JPH0517515A - Production of solid catalyst component for polymerizing olefin and method for polymerizing olefin using the same - Google Patents

Abstract

PURPOSE:To obtain the subject highly active component capable of providing polyolefins with excellent productivity by introducing a conjugated alkadienyl into a specific inorganic compound treated with an organosilicon compound, then metalating the resultant compound and reacting the aforementioned product with a transition metallic compound. CONSTITUTION:An inorganic compound (e.g. silica) having surface hydroxyl groups is initially treated with an organosilicon compound (e.g. dimethyldichlorosilane) expressed by the formula 2Si2 (R is 1-20C hydrocarbon residue; X is halogen) to provide a compound, which is subsequently brought into contact with an organic compound (e.g. biscyclopentadienylmethylhydroxyethylmethane) expressed by the formula (A and B are conjugated alkadienyl; C and D are hydroxyl group-containing 1-50C hydrocarbon residue; E is C, Si, etc.). The resultant compound is then subjected to metalation treatment with an organometallic compound (e.g. methyl-lithium) expressed by the formula MR' (M is group I metal of the periodic table; R' is 1-20C hydrocarbon residue) and subsequently brought into contact with a transition metallic compound (e.g. titanium tetrachloride) expressed by formula M'X' (M' is group IV or V metal of the aforementioned periodic table; X' is X).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a solid catalyst component for olefin polymerization and a method for polymerizing an olefin using this catalyst component, and more particularly to a method for producing a metallocene catalyst for producing a polyolefin and an olefin using the same. The present invention relates to a polymerization method of.

[0002]

2. Description of the Related Art A method for polymerizing an olefin using a metallocene compound having a group having a conjugated π electron, particularly cyclopentadiene and its derivative as a ligand, and methylaluminoxane obtained by the reaction of trimethylaluminum and water is known. ing. For example, JP-A-58-19309 discloses a method for polymerizing olefins using biscyclopentadienyl zirconium dichloride and methylaluminoxane as a catalyst.

[0003]

DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention
The method according to, for example, has a large activity per transition metal and is an excellent method, but the bulk specific gravity of the produced polymer after polymerization is small, and it is difficult to handle, and when applied to a gas phase or liquid phase polymerization method, the polymerization is Adhesion of the polymer to the container wall occurs, heat removal becomes difficult due to poor heat transfer, and polymer mass is generated.There are problems in using these as catalysts for polyolefin production on an industrial scale. there were.

[0004]

[Means for Solving the Problems] The present inventors completed the present invention by solving the above problems and earnestly studying a method for producing a highly active polyolefin with high productivity.

That is, the present invention provides a compound represented by the following general formula 5 (wherein A and B are the same or different conjugated alkadienyl groups, C and D are the same or different from each other, and at least one hydroxyl group is present in one or both of them. 1 to 50 carbon atoms
Hydrocarbon residue of E, an organic compound represented by E is an atom selected from carbon, silicon, germanium and tin),

[0006]

[Chemical 5] An inorganic compound having a surface hydroxyl group is contacted with a compound treated with an organosilicon compound represented by the following general formula (6) (wherein R is a hydrocarbon residue having 1 to 20 carbon atoms and X is a halogen atom):

[0007]

## STR00006 ## R ₂ SiX _{2 The} obtained compound is represented by the following general formula (wherein M is a metal atom selected from Group 1 of the periodic table, R'is a hydrocarbon residue having 1 to 20 carbon atoms). ) After metallization treatment with an organometallic compound represented by

[0008]

Embedded image MR ′ A general formula of the following chemical formula 8 (wherein M ′ is a group 4 or 5 of the periodic table)
Of a solid catalyst component for olefin polymerization, which comprises contacting with a transition metal compound represented by a metal atom selected from the group, X'is a halogen atom, and polymerizing an olefin using this solid catalyst component Is a method for polymerizing olefins.

[0009]

Embedded image M'X '

The method for producing the catalyst component of the present invention will be described in detail below.

In the present invention, first, an organic compound having a hydroxyl group and a conjugated alkadienyl group represented by the general formula (Formula 5) and an inorganic compound having a surface hydroxyl group are added to the organic silicon represented by the general formula (Formula 6). The compound treated with the compound is reacted to introduce a conjugated alkadienyl group onto the inorganic compound.

