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2,6-diimine pyridinocycloheptane iron and cobalt complex catalyst and preparation method therefor and application thereof

A technology of complexes and catalysts, applied in iron organic compounds, nickel organic compounds, organic chemistry, etc., can solve the problems of restricting the development of basic research, poor thermal stability of complexes, and limiting the application research of metal complex catalysts

Active Publication Date: 2016-02-10
INST OF CHEM CHINESE ACAD OF SCI
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

However, as a new catalyst system, there are still some difficulties in basic research and constraints to promote industrialization
First of all, the limitation of catalyst type, there are not many catalyst systems available for screening, which restricts the development of basic research
Secondly, since the rate of chain transfer termination increases with the increase of temperature, and the thermal stability of the complex itself is poor, this will inevitably cause the activity to decrease with the increase of reaction temperature.
These have limited the application research of metal complex catalysts to a certain extent.

Method used

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  • 2,6-diimine pyridinocycloheptane iron and cobalt complex catalyst and preparation method therefor and application thereof
  • 2,6-diimine pyridinocycloheptane iron and cobalt complex catalyst and preparation method therefor and application thereof
  • 2,6-diimine pyridinocycloheptane iron and cobalt complex catalyst and preparation method therefor and application thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0092] Example 1. Preparation of (E)-N-(2-((E)-1-(2,6-diisopropylaniline) ethyl)-5,6,7,8-tetrahydrocycloheptane The synthetic method of pyridine-9-dienamine (L3, namely R=i-Pr in the formula V; R 1 = Compound of H):

[0093] 1) Add 2-chloro-5,6,7,8-tetrahydrocycloheptane pyridin-9-one (33.3g, 170mmol, formula II) and 67.7g of tributyl (1-ethyl Oxyvinyl)tin (187mmol), 1,4-dioxane 300ml, catalyst [1,1'-bis(diphenylphosphino)ferrocene]palladium dichloride 3.11g (2.5mol%), After 16 hours of reflux, the reaction was complete, and the post-treatment was separated on a silica gel column. The target product was eluted with an eluent whose ratio of eluent was ethyl acetate:petroleum ether=1:50, and 25.9 g of white solid powder was obtained, which was represented by formula III The compound was shown in a yield of 75% (melting point: 88-90°C).

[0094] 2) Add 20 mg of p-toluene to a solution of the compound (0.20 g, 1 mmol) shown in formula III and 2,6-diisopropylaniline (0.39 g, 2.2...

Embodiment 2

[0102] Example 2. Preparation of (E)-N-(2-((E)-1-(2,6-dimethylaniline) ethyl)-5,6,7,8-tetrahydrocycloheptapyridine -the synthetic method of 9-dienamine (L1, namely R=Me among the formula V; R 1 = Compound of H):

[0103] Use the same method as in Example 1 (only 2,6-diisopropylaniline in step 6 described in Example 1 is replaced by 2,6-dimethylaniline) to obtain 0.21g of yellow oil, which is The dienyl amine pyridine ligand compound L1 belonging to formula V (wherein, R is a methyl group, R 1 For hydrogen), the yield is 51.3%.

[0104] The structural confirmation data are as follows:

[0105] 1 HNMR (400MHz, CD 2 Cl 2 ): δ8.36(d, J=8.0Hz, 1H, L1-Py-H), 8.25(d, J=8.0Hz, 1H, L1'-Py-H), 7.64(d, J=8.0Hz, 1H,L1-Py-H),7.52(d,J=8.0Hz,1H,L1'-Py-H),7.04(m,4H,L1-Ar-H),6.98(d,J=7.8Hz, 4H, L1'-Ar-H), 6.90(t, J=7.6Hz, 2H, L1-Ar-H), 6.85(t, J=7.8Hz, 2H, L1'-Ar-H), 6.41(s ,1H,L1'-NH-),4.59(t,J=6.8Hz,1H,L1'-CH=),2.92(t,J=6.0Hz,2H,L1-CH 2 -),2.76(t,J=6.4Hz,2H,L1'-CH 2 -),2.34(s,3H,L...

Embodiment 3

[0110] Example 3. Preparation of (E)-N-(2-((E)-1-(2,6-diethylaniline) ethyl)-5,6,7,8-tetrahydrocycloheptanepyridine -the synthetic method of 9-dienamine (L2, namely R=Et among the formula V; R 1 = Compound of H):

[0111] Use the same method as in Example 1 (only replace 2,6-diisopropylaniline with 2,6-diethylaniline in step 6 described in Example 1) to obtain 0.20 g of a yellow solid, which is the attribution The dienyl amine pyridine ligand compound L2 of formula V (wherein, R is ethyl, R 1 is hydrogen), the yield is 42.9% (melting point: 130-131°C).

[0112] The structural confirmation data are as follows:

[0113] The schematic diagram of the crystal structure is as figure 2 shown. It can be seen from the figure that the angle between the pyridine ring and the aniline is approximately perpendicular.

[0114] 1 HNMR (400MHz, CD 2 Cl 2): δ8.30(d, J=8.0Hz, 1H, L2-Py-H), 8.20(d, J=8.0Hz, 1H, L2'-Py-H), 7.85(d, J=8.0Hz, 1H, L2-Py-H), 7.61(d, J=8.0Hz, 1H, L2'-Py-H), 7...

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Abstract

The invention discloses a 2,6-diimine pyridinocycloheptane iron and cobalt complex catalyst and a preparation method therefor and an application thereof. The structural formula of the complex is represented by a formula I, wherein R is selected from at least one of methyl, ethyl or isopropyl; R1 is selected from methyl or hydrogen; M represents Fe or Co. The preparation method comprises the step of: carrying out a reaction on a ligand as shown in a formula V and FeCl2.4H2O or CoCl2 to obtain a complex represented by the formula I under a room temperature condition. The invention designs and synthesizes a complex which contains a 2,6-dienamine pyridine ligand and iron and cobalt metals. The series of complexes, under the action of a co-catalyst methylaluminoxane or modified methylaluminoxane, can better catalyze vinyl polymerization to obtain a polymer with high molecular weight. Meanwhile, the activity of the catalyst is further high, and the highest activities respectively reach 1.56*10<7> / mol(Fe) / h and 2.09*10<7>g / mol(Co) / h. The catalyst has a wide industrial prospect. The formula is as shown in the description, wherein Ar represents a formula shown in the description.

Description

technical field [0001] The invention belongs to the field of complex catalysis, and in particular relates to a preparation method of a 2,6-diiminopyridocycloheptane iron and cobalt complex and its application in catalyzing ethylene polymerization. Background technique [0002] The polyolefin industry has an output value of billions of dollars in the world every year. Although this industry has been developed for nearly a hundred years and has a large scale and is relatively mature, polyolefin is still the fastest growing field in the polymer industry. Polyolefin has many advantages such as excellent material performance, processing performance, safety and non-toxicity. Through copolymerization and modification, it can be developed to have high heat resistance, high impact resistance, high transparency, low heat sealing temperature, magnetic conductivity, thermal conductivity, Materials with high shielding properties are widely used in agriculture, industry, military, medical...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07F15/03C07F15/04C07D221/04C08F10/02C08F4/70
CPCY02P20/52
Inventor 黄放邢其锋杨文泓胡信全孙文华
Owner INST OF CHEM CHINESE ACAD OF SCI
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