JP3258977B2 - Olefin polymerization method - Google Patents

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 the catalyst component, and more particularly to a method for producing a metallocene catalyst for producing a polyolefin and an olefin using the same. And a polymerization method.

[0002]

2. Description of the Related Art There is known a method of polymerizing a metallocene compound having a group having a conjugated π electron, particularly cyclopentadiene or a derivative thereof as a ligand, and an olefin using a catalyst of methylaluminoxane obtained by reacting trimethylaluminum with water. ing. For example, Japanese Patent Application Laid-Open No. 58-19309 discloses a method for polymerizing olefins using biscyclopentadienyl zirconium dichloride and methylaluminoxane as catalysts.

[0003]

SUMMARY OF THE INVENTION The above-mentioned Japanese Patent Application Laid-Open No. 58-19309 is disclosed.
The method by which the activity per transition metal is large and is an excellent method, but the bulk specific gravity of the resulting polymer after polymerization is small, handling is difficult, and when applied to a gas phase or liquid phase polymerization method, There are problems in using these as catalysts for polyolefin production on an industrial scale, such as adhesion of the polymer to the vessel wall, making it difficult to remove heat due to poor heat transfer, and the formation of polymer agglomerates. there were.

[0004]

Means for Solving the Problems The present inventors have solved the above-mentioned problems and have intensively studied a method for producing a polyolefin with high productivity with high productivity, and completed the present invention.

That is, the present invention relates to 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, and one or both have at least one hydroxyl group. 1-50 carbon atoms
A hydrocarbon residue, E is an atom selected from carbon, silicon, germanium, and tin);

[0006]

Embedded image A compound obtained by treating an inorganic compound having a surface hydroxyl group with an organosilicon compound represented by the following general formula (where R is a hydrocarbon residue having 1 to 20 carbon atoms and X is a halogen atom)

[0007]

Embedded image An organometallic compound represented by the following general formula (where M is a metal atom selected from Group 1 of the periodic table, and R 'is a hydrocarbon residue having 1 to 20 carbon atoms): After metallizing with

[0008]

Embedded image A solid catalyst for olefin polymerization, which is brought into contact with a transition metal compound represented by the following general formula (8), wherein M 'is a metal atom selected from titanium, zirconium and hafnium, and X' is a halogen atom. An olefin polymerization method comprising the steps of producing a component and polymerizing an olefin using the solid catalyst component.

[0009]

Embedded image

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 (Chemical Formula 5) and an inorganic compound having a surface hydroxyl group are combined with an organic silicon compound represented by the general formula (Chemical Formula 6). The compound treated with the compound is reacted to introduce a conjugated alkadienyl group on the inorganic compound.

The method of treating an inorganic compound having a surface hydroxyl group with an organosilicon compound is preferably carried out by bringing the two into contact in an autoclave at a temperature of 0 to 300 ° C. The use ratio of the organosilicon compound to the inorganic compound having a surface hydroxyl group is from 1 to 100,000 times, usually from 1 to 1000 times in molar ratio to 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 the like, or a saturated hydrocarbon compound such as pentane, hexane, heptane, octane, nonane, decane, cyclopentane, and cyclohexane. The ratio of the organic compound having a hydroxyl group and a conjugated alkadienyl group to be used is as follows.
The amount is from 01 to 10,000 mmol, usually from 0.1 to 100 mmol.

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

A and B are, for example, a monocyclic or polycyclic conjugated alkadienyl group having 5 to 30 carbon atoms. Specifically, a cyclopentadienyl group or a part or all of the hydrogen is substituted with a carbon atom. A compound substituted with an alkyl group of 1 to 10 (here, the alkyl group may have a structure in which the terminal is bonded to a cyclopentadiene ring again), an indenyl group, a fluorenyl group, or part or all of 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 C1 to C50 hydrocarbon residue having at least one hydroxyl group in one or both. 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, cyclopentadienylfluorenylmethylhydroxymethyl Phenylethylmethane and the like.

