JP3256276B2 - Stabilized transition metal compound and storage method thereof - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a stabilized solution of a transition metal compound, and more particularly, to a method of storing a solution of a transition metal compound which can be stored for a long period of time.

[0002]

2. Description of the Related Art As a polymerization catalyst for olefins, a group having a conjugated π electron, in particular, a transition metal compound having cyclopentadiene or a derivative thereof as a ligand, and an alkylaluminoxane obtained by reacting a trialkylaluminum with water are used. Things are known. For example,
58-19309 discloses a method for polymerizing olefins using biscyclopentadienyl zirconium dichloride and methylaluminoxane as catalysts. Also JP-A-61-13031
4, JP-A-61-264010, JP-A-1-301704 and JP-A-2-301
41303 discloses a method for producing isotactic poly-α-olefin or syndiotactic poly-α-olefin and a polymerization catalyst for producing these stereoregular poly-α-olefins. All of the catalyst systems used use aluminoxane as a cocatalyst.

Recently, it has been reported that an isolated cationic metallocene compound having cyclopentadiene or a derivative thereof as a ligand has polymerization activity for olefins alone without the coexistence of methylaluminoxane as a cocatalyst. Have been. For example, RFJORDAN et al. In J. Am. Chem. Soc., 1986, 108: 7410-7411, zirconium cation having tetraphenylborane as an anion and having two cyclopentadienyl groups and a methyl group as ligands. The complex was isolated by using a donor such as tetrahydrofuran as a ligand, and it was reported that the isolated complex had ethylene polymerization activity in methylene chloride.

Further, Turner et al., J. Am. Chem. Soc., 1989
Volume 111, pages 2728-2729 and Tokiohei 1-501950, Tokiohei 1-5020
A transition metal compound capable of reacting with at least one proton having a cyclopentadienyl group or a derivative thereof having a substituent at 36 as a ligand, and a compound providing a stable anion having a cation capable of providing a proton It has been reported that an ion-pair type metallocene complex formed from has olefin polymerization activity. In addition, JP-A-3-139504, JP-A-3-17905, JP-A-3-17906,
JP-A-3-207703 and JP-A-3-207704 also disclose olefin polymerization methods without using aluminoxanes.

Further, Zambelli et al., Macromolecules, 1989.
Vol. 22, pp. 2186-2189 shows that isotactic polypropylene can be obtained by polymerizing propylene using a zirconium compound having a cyclopentadienyl group derivative as a ligand and a catalyst combining trimethylaluminum and fluorodimethylaluminum. It has been reported that the active species is also a metallocene compound in an ion-pair form.

[0006]

Conventionally, transition metal compounds having cyclopentadiene or a derivative thereof as a ligand have low solubility in hydrocarbon solvents, and are unstable except for transition metal compounds having a halogen as a ligand. It is known that a large amount of the compound is decomposed, particularly in a solution dissolved in a hydrocarbon compound, by a very small amount of impurities such as moisture and air or light. Therefore, when used as a catalyst as described above, a solution in which a transition metal compound is once dissolved in a hydrocarbon compound is stored, and the activity of polymerization is almost lost. It was necessary to prepare a compound solution.

[0007]

Means for Solving the Problems The present inventors have solved the above-mentioned problems and have intensively studied the stability of a solution of a transition metal compound which does not show a decrease in activity even after being stored for a long period of time. completed.

[0008] Thus, the present invention, a) the following general formula (Formula 1), (Formula 2) or (Formula 3) (wherein, Cp is different from one another identical or, cyclopentadienylide coordinated to M
Group, indenyl group, fluorenyl group or a part thereof
Or a hydrocarbon residue in which all hydrogens have 1 to 10 carbon atoms
In those substituted, Cp 'is a cyclopentadienyl which is mutually the same or cross-linked with R coordinated to different M
Group, indenyl group, fluorenyl group or a part thereof
Or all hydrogens are hydrocarbon residues having 1 to 10 carbon atoms
In the substituted one , R represents a residue containing a divalent nitrogen atom, oxygen atom, silicon atom, phosphorus atom, or sulfur atom, or a linear saturated hydrocarbon residue which may have a side chain, or a straight-chain saturated hydrocarbon residue. some or all silicon atoms of the carbon atoms of the chain, the residue which is substituted by germanium atoms or tin atoms, M is the period
A metal atom of Group 4 of the Table , and X is nitrogen coordinated to M
A ligand containing an atom or an oxygen atom , n is an integer of 1, 2 or 3)

[0009]

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[0010]

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[0011]

Embedded image A stabilized transition metal compound- containing catalyst component mixed with an organoaluminum compound, and the present invention is characterized in that the stabilized transition metal compound-containing catalyst component is stored as a hydrocarbon compound solution. This is a method for preserving the stabilized transition metal compound- containing catalyst component .

