JP2003012682A - Zirconium compound, its production method and its use - Google Patents

Abstract

(57) Abstract: A novel metallocene zirconium compound having a racemic structure used as a highly active olefin polymerization catalyst component, a method for producing the same, a highly active olefin polymerization catalyst component, and an efficient olefin polymer. To provide uses of zirconium compounds for efficient production. SOLUTION: Racemic-ethylenebis (1-indenyl)
Zirconium diphenoxide. A method for producing racemic-ethylenebis (1-indenyl) zirconium diphenoxide using racemic-ethylenebis (1-indenyl) zirconium dichloride as a raw material. An olefin polymerization catalyst component comprising racemic-ethylenebis (1-indenyl) zirconium diphenoxide. Use of racemic-ethylenebis (1-indenyl) zirconium diphenoxide as a catalyst component in olefin homopolymerization or copolymerization of multiple olefins.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel metallocene-based zirconium compound used as a catalyst component for olefin polymerization, a method for producing the same, and its use.

[0002]

BACKGROUND OF THE INVENTION A racemic metallocene zirconium compound useful as a catalyst component for olefin polymerization is disclosed in European Patent Application EP
Although the publication No. 0834514 discloses a production example of a compound having a zirconium-amide bond or a zirconium-chloride bond, it does not disclose a production example of a compound having a zirconium-phenoxide bond. The object of the present invention is to provide a novel racemic metallocene-based zirconium compound used as a highly active olefin polymerization catalyst component, a method for producing the same, a highly active olefin polymerization catalyst component, and an efficient production of an olefin polymer. The purpose of the present invention is to provide a use of the zirconium compound.

[0003]

The present invention is directed to racemic-ethylenebis (1-indenyl) zirconium diphenoxide and racemic-ethylenebis (1-indenyl).
The present invention relates to a method for producing racemic-ethylenebis (1-indenyl) zirconium diphenoxide using zirconium dihalide as a raw material. Further, the present invention relates to a catalyst component for olefin polymerization consisting of racemic-ethylenebis (1-indenyl) zirconium diphenoxide, wherein racemic-ethylenebis as a catalyst component in homopolymerization of olefins or copolymerization of a plurality of olefins. It relates to the use of (1-indenyl) zirconium diphenoxide. Hereinafter, the present invention will be described in more detail.

[0004]

BEST MODE FOR CARRYING OUT THE INVENTION The racemic-ethylenebis (1-indenyl) zirconium diphenoxide of the present invention is produced by using racemic-ethylenebis (1-indenyl) zirconium dihalide as a raw material. Preferably, a racemic-ethylenebis (1-indenyl) zirconium diphenoxide is produced by reacting a compound obtained by reacting phenol with a strong base with racemic-ethylenebis (1-indenyl) zirconium dihalide. To be done.

As the racemic-ethylenebis (1-indenyl) zirconium dihalide used as a raw material, racemic-ethylenebis (1-indenyl) zirconium dichloride is particularly preferable. The amount of phenol used relative to racemic-ethylenebis (1-indenyl) zirconium dihalide is usually in the range of 1.8 to 2.4 mole times, preferably 2.0 to 2.2 mole times.

The strong base is preferably an organic alkali metal compound, an alkali metal hydride or an organic magnesium compound. These are easier to handle than alkali metals such as sodium metal, and can simplify the manufacturing equipment. Specific examples of the organic alkali metal compound include, for example, methyllithium, ethyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium, lithium trimethylsilylacetylide, lithium acetylide, trimethylsilylmethyllithium, vinyllithium, phenyllithium, allyl. Examples thereof include organic alkali metal compounds such as organic lithium compounds such as lithium, and examples of these compounds in which lithium is changed to sodium, potassium, rubidium, and cesium can also be exemplified. An alkali metal compound having an alkyl group having 1 to 10 carbon atoms is preferable, and a lithium, sodium or potassium compound having an alkyl group having 1 to 10 carbon atoms is more preferable.
More preferably, it is an alkyllithium compound having an alkyl group having 1 to 10 carbon atoms.

The alkali metal hydrides include hydrides of lithium, sodium, potassium, rubidium and cesium, preferably sodium hydride or potassium hydride. The organic magnesium compound is, for example, a dialkyl magnesium compound or an alkyl magnesium halide, and specifically, dimethyl magnesium, diethyl magnesium, di-n-butyl magnesium, diisopropyl magnesium, n-butyl ethyl magnesium, methyl magnesium iodide,
Methyl magnesium chloride, isopropyl magnesium halide and the like can be mentioned. Alkyl magnesium halide is preferred.