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

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

Examples of R include an alkyl group such as methyl, ethyl, propyl and butyl, and an aryl group such as phenyl, tolyl, xylyl and benzyl. X represents fluorine,
Halogen atoms such as chlorine, bromine and iodine are exemplified.

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

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

This reaction may be carried out in a solvent at a temperature in the range of -78 ° C to 100 ° C in an inert atmosphere in the same manner as a usual metalation reaction. Solvents 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, and the like. And ether solvents such as 2,2-dimethoxyethane. The use ratio of the organometallic compound to the conjugated alkadienyl group is 1 to 100 in molar ratio.
Times, usually 1 to 10 times.

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

R ′ is methyl, ethyl, propyl,
Alkyl groups such as butyl, phenyl, tolyl, xylyl,
Examples of the aryl group include benzyl and the like, and examples of M include an alkali metal of Group 1 of the periodic table such as lithium, sodium, and potassium. Specific examples include methyllithium, butyllithium, phenyllithium and the like.

In the present invention, a conjugated alkadienyl group is introduced into an inorganic compound which has been treated with an organosilicon compound, and then a metalated compound is reacted with a transition metal compound represented by the above general formula (Formula 8). Carrying is carried out.

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, 1,2-dichloroethane or the like. The reaction was carried out in an inert atmosphere at -78
What is necessary is just to make both components contact in the temperature range of 100 degreeC to 100 degreeC.
The molar ratio of the transition metal compound to the metalated compound is 0.1 to 1 times, usually 0.5 to 1 times.

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

Examples of M ′ include transition metal atoms selected from titanium, zirconium and hafnium, X ′ is fluorine,
Halogen atoms such as chlorine, bromine and iodine are exemplified. Specific examples include titanium tetrachloride, zirconium tetrachloride, hafnium tetrachloride, titanium tetrabromide, zirconium tetrabromide, and hafnium tetrabromide.

The transition metal catalyst thus supported on the inorganic compound has good properties as a solid catalyst component for use in gas-phase or liquid-phase polymerization of olefins.
In the polymerization of the olefin, the obtained solid catalyst component,
After contacting the aluminoxane obtained by the reaction between the alkyl aluminum and water, or after contacting the obtained solid catalyst component with the trialkyl aluminum,
A compound containing an organic boron compound anion, an organic aluminum compound anion, or the like is used by reacting.

As the aluminoxane, a compound represented by the following general formula (Chemical formula 9) or (Chemical formula 10) (wherein, R ″ is a hydrocarbon residue having 1 to 3 carbon atoms, and n is an integer of 1 to 50) Illustrative, 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]

Embedded image

[0033]

[Formula 10]

Compounds containing an organoboron compound anion, an organoaluminum compound anion and the like include (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 to 10,000 in molar ratio with metal catalyst
Times, usually 0.5 to 5000 times.

As the trialkyl aluminum, triethyl aluminum, triisobutyl aluminum,
Tri-n-hexylaluminum, tri-n-octylaluminum and the like can be exemplified, and the usage ratio of trialkylaluminum to the solid catalyst component is 1 to 10,000 times, usually 1 to 10 times, in molar ratio with the supported transition metal catalyst. 5000
It is twice.

Examples of the olefin 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-
1, decene-1, undecene-1, dodecene-1, tridecene-1, tetradecene-1, pentadecene-1, hexadecene-1, octadecene-1, etc., and 3-methylbutene-1 , 4-methylpentene-1, 4,4-dimethylpentene-1 and the like, and cyclic olefins such as cyclopentene and norbornene. These olefins are used not only for homopolymerization but also for mutual copolymerization.

The olefin polymerization conditions are not particularly limited, and may be a solvent polymerization method using an inert medium,
A bulk polymerization method or a gas phase polymerization method in which substantially no inert medium is present can be used. The polymerization temperature is -100 to 200 ° C,
The polymerization pressure is from normal pressure to 100 kg / cm ² .

