Titanium complex containing polynitro-substituent phenoxyimine ligand, preparation method and use

Abstract

The invention discloses a titanium complex containing a polynitro-substituent phenoxyimine ligand, a preparation method and an application. Its preparation method is obtained by the reaction of phenoxyimine ligand with polynitro-substituent and titanium tetrachloride in dichloromethane solvent through coordination and dehydrochlorination, while ligand L is obtained from 4,6-di Nitro‑2‑aminophenol and 5‑nitrosalicylaldehyde are prepared in high yield through condensation reaction. The invention has the characteristics of cheap and easy-to-obtain raw materials and low preparation cost, and the prepared titanium complex C containing polynitro-substituent phenoxyimine ligands needs less activating dose when catalyzing ethylene polymerization, and can catalyze ethylene polymerization. It has the characteristics of ultra-high activity, high polymerization temperature resistance and long activity time, less cooling water consumption during polymerization reaction, moderate molecular weight distribution of catalytic polymerization products and high molecular weight of polymerization products, and has broad industrial application prospects.

Description

technical field

[0001] The invention belongs to the technical field of titanium complex catalysts containing phenoxyimine ligands. It specifically relates to a titanium complex containing polynitro-substituent phenoxyimine ligands, a preparation method and application. Background technique

[0002] The development of the ethylene industry is the main symbol to measure the development of a country's petrochemical industry. Polyethylene is currently the world's largest polymer material product. Catalysts are the core of the development of the polyethylene industry. Ziegler-Natta (Z-N) catalysts, metallocene catalysts and non-transition metallocene catalysts are the three main catalysts for ethylene polymerization.

[0003] Non-transition metallocene catalysts include early transition metal catalysts and non-late transition metal catalysts; because late transition metal complexes have a strong tendency to eliminate β-H when catalyzing ethylene polymerization; most late transit...

Examples

Embodiment 1

[0035] A titanium complex containing polynitro-substituent phenoxyimine ligands and a preparation method thereof. The titanium complex containing the polynitro-substituent phenoxyimine ligand is denoted as C, and its structural formula is:

[0036]

[0037] Among them: "------" represents a coordination bond.

[0038] Concrete steps of the preparation method of the titanium complex C containing the polynitro substituent phenoxyimine ligand are:

[0039] Step 1, preparation of ligand L

[0040] The structural formula of ligand L is:

[0041]

[0042] Preparation of Ligand L: Dissolve 10 mmol of 4,6-dinitro-2-aminophenol in 100 mL of tetrahydrofuran, then add 10 mmol of 5-nitrosalicylaldehyde, and then add 0.25 mL of formic acid to obtain reaction system I. The reaction system I was stirred at 50° C. for 10 h, and cooled at 10° C. to precipitate a solid. Then recrystallized in a mixed solvent of tetrahydrofuran and ethanol, then filtered under reduced pressure, and dri...

Embodiment 2

[0053] A use of a titanium complex C containing a polynitro-substituent phenoxyimine ligand, the titanium complex C is used to catalyze ethylene polymerization, and the specific steps are:

[0054] Step 1. Under the protection of an argon atmosphere, add 100 mL of toluene to the reaction kettle, and then add 1.0 mL of toluene solution with a concentration of 4 μmol / L of titanium complex C containing polynitro-substituent phenoxyimine ligands, Then add triethylaluminum, the molar ratio of triethylaluminum to titanium complex C containing polynitro-substituent phenoxyimine ligands is 200:1 to obtain a toluene solution system of the catalyst.

[0055] Step 2: Feed ethylene into the toluene solution system of the catalyst to saturation, polymerize at 70° C. and normal pressure for 1 hour, and then terminate the polymerization with ethanol solution containing 10% hydrochloric acid.

[0056] Step 3: discharge the material from the reaction kettle, filter to obtain a crude polymer pr...

