Chromium pyridinediimide complexes, methods for their preparation and use for the preparation of polyolefins

A technology of complexes and ligand compounds, applied in the field of polyolefin catalysts, can solve the problems of poor thermal stability of late transition metal complexes, reduced catalyst activity, complex catalytic products and the like

Active Publication Date: 2022-04-08
INST OF CHEM CHINESE ACAD OF SCI
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

For example, the thermal stability of the late transition metal complex itself is poor, which easily causes the activity of the catalyst to decrease with the increase of the reaction temperature; the polymer molecular weight distribution obtained by the catalyst system is wide, and the catalytic product is complex, except polymer oligomers

Method used

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  • Chromium pyridinediimide complexes, methods for their preparation and use for the preparation of polyolefins
  • Chromium pyridinediimide complexes, methods for their preparation and use for the preparation of polyolefins
  • Chromium pyridinediimide complexes, methods for their preparation and use for the preparation of polyolefins

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0091] Example 1. Preparation of Compound IA (2-acetyl-6-(1-(2,4-bis(benzhydryl)-6-chloro-anilino) ethyl)pyridine)

[0092] Weigh 4.00g (24.5mmol) of 2,6-diacetylpyridine, 11.27g (24.5mmol) of 2,4-bis(benzhydryl)-6-chloro-aniline and add it to the reaction flask, Add about 150 mL of toluene, and then add a catalytic amount (20%) of p-toluenesulfonic acid in the reaction system. After 10 h of stirring at reflux temperature, the reaction mixture was filtered under heating, and all volatiles were evaporated under reduced pressure. Then, the obtained crude product was subjected to column chromatography through a basic alumina column, and was eluted with a mixed solvent of petroleum ether and ethyl acetate as an eluent (25 / 1), and the solvent was removed to obtain 3.39 g of a light yellow powder , namely compound IA, yield: 22%.

[0093]

[0094] The structural confirmation data are as follows:

[0095] FTIR (cm -1 ):3025(w), 2928(m), 1699(ν(C=O), s), 1658(ν(C=N), s), 1581(m...

Embodiment 2

[0099] Example 2. Ligand L1 (2-(1-(2,4-bis(benzhydryl)-6-chloro-anilino)ethyl)-6-(1-(2,6-dimethyl - the preparation of anilino) ethyl) pyridine)

[0100] Weigh 2.00g (3.19mmol) of compound IA and catalytic equivalent p-toluenesulfonic acid (0.638mmol) into 40mL of toluene solvent, heat and stir to reflux, then add 0.42g (3.50mmol) 2,6-dimethyl Aniline was transferred to the reaction flask, and the reaction mixture was heated to reflux for 10h. Cool to room temperature and evaporate volatiles in vacuo. Then, the obtained unprocessed residual solid was subjected to column chromatography (using a mixed solvent of petroleum ether and ethyl acetate 200:1 (v / v) as eluent) to elute through a basic alumina column, and the solvent was removed. 0.23 g of light yellow powder was obtained, namely ligand L1, yield: 20%.

[0101]

[0102] The structural confirmation data are as follows:

[0103] FTIR (cm -1 ):3028(w), 2937(w), 1643(ν(C=N), s), 1569(w), 1496(w), 1453(s), 1365(s), 132...

Embodiment 3

[0106] Example 3. Ligand L2 (2-(1-(2,4-bis(benzhydryl)-6-chloro-anilino)ethyl)-6-(1-(2,6-diethyl) - the preparation of anilino) ethyl) pyridine)

[0107] Weigh 2.00g (3.19mmol) of compound IA and catalytic equivalent p-toluenesulfonic acid (20%) into 40mL of toluene solvent, heat and stir to reflux, then add 0.52g (3.50mmol) 2,6-diethyl Aniline was transferred to the reaction flask, and the reaction mixture was heated to reflux for 10h. Cool to room temperature and evaporate volatiles in vacuo. Then, the obtained unprocessed residual solid was subjected to column chromatography (using a mixed solvent of petroleum ether and ethyl acetate 200:1 (v / v) as eluent) to elute through a basic alumina column, and the solvent was removed. 0.20 g of light yellow powder was obtained, namely ligand L2, yield: 18%.

[0108]

[0109] The structural confirmation data are as follows:

[0110] FTIR (cm -1 ):3024(w), 2930(w), 1639(ν(C=N), s), 1567(w), 1493(w), 1449(s), 1365(s), 1326(w), 1...

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Abstract

The application discloses a class of highly thermally stable diimine pyridine ligand compounds and chromium complexes that can be used to prepare saturated linear polyethylene. This type of complex contains electron-withdrawing substituent and bulky substituent benzhydryl, has a single catalytic active center, has high catalytic activity, and the molecular weight distribution of the obtained catalytic product is narrow and evenly distributed. In addition, the catalytic system also has the advantages of high thermal stability and low cost, and has broad application prospects. Also disclosed are the preparation method of the ligand compound and its chromium complex, and the use of the chromium complex for catalyzing olefin polymerization, especially ethylene polymerization.

Description

technical field [0001] The invention relates to the technical field of polyolefin catalysts, in particular to a pyridinediimine chromium complex, a preparation method thereof and an application for preparing polyolefins. Background technique [0002] The use of chromium as a catalyst metal center has a long and illustrious record in the history of olefin polymerization. Since Hogan and Phillips Petroleum Company discovered that chromium oxide (CrO 3 / SiO 2 ) can be used as a highly active polymerization catalyst for the formation of high-density polyethylene (HDPE), research in this field has continued to this day. Amazingly, this heterogeneous Phillips process was licensed in less than 4 years and is now used to produce 40-50% of the world's HDPE. In the process of exploring the reaction mechanism and active species of heterogeneous chromium-based catalysts, many types of homogeneous catalysts have been discovered. Some catalysts themselves have been shown to be highly ...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07F11/00C07D213/53C08F10/00C08F110/02C08F4/78C08F4/622
CPCC07F11/005C07D213/53C08F10/00C08F110/02C07B2200/00C08F4/62089C08F4/78Y02P20/52
Inventor 孙文华巴德拉尔·贡苏克张秋月马艳平
Owner INST OF CHEM CHINESE ACAD OF SCI
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