JPH07103185B2 - Catalyst for polyolefin production - Google Patents

Description

TECHNICAL FIELD The present invention relates to a catalyst for producing a polyolefin. More specifically, new transition metal compounds bis 2,3 and 4
The present invention relates to the catalyst composed of a substituted cyclopentadienyl transition metal dihalide and a specific aluminoxane.

[Conventional technology and its problems]

Kaminsky catalyst, ie bis (cyclopentadienyl)
A catalyst consisting of zirconium dichloride and aluminoxane can polymerize olefins with high activity,
It is known from JP-A-58-19309, Makromol. Chem., Vol. 4, page 417 (1983). Further, recently, a technique of using various transition metal compounds for adjusting the molecular weight, the molecular weight distribution or the copolymerizability has been known (JP-A-60-
35006, JP60-350007, JP60-3500
No. 6). In addition, although these patents describe that a transition metal compound having a substituted cyclopentadienyl group is used as a catalyst, a specific description using a transition metal having a 2,3 and 4-substituted cyclopentadienyl group ( There is no example).

Further, JP-A-61-236804 describes a method for producing an ethylenic wax containing an unsaturated bond at the end,
The detailed content of the unsaturated bond is completely mentioned.

These conventional Kaminsky catalysts have problems that the yield and molecular weight of polyolefin are not sufficiently high, and the structure of the terminal unsaturated bond of the obtained polyolefin cannot be regulated at all.

As a result of repeated studies to solve the above problems, the present inventors have found that a catalyst composed of the novel organic transition metal compound and a specific aluminoxane regulates the structure of the unsaturated bond at the polyolefin terminal. The inventors have found that it can be a vinylidene type, and have arrived at the present invention based on this finding.

[Means for solving problems]

The present invention includes the following main configuration (1) and (2) to (3)
The embodiment has a configuration.

(1) A. Transition metal compound represented by general formula [I] (▲ R ¹ _n ▼ -C ₅ H _5-n ) ₂ ZrX ₂ ...... [I] (however, ▲ R ¹ _n ▼ -C ₅ H _5-n represents a substituted cyclopentadienyl group, n represents an integer of 2 to 4, R ¹ represents an alkyl group having 1 to 5 carbon atoms, and X represents a halogen atom.) And B. general formula [ II] or general formula [III] (However, m is a number from 4 to 20, and R ² represents a hydrocarbon group.)
C3 containing aluminoxane as the active ingredient
A catalyst for producing the above olefin polymer.

(2) The catalyst according to the above item (1), wherein X is chlorine in the transition metal compound represented by the general formula [I].

(3) In the transition metal compound represented by the general formula [I], ▲ R ¹ _n ▼ -C ₅ H _5-n is 1,2,3-, 1,2,4-or 1,2,
The first (1) which is a 3,4-substituted cyclopentadienyl group
The catalyst according to the item.

The transition metal compound (A) of the catalyst component of the present invention is 2,3
And a compound having two 4-substituted cyclopentadienyl groups, each having two halogen atoms.

The 2-substituted cyclopentadienyl group includes 1,2- and 1,3- ▲
There are two types of R ¹ ₂ ▼ -C ₅ H ₃ , but in the present invention,
It is a 1,3-substitution product. Further, 3 to be substituted cyclo preventor cyclopentadienyl group, 1,2,3- and 1,2,4- ▲ R ¹ ₃ ▼ -C ₅ but two H ₂ is present, but also includes any. R ¹ is a methyl group,
Ethyl group, propyl group, isopropyl group, butyl group, se
It is a hydrocarbon group such as a c-butyl group, a tert-butyl group and a pentyl group, preferably a methyl group and an ethyl group.
X is a halogen atom such as fluorine, chlorine, bromine or iodine, preferably chlorine.

Further, as the transition metal compound, specifically, bis (1,3
-Dimethylcyclopentadienyl) zirconium dichloride, bis (1,3-diethylcyclopentadienyl) zirconium dichloride, bis (1,3-dimethycyclopentadienyl) zirconium dibromide, bis (1,2,3-
Trimethylcyclopentadienyl) zirconium dichloride, bis (1,2,3-trimethylcyclopentadienyl) zirconium dibromide, bis (1,2,4-trimethylcyclopentadienyl) zirconium dichloride, bis (1,2, 4-trimethylcyclopentadienyl) zirconium dibromide, bis (1,2,4-trimethylcyclopentadienyl) zirconium diiodide, bis (1,2,
4-trimethylcyclopentadienyl) zirconium difluoride, bis (1,2,3,4-tetramethylcyclopentadienyl) zirconium dichloride, bis (1,2,3,4
Examples thereof include zirconium compounds such as -tetramethylcyclopentadienyl) zirconium dibromide.