The strong base is preferably an organic alkali metal compound or an alkali metal hydride, and particularly preferably alkyl lithium. The amount of the strong base used relative to the phenol is usually 0.5 to 3 equivalents, preferably 0.7 to 1.5 equivalents. When an organic alkali metal compound, an alkali metal hydride or an organic magnesium compound is used as a strong base, the amount used is usually 0.5 to 3 mole times, preferably 0.7 to
It is in the range of 1.5 molar times.

These reactions are generally carried out in the presence of a solvent. Examples of the solvent used include benzene, toluene, aromatic hydrocarbon solvents such as xylene and mesitylene, pentane, hexane and heptane. Aliphatic hydrocarbon solvent such as octane, ether solvent such as diethyl ether, tetrahydrofuran, 1,4-dioxane, amide solvent such as hexamethylphosphoramide, dimethylformamide, acetonitrile, propionitrile, acetone, diethyl ketone Aprotic solvents such as polar solvents such as methyl isobutyl ketone and cyclohexanone, and halogen-based solvents such as dichloromethane, dichloroethane, chlorobenzene and dichlorobenzene. These solvents may be used alone or in admixture of two or more, and the amount used is racemic-
It is usually 1 to 200 times by weight, preferably 3 to 50 times the ethylene bis (1-indenyl) zirconium dihalide.
It is in the range of weight times.

The reaction temperature is usually in the range of -100 ° C to 200 ° C, preferably -40 ° C to 180 ° C. More preferably, it is in the range of 0 ° C to 160 ° C.
Most preferably, it is 40 ° C to 140 ° C.

From the reaction solution containing racemic-ethylenebis (1-indenyl) zirconium diphenoxide obtained by the above reaction, if there is a solid component by-produced by the reaction, it is filtered in the presence of a predetermined solvent. Separate and
Further, after heating and concentrating the solvent, or by allowing the solvent to stand alone in a cool and dark place in another solvent alone or in a mixed solvent, crystals of the complex are isolated. At the time of filtration, a halogenated solvent may be added to improve the filterability.
Dichloromethane is preferred as the halogenated solvent.

The racemic-ethylenebis (1-indenyl) zirconium diphenoxide of the present invention is useful as a highly active olefin polymerization catalyst component, and can be made highly active by contacting it with various activating cocatalyst components. It can form a catalyst for olefin polymerization. The racemic-ethylenebis (1-indenyl) zirconium diphenoxide of the present invention is used as a catalyst component in the homopolymerization of olefins or the copolymerization of a plurality of olefins to realize efficient production of olefin polymers.

Examples of the olefin referred to herein include ethylene and α-olefins, for example, ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-.
Examples include pentene, 1-hexene, 1-octene, 1-decene. The racemic-ethylene bis (1-indenyl) zirconium diphenoxide of the present invention is particularly preferably used as a catalyst component in the copolymerization of ethylene with an α-olefin having 4 to 8 carbon atoms. -By using it as a catalyst component for gas phase polymerization in the copolymerization with butene, its excellent performance can be greatly enjoyed.

[0014]

The present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto. The measured value of each item in the examples was measured by the following method.

(1) ¹ H-NMR measurement JEOL JNM-EX270 was used. The CDCl ₃ used as a deuterated solvent, was measured at room temperature.

(2) The content of the repeating unit derived from α-olefin in the copolymer was measured by using an infrared spectrophotometer (FT-IR7300, manufactured by JASCO Corporation) to obtain the characteristic absorption of ethylene and α-olefin. The number of short chain branches per 1000 carbon atoms (SC
Represented as B).

(3) Intrinsic viscosity = [η]: Measured in a tetralin solution at 135 ° C. using an Ubbelohde viscometer (unit: dl / g).

(4) Melt flow rate = MFR: JI
According to the method defined in SK7210-1995, 1
It is a melt flow rate value measured at a load of 21.18 N (2.16 kg) at 90 ° C. (unit: g / 10 minutes).

(5) Swell ratio = SR: Strand diameter obtained during MFR measurement is 2.095 m which is the inner diameter of the die.
It is a value divided by m.

(6) Melt flow rate ratio = MFRR:
According to the method specified in JIS K7210-1995, 190 ° C, load 211.82N (21.60kg)
The melt flow rate value measured by
It is a value divided by the melt flow rate value (MFR) measured by N (2.16 kg). For the above melt flow rate measurement, 1000 pp of antioxidant was previously prepared.
A polymer compounded with m was used.

