

Method used

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  • [NNNN] tetradentate ligand fourth subgroup metal complex and application thereof
  • [NNNN] tetradentate ligand fourth subgroup metal complex and application thereof
  • [NNNN] tetradentate ligand fourth subgroup metal complex and application thereof

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preparation example Construction

[0077] The invention provides a kind of preparation method of polyolefin, comprising:

[0078] Ethylene is homopolymerized in the presence of a catalyst to obtain polyolefins;

[0079] The catalyst includes a main catalyst and a co-catalyst; the main catalyst includes the novel [NNNN] tetradentate ligand fourth subgroup metal complex described in any one of the above technical solutions.

[0080] The present invention provides a kind of preparation method of polyolefin, it is characterized in that, comprises:

[0081] Copolymerize ethylene and α-olefin in the presence of a catalyst to obtain polyolefin;

[0082] The catalyst includes a main catalyst and a co-catalyst; the main catalyst includes the novel [NNNN] tetradentate ligand fourth subgroup metal complex described in any one of claims 1-4.

[0083] With a new type of [NNNN] tetradentate ligand fourth subgroup metal complex described in the present invention as an active component, it can be used to catalyze the homopol...

Embodiment 1

[0090]Under a nitrogen atmosphere, weigh N,N'-dimethyl-substituted diamine (10mmol) and KOH (20mmol), add an appropriate amount of DMF, heat to 120°C, add o-fluorobenzaldehyde (20mmol) at this temperature, Heat to reflux for 12 hours, cool to room temperature, extract with dichloromethane and water, collect the organic phase, dry over anhydrous magnesium sulfate, remove the solvent in vacuo, recrystallize from methanol, filter, and dry to obtain an intermediate product.

[0091] Under a nitrogen atmosphere, the above-obtained intermediate product (5 mmol) and the corresponding amine (10 mmol) were dissolved in 50 mL of anhydrous tetrahydrofuran, 2 g of 4A molecular sieves and two drops of formic acid were added, and the reaction was carried out at room temperature for 8 h, and then lithium aluminum hydride (15 mmol) was added. Heat to reflux for 8 hours, return to room temperature, quench the reaction with saturated ammonium chloride solution, filter, wash the filter cake with ...

Embodiment 2

[0095] On the basis of Example 1, complexes N1-N12 were further prepared:

[0096] The experimental data are as follows:

[0097] N1, yield: 0.2674g, yield: 58.3%, element analysis: measured (calculated): C: 68.09 (68.11); H: 9.20 (9.23); N: 12.24 (12.22);

[0098] N2, yield: 0.3573g, yield: 71.2%, elemental analysis: measured (calculated): C: 62.23 (62.22); H: 8.41 (8.44); N: 11.13 (11.16);

[0099] N3, yield: 0.3518g, yield: 66.4%, elemental analysis: measured (calculated): C: 63.42 (63.46); H: 8.73 (8.75); N: 0.56 (10.57);

[0100] N4, yield: 0.3957g, yield: 69.4%, elemental analysis: measured (calculated): C: 64.43 (67.44); H: 6.70 (6.72); N: 9.80 (9.83);

[0101] N5, yield: 0.3351g, yield: 56.0%, elemental analysis: measured (calculated): C: 68.27 (68.29); H: 7.05 (7.08); N: 9.35 (9.37);

[0102] N6, yield: 0.3624g, yield: 70.2%, elemental analysis: measured (calculated): C: 62.85 (62.86); H: 8.57 (8.60); N: 10.84 (10.86);

[0103] N7, yield: 0.3352g, yield: 64.5%, el...

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Abstract

The invention provides a [NNNN] tetradentate ligand fourth subgroup metal complex which has a structure as shown in a formula (I), wherein n is 2-4; R is an alkyl group of C1 to C30, an aryl group of C6 to C30 or a substituted aryl group of C6 to C30; X is halogen, a C1-C30 alkyl group, a silicon group, an amino group or a C6-C30 aryl group; and M is a fourth subgroup transition metal. The [NNNN] tetradentate ligand fourth subgroup metal complex provided by the invention has good thermal stability. In use, the catalyst has the characteristics of low usage amount of a cocatalyst, high catalytic activity, good thermal stability and long catalytic life; the catalyst can catalyze ethylene polymerization to obtain ultrahigh molecular weight polyethylene, ethylene and 1-octylene copolymerization, and the comonomer insertion rate is high.

Description

technical field [0001] The invention relates to the technical field of olefin polymerization catalysts, in particular to a novel [NNNN] tetradentate ligand fourth subgroup metal complex and its application. Background technique [0002] Polyolefin products have become the most popular resin materials due to their many advantages such as easy availability of raw materials, low price, convenient production and processing, and superior performance. In the current industrial production, polyolefin products occupy a large proportion. Both polyethylene (PE) and linear low-density polyethylene (LLDPE) are important synthetic resins with a wide range of uses. In the process of producing linear low-density polyethylene, adding unsaturated olefin comonomers with more than 3 carbon atoms to copolymerize with ethylene can reduce the density of the polymer, improve the mechanical strength and toughness of the polymer, and improve the machinability and heat resistance. performance. The...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07F7/28C07F7/00C08F110/02C08F210/16C08F4/642
CPCC07F7/003C07F7/28C08F110/02C08F210/16C08F4/64186C08F210/14Y02P20/52
Inventor 佟小波李彪刘龙飞赵永臣董全文王耀伟栾波
Owner SHANDONG JINGBO PETROCHEM
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