Aluminoxane (B) which is another constituent component of the present invention
Is an organoaluminum compound represented by the general formula [I] or the general formula [II]. R ² is a hydrocarbon group such as a methyl group, an ethyl group, a propyl group and a butyl group, preferably a methyl group and an ethyl group. m is an integer of 4 to 20, preferably 6 or more, and particularly preferably 10 or more. The production method of this kind of compound is known, for example, trialkyl is added to a hydrocarbon medium suspension of a compound containing adsorbed water, a salt containing water of crystallization (copper sulfate hydrate, aluminum sulfate hydrate, etc.). The method of adding aluminum and making it react can be illustrated.

In the method using the catalyst of the present invention, the olefin used in the polymerization reaction is propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-
Α- such as decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene
It is an olefin, and a mixed component of two or more of these may be subjected to polymerization.

As the polymerization method, any of suspension polymerization, solution polymerization and gas phase polymerization is possible. As a polymerization solvent for liquid phase polymerization, butane, pentane, hexane, octane, decane, dodecane, hexadecane, octadecane and other aliphatic hydrocarbons, cyclopentane, methylcyclopentane, cyclohexane, cyclooctane and other alicyclic hydrocarbons Aromatic hydrocarbons such as hydrogen, benzene, toluene, xylene, and petroleum fractions such as gasoline, kerosene, and light oil are used.
Of these, aromatic hydrocarbons are preferred. The olefin pressure in the reaction system is normal pressure to 50 kg / cm ² G, and the polymerization temperature is -5.
It is in the range of 0 ° C to 230 ° C, preferably -20 ° C to 200 ° C.
The molecular weight at the time of polymerization can be controlled by a known means, for example, measuring the temperature.

In the method of using the catalyst of the present invention, (A) a transition metal compound,
A mixture of both components of (B) aluminoxane in advance may be supplied to the reaction system, or both components (A) and (B) may be supplied to the reaction system. In any case, the concentration of both components in the polymerization system, the molar ratio is not particularly limited, but preferably a transition metal concentration of 10 ^-4 to 10
It is in the range of ^-9 mol /, and the molar ratio of Al / metal atom is 100 or more, particularly 1000 or more.

The structure of the terminal unsaturated bond of the polyolefin produced using the catalyst of the present invention can be fixed by IR spectrum. For example, vinylidene type is 3095-3077 cm ^-1 , 17
90~1785cm ^-1, 1661~1639cm ^-1, it can be determined at the peak of such 892~883cm ^-1.

〔The invention's effect〕

Use of the catalyst of the present invention, which uses a transition metal compound having two 2,3 and 4-substituted cyclopentadienyl groups as a novel transition metal compound combined with aluminoxane, regulates the structure of the unsaturated bond at the terminal of the polyolefin. To give a vinylidene group.

〔Example〕

Next, the catalyst of the present invention and the method of using the same will be specifically described with reference to examples.

Example 1 [Bis (1,2,4-trimethylcyclopentadienyl) zirconium dichloride] All reactions were carried out under an inert gas atmosphere. The reaction solvent used was previously dried. In a 500 ml glass reaction vessel, 1,2,4-trimethylcyclopentadiene 5.5 g (51 mmol) was added to tetrahydrofuran 150 ml.
And was added dropwise with 36 ml of a 15% solution of n-butyllithium / hexane. After stirring at room temperature for 1 hour, 1,2,4-
A white suspension of trimethylcyclopentadienyl lithium was cooled to 0 ° C., and 5.9 g (25 mmol) of zirconium tetrachloride was added in 5 batches. The reaction solution was slowly warmed to room temperature and stirred for 48 hours. The solvent was distilled off under reduced pressure from the yellow solution containing white precipitate (LiCl), and the mixture was extracted with 300 ml of methylene chloride and filtered. Concentrate the yellow filtrate, add pentane,
After cooling to -30 ° C, 4.0 g of white crystals were obtained. Sublimation (130-1
After purification at 40 ° C / 1 mmHg), 3.5 g (yield 36%) of the desired product was obtained. The melting point of this compound was 172-173 ° C.

Example 2 [Polymerization] 450 ml of purified toluene, 6.3 mmol of methylaluminoxane (molecular weight 909) manufactured by Toyo Stoufer Chemical Co., Ltd., and bis (1 0.02 mmol of 2,2,4-trimethylcyclopentadienyl) zirconium dichloride was sequentially added, and the temperature was raised to 50 ° C.