(7) Elemental analysis: Zn: A sample was placed in an aqueous solution of sulfuric acid (1M), and then ultrasonic waves were applied to extract metal components. The obtained liquid portion was quantified by ICP emission spectrometry. F: The combustion gas generated by burning the sample in a flask filled with oxygen was treated with an aqueous sodium hydroxide solution (1
0%), and the obtained aqueous solution was quantified using the ion electrode method.

Example 1 (1) Production of racemic-ethylenebis (1-indenyl) zirconium diphenoxide In a 2 liter four-necked flask substituted with argon, 13.9 g (148 mmol) of phenol and 6 toluene were added.
00 ml was added and the mixture was stirred. After cooling to 5 ° C, n
BuLi hexane solution (1.6 mol / liter) 9
2.3 ml (148 mmol) was gradually added dropwise. The contents became a white slurry. Racemic-ethylenebis (1-indenyl) zirconium dichloride 28.2
After gradually adding g (67.3 mmol), toluene
100 ml was added. The contents became an orange slurry. The mixture was stirred under reflux conditions for 3 hours. The contents became a yellow slurry. A white solid had precipitated. Upon standing overnight, a white solid had settled down. The supernatant clear yellow solution was separated with a syringe into a flask separately purged with argon. Further, 500 ml of dichloromethane was added to the precipitated white solid slurry, which was filtered through Celite.
Filterability was improved by adding dichloromethane. The filtrate was combined with the above clear yellow clear solution.
Upon concentration, a yellow solid precipitated. After concentrating to about 100 ml and leaving it in the refrigerator overnight, a yellow solid was separated.
23.4 g of racemic-ethylenebis (1-indenyl) zirconium diphenoxide was obtained as the first crystal. When hexane was added to the filtrate, a yellow solid was further precipitated. This was separated to obtain 2.7 g of a second crystal. The total yield together with the first crystal was 26.1 g (48.9 mmol).
Yield 73%. ¹ H-NMR: δ 7.86 (d, 2H), 6.97-
7.30 (m, 10H), 6.74 (m, 2H), 6.
30 (m, 4H), 6.22 (d, 2H), 6.10
(D, 2H)

[Embodiment 2] (1) Add a 5 liter four-necked flask filled with nitrogen with a TE
2 liters of trahydrofuran, hexa of diethyl zinc
Solution (2M) 1.35 liters (2.7 mol)
And cooled to -50 ° C. To this, pentafluorophene
251.5 g (1.37 mol) of the novola tetrahydrate
Drop the solution dissolved in 390 ml of lofran in 25 minutes.
Defeated After dripping, gradually raise the temperature to room temperature and 3:00
Stirring was performed. Then, heat to 45 ° C and stir for 1 hour
did. Reduce the temperature to 20 ° C with an ice bath, and ₂O 37.7
2 g (2.09 mol) was added dropwise over 1.4 hours. That
As a result, it was divided into a yellow transparent liquid material and a yellow gel material. drop
After the bottom is finished, stir for 2 hours and heat to 40 ° C.
The mixture was further stirred for 1 hour. Let stand overnight at room temperature
After that, 72% by weight of the yellow transparent liquid material and a yellow gel
Place all of the items in separate flasks that have been purged with nitrogen.
After removing the volatile components by distillation,
Drying was carried out at 8 ° C for 8 hours. After that, from yellow transparent liquid
Dissolved in 3 liters of tetrahydrofuran.
5 liters containing solid matter derived from yellow gel.
Transferred to a tor flask. Let stand for 69 hours at room temperature
After that, vacuum drying was performed at 120 ° C. for 8 hours. as a result,
374 g of a solid product was obtained.

(2) Synthesis of component (A) In a 5-liter four-necked flask purged with nitrogen, 374 g of the solid product synthesized in (1) above and 3 liters of tetrahydrofuran were placed and stirred. Silica heat-treated at 300 ° C. under a nitrogen stream (Silopol 948, manufactured by Devison; pore volume = 1.61 m)
1 / g; specific surface area = 296 m ² / g) 282 g was added. After heating to 40 ° C. and stirring for 2 hours, the solid component was allowed to settle, and the upper layer slurry component was removed. As a washing operation, 3 liters of tetrahydrofuran was added to this, and after stirring, the solid component was allowed to settle and the slurry component in the upper layer was removed. The above washing operation was repeated 5 times in total. After removing the liquid component with a glass filter, it was dried at 120 ° C. for 8 hours under reduced pressure to obtain 452 g of component (A). Elemental analysis result Zn = 2.8 m
It was mol / g and F = 3.6 mmol / g.