[0038]

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

Example 1 (Synthesis of an organic compound having a hydroxyl group and a conjugated alkadienyl group) 4-hydroxy compound having a hydroxyl group protected by a trimethylsilyl group
0.14 mol of hydroxy-2-butanone and 0.280 mol of cyclopentadiene were added to 0.14 mol of pyrrolidine in 70 ml of methanol.
8 mol was added dropwise at 0 ° C. over 30 minutes. The reaction was carried out at room temperature overnight, 0.20 mol of acetic acid was added at 0 ° C., and the diethyl ether soluble part was extracted. The diethyl ether solution was washed with water and dried over anhydrous sodium sulfate, and then volatile components were distilled off to obtain 0.069 mol of methylhydroxyethylfulvene.

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

After an aqueous solution of hydrochloric acid was added 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 obtain 0.1.
0255 mol of cyclopentadienylfluorenylmethylhydroxyethylmethane were obtained. An additional 0.0202 mol of the desired product was obtained from the supernatant.

(Reaction of Inorganic Compound Having Surface Hydroxyl Group with Organosilicon Compound and Synthesis of Transition Metal Catalyst Component) In a 300 ml autoclave, 10 g of silica gel (# 951 manufactured by Devison) was dehydrated at 200 ° C. for 6 hours under a stream of N _2. It was placed,
A glass container containing 41.2 mmol of dimethyldichlorosilane was fixed in a 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 cyclopentadienylfluorenylmethylhydroxyethylmethane, and the mixture was reacted at room temperature overnight.
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 at −78 ° C. to the suspension. Reacted. The solvent was distilled off from the reaction solution under reduced pressure, and 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., and the temperature was gradually raised, followed by reaction at room temperature for 2 days. After the supernatant was removed by decantation, drying under reduced pressure gave 3.9 g of a yellow-orange solid.

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

Example 2 (Synthesis of an organic compound having a hydroxyl group and a conjugated alkadienyl group) Synthesis was performed in 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
11.3 g was obtained.

To 3.0 g of the above product, 50 ml of a tetrahydrofuran solution containing 3.3 mmol of cyclopentadienylfluorenylmethylhydroxyethylmethane was added, and the mixture was reacted at room temperature overnight. Then, 20 ml of tetrahydrofuran was added, and 30.16 mmol of n-butyllithium was added. 10 ml of an n-hexane solution containing
C., and the temperature was gradually raised to room temperature, and then the reaction was performed overnight. The solvent was distilled off from the reaction solution under reduced pressure, and 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,
A suspension 50 of n-pentane containing 0.7 g of zirconium tetrachloride
Then, the mixture was 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 5.2 g of a yellow-orange solid.

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

[0052]

By using the catalyst obtained by the present invention, it is possible to produce a polyolefin with high productivity, and its industrial value is high.

[Brief description of the drawings]

FIG. 1 is a flowchart for helping an understanding of the present invention.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-4-283205 (JP, A) JP-A-58-27705 (JP, A) JP-A-60-149605 (JP, A) JP-A-1- 292008 (JP, A) (58) Field surveyed (Int. Cl. ⁷ , DB name) C08F 4/60-4/70

Claims (1)

(57) [Claims] 1. A compound represented by the following general formula (1) wherein A and B are the same or different conjugated alkadienyl groups, C and D are the same or different, and one or both have carbon atoms having at least one hydroxyl group. An organic compound represented by 1 to 50 hydrocarbon residues, E is an atom selected from carbon, silicon, germanium and tin); A compound obtained by treating an inorganic compound having a surface hydroxyl group with an organosilicon compound represented by the following general formula (wherein R is a hydrocarbon residue having 1 to 20 carbon atoms and X is a halogen atom): Embedded image An organometallic compound represented by the following general formula (where M is a metal atom selected from Group 1 of the periodic table, and R 'is a hydrocarbon residue having 1 to 20 carbon atoms): After metallizing with The following general formula (4) wherein M ′ is titanium, zirconium,
Metal atom selected from hafnium, X 'is a halogen atom)
A method for polymerizing olefins, comprising polymerizing an olefin using a solid catalyst component produced by contacting with a transition metal compound represented by the formula: Embedded image