In the present invention, the transition metal compound may be represented by the general formula (Chem. 4), (Chem. 5) or (Chem. 6)
Can be exemplified.

Wherein Cp is the same as or different from each other;
A cyclopentadienyl group, an indenyl group,
A fluorenyl group or some or all of its hydrogens are carbon
Substituted with several to ten hydrocarbon residues
You.

Cp 'is a cyclopentadienyl group bridged by R and coordinated to the same or different M,
Nil group, fluorenyl group or a part or all of
Hydrogen replaced by a hydrocarbon residue having 1 to 10 carbon atoms
Things.

The divalent group represented by R is -O-, -S-
, -SS-, -SO-, -SO _2- , -CO-, -NR-, -PR-, -POR-
, -OSiR ₂ O- or a methylene group represented by the following formula (Chem. 7) or a silylene group or germylene group in which part or all of the carbon atoms of the methylene group are substituted with a silicon atom, a germanium atom, or a tin atom And those having a stannylene group.

[0016]

## STR7 ##-(R ₂ C) k- (R ₂ Si) l-(R ₂ Ge) p-(R ₂ Sn) q − (wherein R is a hydrogen atom or a hydrocarbon having 1 to 20 carbon atoms) And each R may be the same or different, and k, l, p, and q are integers of 0 to 4;
Represents an integer satisfying ≦ k + 1 + p + q ≦ 4. )

X includes a nitrogen atom and an oxygen atom coordinated to M.
Specifically, NR ′ ₂ , OR ′, OCR
' ₂ . n depends on the valence of M,
Or 3. When n is 2 or more, Xs may be mutually cross-linked, and a chelating ligand is also exemplified.

In the present invention, the transition metal compound represented by the above general formula (4), (5) or (6) is brought into contact with an organoaluminum compound and a hydrocarbon compound solution to form a uniform solution. Are synthesized. The organoaluminum compound used here has residues such as halogen, oxygen, hydrogen, alkyl, alkoxy, and aryl as ligands, and these ligands may be the same or different. However, at least one has an alkyl group. For example, an alkyl aluminum compound in which 1 to n alkyl residues having 1 to 12 carbon atoms are bonded, an alkyl aluminum halide, an alkyl aluminum hydride, an alkyl aluminum alkoxide, or the like can be used.

For example, trimethyl aluminum, triethyl aluminum, tri-n-propyl aluminum, triisopropyl aluminum, tributyl aluminum, triisobutyl aluminum, tripentyl aluminum, trihexyl aluminum, triheptyl aluminum, trioctyl aluminum, tridecyl aluminum, isodecyl aluminum Prenyl aluminum, diethyl aluminum hydride, diisopropyl aluminum hydride, diisobutyl aluminum hydride, diethyl aluminum chloride, di-n-propyl aluminum chloride, diisopropyl aluminum chloride, diisobutyl aluminum chloride, diethyl aluminum ethoxide, diisopropyl aluminum isopropoxide, d Le sesquichloride, isopropyl aluminum sesquichloride, isobutyl aluminum sesquichloride, ethyl aluminum dichloride, isopropyl aluminum dichloride, isobutyl aluminum dichloride, ethyl aluminum diisopropoxide, and the like. Among these aluminum compounds, a trialkylaluminum compound is particularly preferred.

The method for producing the stabilized transition metal compound can be easily obtained by mixing the transition metal compound with an organoaluminum compound. The method of mixing is arbitrary. In short, if these compounds are brought into contact, a stabilized transition metal compound can be easily obtained.

In the present invention, a stabilized transition metal compound solution can be obtained more easily by using a hydrocarbon compound when mixing the transition metal compound and the organoaluminum compound. In this case, even if a transition metal compound having a lower solubility is used, the transition metal compound and the organoaluminum compound react in the hydrocarbon compound solution to be solubilized, so that a stable transition metal compound hydrocarbon compound solution is obtained. Can be Moreover, even if the solution of the stabilized transition metal compound hydrocarbon compound obtained in this way is stored for a long period of time, the metallocene compound is decomposed to generate insolubles, or it may be used as an olefin polymerization catalyst. Even if it is used, it is possible to prevent the activity from decreasing or becoming inactive.