The method of treating the inorganic compound having a surface hydroxyl group with the organosilicon compound is preferably carried out by bringing them into contact with each other in a temperature range of 0 to 300 ° C. in an autoclave. The use ratio of the organosilicon compound to the inorganic compound having a surface hydroxyl group is 1 to 100000 times, usually 1 to 1000 times, in terms of molar ratio with the surface hydroxyl group.

The reaction with an organic compound having a hydroxyl group and a conjugated alkadienyl group is carried out by treating an inorganic compound having a surface hydroxyl group with an organic silicon compound and an organic compound having a hydroxyl group and a conjugated alkadienyl group with benzene, toluene and xylene. And an aromatic hydrocarbon compound such as pentane, hexane, heptane, octane, nonane, decane, cyclopentane, and cyclohexane. The usage rate of the organic compound having a hydroxyl group and a conjugated alkadienyl group is 0 per 1 gram of a compound obtained by treating an inorganic compound having a surface hydroxyl group with an organosilicon compound.
It is from 01 to 10000 mmol, usually from 0.1 to 100 mmol.

In the present invention, the organic compound represented by the above-mentioned general formula (Formula 5) can be a ligand of the transition metal compound represented by (Formula 8), and A, B, C, and
Compounds in which D and E are as shown below are exemplified.

Examples of A and B include monocyclic or polycyclic conjugated alkadienyl groups having 5 to 30 carbon atoms. Specifically, a cyclopentadienyl group or a part or all of hydrogen thereof has carbon atoms. 1 to 10 substituted with an alkyl group (wherein the alkyl group may have a structure in which the terminal is again bound to the cyclopentadiene ring), an indenyl group, a fluorenyl group or part or all of the hydrogen thereof Examples thereof include those substituted with an alkyl group having 1 to 10 carbon atoms.

C and D are the same or different from each other and are a hydrocarbon residue having 1 to 50 carbon atoms having at least one hydroxyl group on one or both of them. For example, hydroxymethyl, hydroxyethyl, hydroxypropyl, hydroxybutyl, hydroxyphenyl, hydroxyphenylmethyl, hydroxyphenylethyl, hydroxyphenylpropyl, hydroxyphenylbutyl and the like can be exemplified. E is an atom selected from carbon, silicon, germanium, and tin.

Specifically, biscyclopentadienylmethylhydroxyethylmethane, cyclopentadienylfluorenylmethylhydroxyethylmethane, biscyclopentadienylmethylhydroxyphenylethylmethane, cyclopentadienylfluorenylmethylhydroxy Examples include phenylethylmethane.

The inorganic compound used in the present invention is not particularly limited as long as it has a surface hydroxyl group, but it is usually an industrially available particulate inorganic oxide, specifically silica, alumina, magnesia, Zinc oxide, boron oxide, titania, zirconia, or composite oxides containing these as the main components (these are 100 to 10
It is preferable to perform dehydration treatment by heating at 00 ° C. for a predetermined time, but of course, it may be used without dehydration treatment. ) Can be illustrated.

In the present invention, examples of the organosilicon compound represented by the above general formula (Formula 6) include compounds in which R and X in the formula are as shown below.

Examples of R include alkyl groups such as methyl, ethyl, propyl, and butyl; aryl groups such as phenyl, tolyl, xylyl, and benzyl; and X as fluorine.
Examples thereof include halogen atoms such as chlorine, bromine and iodine.

Specific examples include dimethyldichlorosilane, dimethyldibromosilane, dibutyldichlorosilane, dibutyldibromosilane, diphenyldichlorosilane, diphenyldibromosilane and the like.

In the present invention, a compound obtained by introducing a conjugated alkadienyl group into an inorganic compound treated with an organosilicon compound is then further treated with an organometallic compound represented by the general formula (Formula 7) to give a conjugated alkadienyl group. Metalization of.