(3) Polymerization After drying under reduced pressure, the inside of the autoclave equipped with a stirrer and having an internal volume of 3 liters, which had been replaced with argon, was evacuated, hydrogen was added so that its partial pressure was 0.024 MPa, and butane was added to 700
50 g of g and 1-butene were charged and the temperature was raised to 70 ° C.
Then, ethylene was added so that the partial pressure would be 1.6 MPa, and the inside of the system was stabilized. As a result of gas chromatography analysis, the gas composition in the system was hydrogen = 1.10 mol.
%, 1-butene = 2.51 mol%. to this,
0.9 ml of a heptane solution of triisobutylaluminum whose concentration was adjusted to 1 mmol / ml was added. Next, 0.25 ml of a toluene solution of racemic-ethylenebis (1-indenyl) zirconium diphenoxide adjusted to a concentration of 2 μmol / ml was added, and subsequently 15.0 mg of the component (A) obtained in (2) above. Was added as a solid catalyst component. Hydrogen was added to keep the total pressure constant.
Polymerization was carried out at 70 ° C. for 60 minutes while feeding a mixed gas of 35 mol% of ethylene and hydrogen. As a result, 55 g of an olefin polymer was obtained. The polymerization activity per solid catalyst component was 3700 g / g solid catalyst component / hour. The obtained olefin polymer is SCB
= 16.1, MFR = 2.1, MFRR = 74, SR =
It was 1.33 and [(eta)] = 1.15.

[Comparative Example 1] (1) Polymerization After drying under reduced pressure, the inside of an autoclave equipped with a stirrer and having an internal volume of 3 liters, which had been replaced with argon, was evacuated, and hydrogen was added so that the partial pressure thereof became 0.024 MPa. To 700
50 g of g and 1-butene were charged and the temperature was raised to 70 ° C.
Then, ethylene was added so that the partial pressure would be 1.6 MPa, and the inside of the system was stabilized. As a result of gas chromatography analysis, the gas composition in the system was hydrogen = 1.00 mol
%, 1-butene = 2.11 mol%. to this,
0.9 ml of a heptane solution of triisobutylaluminum whose concentration was adjusted to 1 mmol / ml was added. Next, 0.25 ml of a toluene solution of racemic-ethylenebis (1-indenyl) zirconium dichloride adjusted to a concentration of 2 μmol / ml was added, and then the component (A) 15 obtained in Example 2 (2) above was added. 0.4 mg was added as a solid catalyst component. Polymerization was carried out at 70 ° C. for 60 minutes while feeding a mixed gas of ethylene and hydrogen containing 0.31 mol% of hydrogen so as to keep the total pressure constant.
As a result, 50 g of an olefin polymer was obtained. The polymerization activity per solid catalyst component was 3250 g / g solid catalyst component / hour. Further, the obtained olefin polymer is S
CB = 13.1, MFR = 4.1, MFRR = 42, S
R = 1.38 and [η] = 1.14.

[0027]

As described in detail above, according to the present invention, a novel racemic metallocene zirconium compound used as a highly active olefin polymerization catalyst component, a method for producing the same, and a highly active olefin polymerization catalyst component are provided. , As well as the use of zirconium compounds for the efficient production of olefin polymers. The olefin polymer obtained by using the novel metallocene zirconium compound of the present invention as a catalyst component is also excellent in performance such as processability.

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 4H049 VN06 VP01 VQ21 VR22 VR42                       VS09 VU14 VW02                 4H050 AA01 AA02 AA03 AB40 AC90                       BD70 WB11 WB13 WB21                 4J028 AA01A AB00A AC19A BA00A                       BA00B BB00A BB00B EA01                       EB03 EC01 EC02

Claims (5)

[Claims] 1. Racemic-ethylene bis (1-indenyl)
Zirconium diphenoxide. 2. Racemic-ethylene bis (1-indenyl)
A method for producing racemic-ethylenebis (1-indenyl) zirconium diphenoxide, which comprises using zirconium dihalide as a raw material. 3. A racemic-ethylenebis (1-indenyl) zirconium dihalide, which is obtained by reacting a compound obtained by reacting phenol with a strong base, and racemic-ethylenebis (1-indenyl) zirconium. A method for producing diphenoxide. 4. Racemic-ethylene bis (1-indenyl)
An olefin polymerization catalyst component comprising zirconium diphenoxide. 5. Use of racemic-ethylenebis (1-indenyl) zirconium diphenoxide as a catalyst component in the homopolymerization of olefins or the copolymerization of multiple olefins.