In the present invention, the temperature at which these are brought into contact is not particularly limited, but it is usually preferable to carry out the temperature at -20 to 100 ° C. The temperature at which they are stored is not particularly limited, but it is also preferable to store them at a temperature of -20 to 100 ° C.

Here, the mixing ratio of the organoaluminum compound to the transition metal compound in the solution is usually 1 to 10,000 times that of the transition metal atom.
Of course, there is no problem even if an excessive amount of the organoaluminum compound is used, but even if it is used in an excessively large amount, there is no difference in stability, and even if the compound is used as a polymerization catalyst, the activity is not further improved and no problem occurs. Economy.

The hydrocarbon compounds used in the present invention include, for example, benzene, besides aliphatic hydrocarbon compounds such as propane, butane, pentane, hexane, heptane, octane, nonane, decane, hexadecane, cyclopentane and cyclohexane. Aromatic hydrocarbon compounds such as toluene, xylene and ethylbenzene and diethyl ether,
Ether compounds or ester compounds such as tetrahydrofuran can also be used, and halogenated hydrocarbon compounds such as methylene chloride can be used as long as they do not react with the organoaluminum compound used.

Although the concentration of the transition metal compound in the transition metal compound solution of the present invention is not particularly limited, it is usually 10 ^-8 to 1 mol / l, preferably 10 ^{-7 to} 0.1 mol / l as the transition metal compound concentration. Liters.

As described above, the stabilized transition metal compound of the present invention can be combined with a conventionally known organometallic compound for olefin polymerization or a compound capable of reacting with a metallocene compound to form an ionic compound. Used for the polymerization of Here, the organometallic compound for olefin polymerization is represented by the following general formula (Chem. 8) or (Chem. 9) (where R is an alkyl group having 1 to 6 carbon atoms, and n is an integer of 1 or more). Aluminoxane compound,

[0027]

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[0028]

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These are produced by various methods, for example, by reacting 1 to 3 moles of water with trialkylaluminum as a raw material. Examples of the trialkylaluminum include trimethylaluminum, triethylaluminum, tripropylaluminum, trin-butylaluminum, triisobutylaluminum, trihexylaluminum, and mixtures thereof.

Examples of the compound which reacts with the metallocene compound to form an ionic compound include an ionic compound formed from an ion pair of a cation and an anion, and an electrophilic compound. These compounds are generally known as Lewis acid compounds, have appropriate Lewis acidity, and have the property of reacting with a neutral metallocene compound used as a catalyst to convert them into ionic compounds. If necessary, it reacts with the transition metal compound represented by the above general formula (Chemical Formula 4), (Chemical Formula 5) or (Chemical Formula 6), and a group represented by X in the formula is transferred to the Lewis acid compound as an electron pair. , Which forms a transition metal cation compound, and does not inactivate the polymerization activity by recombining or strongly coordinating the transition metal cation compound with the Lewis acid itself or the anion that has formed an ion pair with the generated transition metal cation compound. Things.

Examples of the cation of the ionic compound include:
Examples thereof include a carbonium cation, a tropylium cation, an oxonium cation, a sulfonium cation, a phosphonium cation, and an ammonium cation.

Examples of the anion of the ionic compound include:
Organic boron compound anion, organic aluminum compound anion, organic phosphorus compound anion, organic arsenic compound anion, organic antimony compound anion, etc., and metal oxides known as metal halides and solid acids as electrophilic compounds And the like.

The olefin used when the stabilized transition metal compound of the present invention is subjected to polymerization is, for example, an olefin having 2 to 25 carbon atoms, and specific examples thereof include ethylene, propylene, butene-1, and pentene-1. , Hexene-
1, heptene-1, octene-1, nonene-1, decene-1, undecene-1, dodecene-1, tridecene-1, tetradecene
-1, pentadecene-1, hexadecene-1, octadecene-1
In addition to linear olefins such as 3-methylbutene-1, 4-methylpentene-1, branched olefins such as 4,4-dimethylpentene-1 and cyclopentene, cyclooctene, and cyclic olefins such as norbornene are exemplified. An olefin can be homopolymerized or a copolymer of olefins can be copolymerized with each other. If necessary, a diene can be copolymerized. Further, in this polymerization system, an aromatic olefin such as styrene can be polymerized, and aromatic olefin alone or copolymerization with the above olefin can be performed.

As the polymerization temperature and the polymerization pressure, general conditions used in a known method are used. The polymerization temperature is -20 to 150 ° C., and the polymerization pressure is normal pressure to 100 kg / cm ^2. .