This reaction may be carried out in a solvent in the temperature range of −78 ° C. to 100 ° C. in an inert atmosphere, similar to the ordinary metallization reaction. Examples of the solvent used at this time include aromatic hydrocarbon compounds such as benzene, toluene and xylene, saturated hydrocarbon compounds such as pentane, hexane, heptane, octane, nonane, decane, cyclopentane and cyclohexane, as well as diethyl ether, tetrahydrofuran, 1 Examples thereof include ether solvents such as 2,2-dimethoxyethane. The usage ratio of the organometallic compound to the conjugated alkadienyl group is 1 to 100 in a molar ratio.
Times, usually 1 to 10 times.

In the present invention, examples of the organometallic compound represented by the above general formula (Formula 7) include compounds in which M and R'in the formula are shown below.

R'is methyl, ethyl, propyl,
Alkyl groups such as butyl, phenyl, tolyl, xylyl,
Examples thereof include aryl groups such as benzyl, and examples of M include alkali metals of Group 1 of the periodic table such as lithium, sodium and potassium. Specifically, methyl lithium, butyl lithium, phenyl lithium, etc. can be illustrated.

In the present invention, a transition metal compound represented by the above general formula (Formula 8) is reacted with a compound obtained by introducing a conjugated alkadienyl group into an inorganic compound treated with an organosilicon compound and then metallizing the compound. Carry.

This reaction can be carried out in the above-mentioned hydrocarbon solvent or ether solvent, and further in a halogenated hydrocarbon solvent such as dichloromethane or 1,2-dichloroethane, but can of course be carried out without solvent. The reaction is the same as the above metallization reaction in an inert atmosphere at -78
Both components may be brought into contact with each other in a temperature range of ℃ to 100 ℃.
The molar ratio of the transition metal compound to the metallized compound is 0.1 to 1 time, usually 0.5 to 1 time.

In the present invention, examples of the transition metal compound represented by the above general formula (Formula 8) include compounds in which M ′ and X ′ are as shown below.

Examples of M'include transition metals of Groups 4 and 5 of the Periodic Table such as titanium, zirconium, hafnium, vanadium, niobium and tantalum, and X'includes fluorine, chlorine, bromine and iodine. The halogen atom of is exemplified. Specific examples include titanium tetrachloride, zirconium tetrachloride, hafnium tetrachloride, vanadium tetrachloride, niobium pentachloride, tantalum pentachloride, titanium tetrabromide, zirconium tetrabromide, hafnium tetrabromide, vanadium tetrabromide, pentaodor. Examples thereof include niobium bromide and tantalum pentabromide.

The transition metal catalyst supported on the inorganic compound in this manner has good properties as a solid catalyst component for use in gas phase or liquid phase polymerization of olefins,
The solid catalyst component obtained in the polymerization of olefins,
Used by contacting aluminoxane obtained by the reaction of alkylaluminum and water, or after contacting the obtained solid catalyst component and trialkylaluminum,
A compound containing an organic boron compound anion, an organic aluminum compound anion, etc. is reacted and used.

As the aluminoxane, a compound represented by the following general formula (Formula 9) or (Formula 10) (wherein R "is a hydrocarbon residue having 1 to 3 carbon atoms, and n is an integer of 1 to 50) Exemplified, as the use ratio of aluminoxane to the solid catalyst component, the molar ratio with the supported transition metal catalyst is 1 to 10
It is 0000 times, usually 1 to 5000 times.

[0032]

[Chemical 9]

[0033]

[Chemical 10]

Further, as a compound containing an organic boron compound anion, an organic aluminum compound anion, etc., (C ₆ H
₅ ) ₃ CB (C ₆ F ₅ ) ₄ , (C ₆ H ₅ ) ₃ CAl (C ₆ F ₅ ) _{4, and the} like. 0.1-10000 in molar ratio with metal catalyst
Times, usually 0.5 to 5000 times.

As the trialkylaluminum, triethylaluminum, triisobutylaluminum,
Examples thereof include tri-n-hexylaluminum and tri-n-octylaluminum. The proportion of trialkylaluminum used relative to the solid catalyst component is 1 to 10000 times the molar ratio with the supported transition metal catalyst, usually 1 to 10 times. 5000
Double.

