Halogen-containing compound and its use, catalyst composition, ethylene oligomerization method, ethylene trimerization method, and ethylene tetramerization method

Abstract

The invention discloses a halogen-containing compound represented by formula I and its use as a ligand for an ethylene oligomerization catalyst composition, wherein Z is a divalent linking group represented by formula II or formula III; the invention also discloses An ethylene oligomerization catalyst composition containing the halogen-containing compound and an ethylene oligomerization method, an ethylene trimerization method and an ethylene tetramerization method using the catalyst composition are disclosed. The fluorine-containing polymer according to the present invention is used as a ligand for the catalyst for ethylene oligomerization, and can effectively improve the catalytic performance of the catalyst system, especially showing significantly improved activity and selectivity in the ethylene oligomerization reaction. The catalyst composition according to the invention has good industrial application prospect and economic value.

Description

technical field

[0001] The present invention relates to a halogen-containing compound, and the present invention also relates to the use of said halogen-containing compound as a ligand of an ethylene oligomerization catalyst composition; the present invention further relates to an ethylene oligomerization catalyst composition and an ethylene compound using said catalyst composition Oligomerization method, ethylene trimerization method and ethylene tetramerization method. Background technique

[0002] Ethylene oligomerization is one of the most important reactions in the olefin polymerization industry. Through oligomerization, cheap small molecule olefins can be converted into products with high added value, such as 1-octene and 1-hexene. As important organic raw materials and chemical intermediates, 1-octene and 1-hexene are mainly used in the production of high-quality polyethylene (PE). The linear low-density polyethylene (LLDPE) produced by the copolymerization of 1-hexe...

Examples

preparation example 1

[0116] Preparation Example 1 is used to prepare halogen-containing compound I 1 .

[0117]

[0118] Halogen compound I 1 The preparation method refers to the above reaction formula, and the specific steps are as follows.

[0119] Under nitrogen protection, add n-butyllithium (11mmol) (6.6mL n-butyllithium hexane solution, the concentration of n-butyllithium is 1.6M) to 15mL of dry tetrahydrofuran in a reaction flask, cool to 0°C, stir 2.2 g (10 mmol) of difluorophenylphosphine chloride was added, and then acetylene (11 mmol) was added. After stirring for 0.5 h, the temperature was raised to room temperature (25° C., the same below), and stirring was continued for 2 h. Catalytic amounts of CuI and cesium carbonate were added, followed by 2.2 g (10 mmol) of difluorophenylphosphine chloride, the temperature was raised to 90° C. and stirred at 90° C. for 4 h. After the reaction, cool to room temperature, filter the reaction mixture, vacuum the filtrate to dryness, and pass t...

preparation example 2

[0123] Preparation example 2 is used to prepare halogen-containing compound I 2 .

[0124] In this preparation example, the halogen-containing compound was prepared by the same method as in preparation example 1, except that difluorophenylphosphine chloride was replaced by dichlorophenylphosphine chloride. The prepared compound is carried out nuclear magnetic resonance analysis, confirms that the prepared compound is the compound shown in formula I, wherein, R 1 , R 2 , R 3 and R 4 Both chlorine, R 5 and R 6 Both are hydrogen.

[0125] h 1 NMR (400MHz, CDCl 3 ): δ=7.30-7.00 (m, 16H), 5.18 (s, 2H).

preparation example 3

[0127] Preparation example 3 is used to prepare halogen-containing compound I 3 .

[0128]

[0129] Halogen compound I 3 The preparation method refers to the above reaction formula, and the specific steps are as follows.