Embodiment 3、 example 4 and example 5

[0059] Change the polymerization reaction conditions (add 1.0 mL of titanium complex C with a concentration of 1 μmol / L, that is, the amount of C is 1 μmol, change the reaction temperature, change the molar ratio of the activator to the complex (Al / Ti)), other reaction conditions are the same as in Example 2 , the polymerization results of Example 3, Example 4 and Example 5 (corresponding to serial number NO.3, NO.4 and NO.5) are shown in Table 1.

[0060] Table 1. A titanium complex C containing polynitro-substituent phenoxyimine ligands 2 (1μmol) catalyzed ethylene polymerization results

[0061]

technical field

[0001] The invention belongs to the technical field of titanium complex catalysts containing phenoxyimine ligands. It specifically relates to a titanium complex containing polynitro-substituent phenoxyimine ligands, a preparation method and application. Background technique

[0002] The development of the ethylene industry is the main symbol to measure the development of a country's petrochemical industry. Polyethylene is currently the world's largest polymer material product. Catalysts are the core of the development of the polyethylene industry. Ziegler-Natta (Z-N) catalysts, metallocene catalysts and non-transition metallocene catalysts are the three main catalysts for ethylene polymerization.

[0003] Non-transition metallocene catalysts include early transition metal catalysts and non-late transition metal catalysts; because late transition metal complexes have a strong tendency to eliminate β-H when catalyzing ethylene polymerization; most late transit...

Examples

Embodiment 1

[0035] A titanium complex containing polynitro-substituent phenoxyimine ligands and a preparation method thereof. The titanium complex containing the polynitro-substituent phenoxyimine ligand is denoted as C, and its structural formula is:

[0036]

[0037] Among them: "------" represents a coordination bond.

[0038] Concrete steps of the preparation method of the titanium complex C containing the polynitro substituent phenoxyimine ligand are:

[0039] Step 1, preparation of ligand L

[0040] The structural formula of ligand L is:

[0041]

[0042] Preparation of Ligand L: Dissolve 10 mmol of 4,6-dinitro-2-aminophenol in 100 mL of tetrahydrofuran, then add 10 mmol of 5-nitrosalicylaldehyde, and then add 0.25 mL of formic acid to obtain reaction system I. The reaction system I was stirred at 50° C. for 10 h, and cooled at 10° C. to precipitate a solid. Then recrystallized in a mixed solvent of tetrahydrofuran and ethanol, then filtered under reduced pressure, and dri...

Embodiment 2

[0053] A use of a titanium complex C containing a polynitro-substituent phenoxyimine ligand, the titanium complex C is used to catalyze ethylene polymerization, and the specific steps are:

[0054] Step 1. Under the protection of an argon atmosphere, add 100 mL of toluene to the reaction kettle, and then add 1.0 mL of toluene solution with a concentration of 4 μmol / L of titanium complex C containing polynitro-substituent phenoxyimine ligands, Then add triethylaluminum, the molar ratio of triethylaluminum to titanium complex C containing polynitro-substituent phenoxyimine ligands is 200:1 to obtain a toluene solution system of the catalyst.

[0055] Step 2: Feed ethylene into the toluene solution system of the catalyst to saturation, polymerize at 70° C. and normal pressure for 1 hour, and then terminate the polymerization with ethanol solution containing 10% hydrochloric acid.

[0056] Step 3: discharge the material from the reaction kettle, filter to obtain a crude polymer pr...

Embodiment 3、 example 4 and example 5

[0059] Change the polymerization reaction conditions (add 1.0 mL of titanium complex C with a concentration of 1 μmol / L, that is, the amount of C is 1 μmol, change the reaction temperature, change the molar ratio of the activator to the complex (Al / Ti)), other reaction conditions are the same as in Example 2 , the polymerization results of Example 3, Example 4 and Example 5 (corresponding to serial number NO.3, NO.4 and NO.5) are shown in Table 1.

[0060] Table 1. A titanium complex C containing polynitro-substituent phenoxyimine ligands 2 (1μmol) catalyzed ethylene polymerization results

[0061]

Images