[0035]

The present invention will be further described with reference to examples.

Example 1 10 mg of isopropyl (cyclopentadienyl-1-fluorenyl) zirconium dimethoxide was dissolved in 10 ml of toluene, and 0.31 g of triethylaluminum was added and mixed.
One-fourth of these catalysts were used and charged to a 2 liter autoclave containing 1 liter of toluene and 0.08 g of triethylaluminum. Then add ethylene and add 8
kg / cm ² -G, 10.7 mg of triphenylmethanetetra (pentafluorophenyl) borane and 10 ml of toluene
Was added into an autoclave to initiate polymerization. Polymerize at 80 ° C for 1 hour while maintaining 8kg / cm ² -G,
Then, the mixture was filtered and dried to obtain 42 g of a polymer.

Then, the remainder of the toluene solution of isopropyl (cyclopentadienyl-1-fluorenyl) zirconium dimethoxide and triethylaluminum was stored at room temperature for one month, and the polymerization of ethylene was carried out in the same manner to obtain 40 g of a polymer. The polymerization performance did not change after storage.

Comparative Example 1 Ethylene was polymerized in the same manner as in Example 1 except that a toluene solution to which triethylaluminum was not added was prepared. The polymerization activity immediately after the solution preparation was the same as the result of Example 1, but after storing at room temperature for one month, polymerization of propylene was carried out in the same manner, and almost no polymerization activity was observed.

Example 2 Instead of isopropyl (cyclopentadienyl-1-fluorenyl) zirconium dimethoxide, 10 mg of dicyclopentadienyl zirconium di (dimethylamide) and 0.39 g of triethylaluminum were dissolved in 10 ml of toluene. Using 1/5 of this solution, ethylene was polymerized in the same manner as in Example 1 using methylaluminoxane instead of triphenylmethanetetra (pentafluorophenyl) boron to obtain 54 g of a polymer. After storing this solution at room temperature for one month, ethylene was polymerized in the same manner to obtain 52 g of a polymer, and the polymerization performance did not change after storage.

Example 3 The polymerization of ethylene was carried out in the same manner as in Example 1 except that 0.52 g of triisobutylaluminum was used instead of triethylaluminum, to obtain 56 g of a polymer. After this solution was stored at room temperature for one month, the polymerization performance hardly changed even when ethylene was polymerized in the same manner. Example 4 Polymerization was performed in the same manner as in Example 1 except that cyclohexane was used instead of toluene. Was carried out to obtain 25 g of a polymer. After storing this solution at room temperature for one month, the polymerization performance was not substantially changed even if ethylene was polymerized in the same manner.

[0041]

By carrying out the method of the present invention, the transition metal compound solution can be stored for a long period of time, and the polymerization can be carried out more stably during the polymerization than when the transition metal compound is used alone. It is expected that a polyolefin can be obtained with high activity per catalyst, which is extremely valuable industrially.

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int. Cl. ⁷ , DB name) C08F 4/642 C08F 10/00-10/14 C08F 110/00-110/14 C08F 210/00-210 / 18

Claims (2)

(57) [Claims] A) a cyclopentadienyl group coordinated to M, in which Cp is the same as or different from each other , indenyl,
Group, fluorenyl group or part or all of hydrogen
Is substituted with a hydrocarbon residue having 1 to 10 carbon atoms
The, Cp 'is different from each other the same or cross-linked with R
A cyclopentadienyl group, an indenyl group,
Fluorenyl group or part or all of hydrogen
Those substituted with a hydrocarbon residue having a prime number of 1 to 10 ,
R is a residue containing a divalent nitrogen atom, an oxygen atom, a silicon atom, a phosphorus atom, or a sulfur atom, or a straight-chain saturated hydrocarbon residue which may have a side chain, or one of its straight-chain carbon atoms. M represents a residue in which part or all of the residue is substituted with a silicon atom, germanium atom or tin atom, and M is a metal atom of Group 4 of the periodic table.
Child, and nitrogen atom X is coordinated to M, containing an oxygen atom
Wherein n is an integer of 1, 2, or 3) and a transition metal compound represented by the following formula: Embedded image Embedded image b) A stabilized transition metal compound- containing catalyst component obtained by mixing an organoaluminum compound. 2. A method according to claim 1 stabilized transition metal compound containing transition metal compounds are stabilized, characterized in that stored in a solution of the catalyst component a hydrocarbon compound containing catalyst component described
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