[0130] Under nitrogen protection, tert-butylacetylene (11mmol) and 15mL of dry tetrahydrofuran were added to a 50mL reaction flask, and then n-butyllithium (11mmol) (6.6mL of n-butyllithium in hexane was added dropwise at 0°C, n The concentration of butyllithium is 1.6M). After the dropwise addition, continue stirring at 0°C for 30 min, then add 2.2 g (10 mmol) of difluorophenylphosphine chloride dropwise, after the dropwise addition, raise the temperature to room temperature (25°C, the same below), and continue stirring for 2 h. Catalytic amounts of CuI and cesium carbonate were added, followed by 2.2 g (10 mmol) of difluorophenylphosphine chloride, the temperature was raised to 90° C. and stirred at 90° C. for 4 h. After the reaction, cool to room t...

technical field

[0001] The present invention relates to a halogen-containing compound, and the present invention also relates to the use of said halogen-containing compound as a ligand of an ethylene oligomerization catalyst composition; the present invention further relates to an ethylene oligomerization catalyst composition and an ethylene compound using said catalyst composition Oligomerization method, ethylene trimerization method and ethylene tetramerization method. Background technique

[0002] Ethylene oligomerization is one of the most important reactions in the olefin polymerization industry. Through oligomerization, cheap small molecule olefins can be converted into products with high added value, such as 1-octene and 1-hexene. As important organic raw materials and chemical intermediates, 1-octene and 1-hexene are mainly used in the production of high-quality polyethylene (PE). The linear low-density polyethylene (LLDPE) produced by the copolymerization of 1-hexe...

Examples

preparation example 1

[0116] Preparation Example 1 is used to prepare halogen-containing compound I 1 .

[0117]

[0118] Halogen compound I 1 The preparation method refers to the above reaction formula, and the specific steps are as follows.

[0119] Under nitrogen protection, add n-butyllithium (11mmol) (6.6mL n-butyllithium hexane solution, the concentration of n-butyllithium is 1.6M) to 15mL of dry tetrahydrofuran in a reaction flask, cool to 0°C, stir 2.2 g (10 mmol) of difluorophenylphosphine chloride was added, and then acetylene (11 mmol) was added. After stirring for 0.5 h, the temperature was raised to room temperature (25° C., the same below), and stirring was continued for 2 h. Catalytic amounts of CuI and cesium carbonate were added, followed by 2.2 g (10 mmol) of difluorophenylphosphine chloride, the temperature was raised to 90° C. and stirred at 90° C. for 4 h. After the reaction, cool to room temperature, filter the reaction mixture, vacuum the filtrate to dryness, and pass t...

preparation example 2

[0123] Preparation example 2 is used to prepare halogen-containing compound I 2 .

[0124] In this preparation example, the halogen-containing compound was prepared by the same method as in preparation example 1, except that difluorophenylphosphine chloride was replaced by dichlorophenylphosphine chloride. The prepared compound is carried out nuclear magnetic resonance analysis, confirms that the prepared compound is the compound shown in formula I, wherein, R 1 , R 2 , R 3 and R 4 Both chlorine, R 5 and R 6 Both are hydrogen.

[0125] h 1 NMR (400MHz, CDCl 3 ): δ=7.30-7.00 (m, 16H), 5.18 (s, 2H).

preparation example 3

[0127] Preparation example 3 is used to prepare halogen-containing compound I 3 .

[0128]

[0129] Halogen compound I 3 The preparation method refers to the above reaction formula, and the specific steps are as follows.

[0130] Under nitrogen protection, tert-butylacetylene (11mmol) and 15mL of dry tetrahydrofuran were added to a 50mL reaction flask, and then n-butyllithium (11mmol) (6.6mL of n-butyllithium in hexane was added dropwise at 0°C, n The concentration of butyllithium is 1.6M). After the dropwise addition, continue stirring at 0°C for 30 min, then add 2.2 g (10 mmol) of difluorophenylphosphine chloride dropwise, after the dropwise addition, raise the temperature to room temperature (25°C, the same below), and continue stirring for 2 h. Catalytic amounts of CuI and cesium carbonate were added, followed by 2.2 g (10 mmol) of difluorophenylphosphine chloride, the temperature was raised to 90° C. and stirred at 90° C. for 4 h. After the reaction, cool to room t...

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