Then, propylene was continuously introduced into this so that the total pressure was maintained at 8 kg / cm ² G, and polymerization was carried out for 1.5 hours. After the reaction, the catalyst component was decomposed with methanol, and the obtained polypropylene was dried. As a result, 260 g of atactic polypropylene was obtained. In the IR spectrum, 1651 cm ^-1 ,
There was a peak at 887 cm ^-1 , and the terminal structure was vinylidene type.

Example 3 [Bis (1,2,3,4-tetramethylcyclopentadienyl) zirconium dichloride] All reactions were carried out under an inert gas atmosphere. The reaction solvent used was previously dried. In a 500 ml glass reaction vessel, 1,2,3,4-tetramethylcyclopentadiene (2.5 g, 20 mmol) was added to 1,2-dimethoxyethane (1).
Dilute with 50 ml of n-butyllithium / hexane 15
% Solution of 15% was added dropwise. After stirring for 1 hour at room temperature, 1,2,
A white suspension of 3,4-tetramethylcyclopentadienyllithium was cooled to 0 ° C and 2.3 g (10
Mmol) was added in 5 portions. Heating the reaction solution,
The mixture was stirred under reflux for 72 hours. The solvent was distilled off under reduced pressure from the yellow solution containing white precipitate (LiCl), and the mixture was extracted with 300 ml of methylene chloride and filtered. The yellow liquid was concentrated, pentane was added, and the mixture was cooled to -30 ° C to obtain 0.16 g of white crystals. Sublimation (130-140 ℃ / 1m
After purification, 0.13 g (yield 3%) of the desired product was obtained. The melting point of this compound was 270-271 ° C.

Example 4 [Polymerization] 450 ml of purified toluene, 6.3 mmol of methylaluminoxane (molecular weight 909) manufactured by Toyo Stoufer Chemical Co., Ltd., and bis (1 , 2,3,4-Tetramethylcyclopentadienyl) zirconium dichloride 0.
02 mmol was sequentially added, and the temperature was raised to 50 ° C.

Then, propylene was continuously introduced into this so that the total pressure was maintained at 8 kg / cm ² G, and polymerization was carried out for 2 hours. After the reaction
The catalyst component was decomposed with methanol, and the obtained polypropylene was dried. As a result, 260 g of atactic polypropylene was obtained. IR spectrum shows 1782 cm ^-1 , 1651
cm ^-1, there is a peak in the 887cm ^-1, the terminal structure was vinylidene type.

Example 5 [Bis (1,3-dimethylcyclopentadienyl) zirconium dichloride] All reactions were carried out under an inert gas atmosphere. The reaction solvent used was previously dried. In a 500 ml glass reaction vessel, 1,3-dimethylcyclopentadiene
3.4 g (36 mmol) was diluted with 150 ml of tetrahydrofuran and 24 ml of 15% n-butyllithium / hexane solution was added.
Was added dropwise at 0 ° C. After stirring at room temperature for 1 hour, the solution of 1,3-dimethylcyclopentadienyllithium was cooled to 0 ° C., and 3.5 g (15 mmol) of zirconium tetrachloride was added in 5 portions. Allow the reaction solution to slowly warm to room temperature and
Stir for hours. The solvent was distilled off under reduced pressure from the yellow solution containing white precipitate (LiCl), and the mixture was extracted with 300 ml of methylene chloride and filtered. The yellow filtrate was concentrated, pentane was added, and the mixture was cooled to -30 ° C to obtain 1.7 g of white crystals. Sublimation (130-140 ℃ / 1mmH
g) After purification, 1.1 g (yield 22%) of the desired product was obtained. The melting point of this compound was 175 to 176 ° C.

Example 6 [Polymerization] 450 ml of purified toluene, 6.3 mmol of methylaluminoxane (molecular weight 909) manufactured by Toyo Stoufer Chemical Co., Ltd., and bis (1 0.03-mmol of 3,3-dimethylcyclopentadienyl) zirconium dichloride was sequentially added, and the temperature was raised to 50 ° C.

Next, propylene was continuously introduced into this so that the total pressure was maintained at 8 kg / cm ² G, and polymerization was carried out for 4 hours. After the reaction
The catalyst component was decomposed with methanol, and the obtained polypropylene was dried. As a result, 450 g of atactic polypropylene was obtained. IR spectrum shows 1651 cm ^-1 , 887c
There was a peak at m ^-1 and the terminal structure was vinylidene type.