Examples of the olefins used in the present invention include olefins having 2 to 25 carbon atoms, specifically ethylene, propylene, butene-1, pentene-1,
Hexene-1, Heptene-1, Octene-1, Nonene-
In addition to linear α-olefins such as 1, decene-1, undecene-1, dodecene-1, tridecene-1, tetradecene-1, pentadecene-1, hexadecene-1 and octadecene-1, 3-methylbutene-1 Examples include branched α-olefins such as 4-methylpentene-1,4,4-dimethylpentene-1, and cyclic olefins such as cyclopentene and norbornene. These olefins are used not only for homopolymerization but also for copolymerization with each other.

The polymerization conditions of the olefin are not particularly limited, and the solvent polymerization method using an inert medium, or
A bulk polymerization method or a gas phase polymerization method which does not substantially contain an inert medium can be used. The polymerization temperature is −100 to 200 ° C.,
The polymerization pressure is from normal pressure to 100 kg / cm ² .

[0038]

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

Example 1 (Synthesis of Organic Compound Having Hydroxyl Group and Conjugated Alkadienyl Group) 4-hydroxy group protected with trimethylsilyl group
Pyrrolidine 0.14 in 70 ml of methanol containing 0.116 mol of hydroxy-2-butanone and 0.280 mol of cyclopentadiene
8 mol was added dropwise at 0 ° C. over 30 minutes. The reaction was carried out at room temperature overnight, 0.210 mol of acetic acid was added at 0 ° C., and the diethyl ether-soluble portion was extracted. The diethyl ether solution was washed with water, dried over anhydrous sodium sulfate, and the volatile matter was distilled off to obtain 0.069 mol of methylhydroxyethylfulvene.

0.066 mol of fluorene in tetrahydrofuran
The solution was dissolved in 100 ml, 26.5 ml of an n-hexane solution containing 0.066 mol of n-butyllithium was added dropwise at -78 ° C, the temperature was gradually raised, and the reaction was carried out at room temperature for 3 hours. The reaction solution was cooled to −78 ° C. again, and after synthesis in the above reaction, 20 ml of a tetrahydrofuran solution containing 0.066 mol of methylhydroxyethylfulvene whose hydroxyl group was protected by a trimethylsilyl group was added dropwise over 30 minutes, and the temperature was gradually raised. Then, the mixture was reacted overnight at room temperature.

After adding a hydrochloric acid aqueous solution to the reaction solution at 0 ° C., the tetrahydrofuran layer was washed with water and dried over anhydrous sodium sulfate. The volatiles were distilled off and the remaining yellow solid was reprecipitated with ethanol / n-pentane to give a volume of 0.
0255 mol of cyclopentadienylfluorenylmethylhydroxyethylmethane were obtained. From the supernatant, an additional 0.0202 mol of the desired product was obtained.

(Reaction of Inorganic Compound Having Surface Hydroxyl Group with Organosilicon Compound and Synthesis of Transition Metal Catalyst Component) 10 g of silica gel (Davison Co. # 951) dehydrated for 6 hours at 200 ° C. under N ₂ flow in an autoclave of 300 ml. It was placed,
A glass container containing 41.2 mmol of dimethyldichlorosilane was fixed in the reactor and reacted at 150 ° C. for 10 hours to obtain 12.7 g of a reaction product.

To 3.0 g of the above product was added 70 ml of a toluene solution containing 5.3 mmol of cyclopentadienylfluorenylmethylhydroxyethyl methane, and the mixture was reacted overnight at room temperature.
The supernatant was removed by decantation and dried under reduced pressure to obtain a light brown solid.

This solid was suspended in 50 ml of tetrahydrofuran, and 10 ml of an n-hexane solution containing 24.62 mmol of n-butyllithium was added dropwise to this suspension at -78 ° C, and the temperature was gradually raised to room temperature and then overnight. It was made to react. The solvent was distilled off from the reaction solution under reduced pressure, the remaining solid component was washed with n-pentane, and dried under reduced pressure to obtain an orange solid.

The above solid and 0.8 g of zirconium tetrachloride were mixed, 60 ml of dichloromethane was added at -78 ° C, the temperature was gradually raised, and the mixture was reacted at room temperature for 2 days. After removing the supernatant by decantation, it was dried under reduced pressure to obtain 3.9 g of a yellow-orange solid.