Comparative Example 1 In a sus autoclave with an internal volume of 1.51 that was sufficiently replaced with nitrogen, purified toluene 450 ml, methylaluminoxane (molecular weight 909) 6.3 mmol and bis (pentamethylcyclopentadienyl) zirconium dichloride 0.02 mmol manufactured by Toyo Stoufer Chemical Co., Ltd. Are added sequentially, and at 50 ℃
The temperature was raised to.

Next, propylene was continuously introduced into this so that the total pressure was maintained at 8 kg / cm ² G, and polymerization was carried out for 4 hours. After the reaction
The catalyst component was decomposed with methanol, and the obtained polypropylene was dried. As a result, 210 g of atactic polypropylene was obtained. IR spectrum shows 1639 cm ^-1 , 991c
There were peaks at m ⁻¹ and 910 cm ⁻¹ , and the terminal structure was vinyl type.

Example 7 [Bis (1,2,3-trimethylcyclopentadienyl) zirconium dichloride] All reactions were performed under an inert gas atmosphere. The reaction solvent used was previously dried. In a 500 ml glass reaction vessel, 1,2,3-trimethylcyclopentadiene (3.5 g, 32 mmol) was diluted with 150 ml of tetrahydrofuran to prepare a 15% solution of n-butyllithium / hexane.
25 ml was added dropwise. After stirring at room temperature for 1 hour, a white suspension of 1,2,3-trimethylcyclopentadienyllithium was cooled to 0 ° C. and 3.7 g (16 mmol) of zirconium tetrachloride was added.
Was added in 5 portions. The reaction solution was slowly warmed to room temperature and stirred for 3 hours. The solvent was distilled off under reduced pressure from the yellow solution containing white precipitate (LiCl), and then the product was sublimated (130 to 140).
℃ / 1mmHg) 0.68g (Yield 11
%) Was obtained. The melting point of this compound was 252-253 ° C.

Example 8 [Polymerization] 450 ml of purified toluene, 6.3 mmol of methylaluminoxane (molecular weight 909) manufactured by Toyo Stoufer Chemical Co., Ltd., and bis (1 0.02 mmol of 2,2,3-trimethylcyclopentadienyl) zirconium dichloride was sequentially added, and the temperature was raised to 50 ° C.

Next, propylene was continuously introduced into this so that the total pressure was maintained at 8 kg / cm ² G, and polymerization was carried out for 4 hours. After the reaction
The catalyst component was decomposed with methanol, and the obtained polypropylene was dried. As a result, 180 g of atactic polypropylene was obtained. IR spectrum shows 1651 cm ^-1 , 887c
There was a peak at m ^-1 and the terminal structure was vinylidene type.

Supplementary explanation of Examples Among the above Examples and Comparative Examples, infrared absorption spectra of atactic polypropylene for Examples 2, 4, 6, 8 and Comparative 1 are shown in FIGS. 1, 2, 3, 4 and 5. In the example
The ¹³ C-NMR data of 2,4 and 8 are shown in Table 1 and the results of Examples 2,4,
The GPC data of 6,8 and Comparative Example 1 are shown in Table 2.

[Brief description of drawings]

1 to 5 show infrared absorption spectra according to Examples or Comparative Examples of the present invention. FIG. 6 is a flow sheet for explaining the constitution of the catalyst of the present invention.

Front page continued (72) Inventor Takaya Mise 21-11, Suwa-cho, Kawagoe City, Saitama Prefecture (72) Inventor Hiroshi Yamazaki 2-41-10, Matsugaoka, Tokorozawa City, Saitama Prefecture (56) Reference JP-A-60-35007 (JP, A) JP-A-63-234005 (JP, A)

Claims (3)

[Claims] 1. A. A transition metal compound represented by the general formula [I] (▲ R ¹ _n ▼ -C ₅ H _5-n ) ₂ ZrX ₂ ...... [I] (however, ▲ R ¹ _n ▼ -C) ₅ H _5-n represents a substituted cyclopentadienyl group, n is an integer of 2 to 4, R ¹ is an alkyl group having 1 to 5 carbon atoms, and X is a halogen atom.) And B. General Formula [II] or general formula [III] (However, m is a number from 4 to 20, and R ² represents a hydrocarbon group.)
C3 containing aluminoxane as the active ingredient
A catalyst for producing the above olefin polymer. 2. The catalyst according to claim 1, wherein in the transition metal compound represented by the general formula [I], X is chlorine. 3. In the transition metal compound represented by the general formula [I], ▲ R ¹ _n ▼ -C ₅ H _5-n is 1,2,3-, 1,2,4- or 1,2,3. The catalyst according to claim (1), which is a 4,4-substituted cyclopentadienyl group.