(Polymerization of propylene) 500 mg of the above catalyst component
And methylaluminoxane (manufactured by Tosoh Akzo Co., Ltd.)
1.0 g was put into an autoclave having an internal volume of 5 liters, 1.5 kg of propylene was added, and polymerization was carried out at 60 ° C. for 2 hours. Unreacted propylene was purged and the polymer was taken out and dried to obtain 22.9 g of syndiotactic polypropylene.
The intrinsic viscosity (hereinafter referred to as η) measured with a 135 ° C. tetralin solution of this polypropylene is 0.72, the ratio of the weight average molecular weight and the number average molecular weight measured with 1,2,4-trichlorobenzene (hereinafter referred to as MW / MN). Is 2.4),
The syndiotacticity in 13 C-NMR is 0.82.
It was 9.

Example 2 (Synthesis of Organic Compound Having Hydroxyl Group and Conjugated Alkadienyl Group) Synthesis was carried out in exactly the same manner as in Example 1.

(Reaction of Inorganic Compound Having Surface Hydroxyl Group with Organosilicon Compound and Synthesis of Transition Metal Catalyst Component) The same procedure as in Example 1 was carried out except that 10 g of γ-alumina (manufactured by Degussa) was used instead of 10 g of silica gel. , Reaction products
Obtained 11.3 g.

To 3.0 g of the above product was added 50 ml of a tetrahydrofuran solution containing 3.3 mmol of cyclopentadienylfluorenylmethylhydroxyethyl methane, and the mixture was reacted overnight at room temperature. Then, 20 ml of tetrahydrofuran was added, and 30.16 mmol of n-butyllithium was added. 10 ml of n-hexane solution containing -78
The mixture was added dropwise at 0 ° C., the temperature was gradually raised to room temperature, and then the reaction was carried out overnight. The solvent was distilled off from the reaction solution under reduced pressure, the remaining solid component was washed with n-pentane, and dried under reduced pressure to obtain a red solid.

The above solid was suspended in 50 ml of n-pentane,
Suspension of n-pentane containing 0.7 g of zirconium tetrachloride 50
ml was mixed, reacted at room temperature for 2 days, and the supernatant was removed by decantation. The remaining solid was washed with n-pentane and dried under reduced pressure to obtain a yellow-orange solid (5.2 g).

(Polymerization of Propylene) Polymerization was carried out in the same manner as in Example 1 to produce syndiotactic polypropylene 1
8.7g was obtained. Η of this polypropylene is 0.46, MW /
MN is 2.4 and syndiotacticity is 0.800
Met.

[0052]

Industrial Applicability By using the catalyst obtained by the present invention, it is possible to produce a polyolefin with high productivity, which is industrially valuable.

[Brief description of drawings]

FIG. 1 is a flow chart for facilitating understanding of the present invention.

Claims (2)

[Claims] 1. A compound represented by the following general formula (1) (wherein A and B are the same or different from each other, a conjugated alkadienyl group, C and D):
Are the same or different from each other, and a hydrocarbon residue having 1 to 50 carbon atoms having at least one hydroxyl group on one or both, E is an organic compound represented by carbon, silicon, germanium, tin) [Chemical 1] An inorganic compound having a surface hydroxyl group is contacted with a compound treated with an organic silicon compound represented by the following general formula (2) (wherein R is a hydrocarbon residue having 1 to 20 carbon atoms and X is a halogen atom): ## STR00002 ## R ₂ SiX _{2 The} obtained compound is represented by the following general formula (3) wherein M is a metal atom selected from the first group of the periodic table, and R'is a hydrocarbon residue having 1 to 20 carbon atoms. After the metallization treatment with the organometallic compound represented by the formula (3), MR 'is represented by the following general formula (4) in which M'is the group 4 or 5 of the periodic table.
A method for producing a solid catalyst component for olefin polymerization, which comprises bringing into contact with a transition metal compound represented by a metal atom selected from the group, X'is a halogen atom). [Chemical 4] M'X ' 2. A method for polymerizing an olefin, which comprises polymerizing an olefin by using the solid catalyst component according to claim 1.