JPH0693030A - Production of solid catalyst component for polymerization of olefin - Google Patents

Abstract

PURPOSE:To produce a catalyst exhibiting high activity and large particle size, free of fine particles, having a high bulk specific gravity and capable of producing a poly-alpha-olefin with a high productivity by bringing an aluminoxane into contact with an inorganic oxide and bringing a transition metal, water, etc., into contact therewith. CONSTITUTION:This method is for producing a solid catalyst by hydrolyzing a trialkylaluminum with water, bringing the resultant aluminoxane of formula I or II (R is a 1 to 4C hydrocarbon residue; n is 1 to 50) into contact with a hydrous or anhydrous inorganic oxide and further bringing the obtained solid catalyst into contact with a transition metal compound represented by formula III or IV (A and B are each a univalent or divalent unsaturated hydrocarbon residue, etc.; R is, e.g. a straight chain saturated hydrocarbon residue containing a divalent nitrogen, etc.; M is a metal belonging to 4 or 5 group in the periodic table; X is, e.g. a halogen bonded to M). In this invented method, a transition metal compound is brought into contact with a solid catalyst component prepared by bringing an aluminoxane into contact with an inorganic oxide and water or oxygen is subsequently brought into contact therewith.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for producing a solid catalyst component for olefin polymerization. Specifically, a solid catalyst component obtained by carrying out a catalytic reaction of aluminoxane with an inorganic oxide is brought into contact with a transition metal compound, and then water and / or oxygen is subjected to a contact treatment to produce a solid catalyst component for olefin polymerization. how to. Alternatively, it relates to a method for producing a solid catalyst component for olefin polymerization by contacting a transition metal compound after a contact treatment of water and / or oxygen with a solid catalyst component obtained by reacting an aluminoxane with an inorganic oxide in advance.

[0002]

As an olefin polymerization catalyst, a transition metal compound such as a metallocene compound having a group having a conjugated π electron, particularly cyclopentadiene and its derivative as a ligand, and an alkyl obtained by the reaction of trialkylaluminum and water. A combination with aluminoxane is known. For example, JP-A-58-19309 discloses a method for polymerizing biscyclopentadienyl zirconium dichloride and olefins using methylaluminoxane as a catalyst, and JP-A-61-130314 and JP-A-61-264010. Kohei
1-301704 and JP-A-2-41303 disclose isotactic poly α-olefins or syndiotactic poly α-
Process for producing olefins and their stereoregular poly α-
Polymerization catalysts for producing olefins are disclosed.

[0003]

The above method is an excellent method in that the activity per transition metal is good, and the stereoregularity and tacticity of the obtained polymer can be selected depending on the kind of the transition metal compound used. However, there is a problem in that the obtained polymer has a small particle size, a bulk specific gravity is small, the properties of the polymerization slurry are poor, and the heat of polymerization cannot be removed, resulting in poor productivity.

In order to solve these problems, we have already proposed to use a transition metal compound and an aluminoxane in combination with an organic aluminum compound as a solid catalyst component supported on an inorganic oxide. That is, it was found that the polymerization activity was low only by using the solid catalyst at the time of polymerization, and the above problem could be solved only by adding an organoaluminum compound and having sufficient activity.

The aluminoxane supported on the inorganic oxide includes those supported chemically by a carrier component and those supported by an action such as adsorption. In any case, the aluminoxane supported on the carrier is insoluble in the solvent, but as shown in JP-A 1-258686, the aluminoxane insoluble in the solvent becomes soluble in the solvent again by being treated with alkylaluminum. It is known that Therefore, when the organoaluminum compound is added to the solid catalyst component supporting the transition metal compound and the aluminoxane on the inorganic oxide, a part of the aluminoxane becomes solubilized,
A fine powdery polymer is likely to be formed during the polymerization. Therefore, the polymerization by this method had no problem in batch reaction or short-time continuous polymerization, but there was a problem that the polymer adhered to the wall of the polymerization vessel when the continuous polymerization was performed for a long time. It was

[0006]

Means for Solving the Problems The inventors of the present invention have solved the above problems by using a method of producing a highly active poly α-olefin having a relatively large bulk density and a small particle size with a small amount of fine powder with high productivity. The present invention has been completed through intensive studies.

That is, the present invention provides the following general formula (Formula 5) or (Formula 6) obtained by hydrolyzing a trialkylaluminum (wherein R is a hydrocarbon residue having 1 to 4 carbon atoms,
n is an integer of 1 to 50. ) The aluminoxane represented by

[0008]

[Chemical 5]

[0009]

[Chemical 6] A solid catalyst component obtained by carrying out catalytic reaction with an inorganic oxide having anhydrous or 10% by weight or less of adsorbed water is further added to the following general formula (Chemical formula 7) or (Chemical formula 8) (in the formulas, A and B). Is a monovalent or divalent unsaturated hydrocarbon residue, or M
Are the same or different ligands each containing a nitrogen atom, an oxygen atom, a silicon atom, a phosphorus atom or a sulfur atom bonded to, and A ′ and B ′ are the same or different monovalent or divalent bridged by R. A valent unsaturated hydrocarbon residue or a ligand containing a nitrogen atom, an oxygen atom, a phosphorus atom or a sulfur atom bonded to M, and R is a divalent nitrogen atom, an oxygen atom, a silicon atom or a phosphorus atom. Or, a residue containing a sulfur atom or a linear saturated hydrocarbon residue which may have a side chain or a part or all of the carbon atoms of the linear chain thereof is substituted with a silicon atom, a germanium atom or a tin atom. A residue, M is a metal atom selected from Group 4 or 5 of the periodic table, and X
Is a transition metal compound represented by a ligand containing a halogen atom, a carbon atom, a nitrogen atom, an oxygen atom, a silicon atom, a boron atom, a phosphorus atom or a sulfur atom bonded to M),

[0010]

[Chemical 7]

[0011]

[Chemical 8] In producing a solid catalyst component for olefin polymerization which is brought into contact with the solid catalyst component obtained by reacting the aluminoxane with an inorganic oxide, or after contacting a transition metal compound with the solid catalyst component, water and And / or a method for producing a solid catalyst component for olefin polymerization, which comprises subjecting it to a contact treatment with oxygen.

Examples of the solvent used in the preparation or polymerization or treatment of the catalyst using the catalyst component of the present invention include propane, butane, isobutane, pentane, hexane, heptane, octane, nonane, decane, cyclopentane, cyclohexane, Saturated hydrocarbon compounds such as cycloheptane and methylcyclohexane, aromatic hydrocarbon compounds such as benzene, toluene and xylene, and halogenated hydrocarbon compounds such as methylene chloride and chlorobenzene can also be used.

Examples of the aluminoxane used in the present invention include compounds represented by the above general formula (Chemical formula 5) or (Chemical formula 6) obtained by hydrolyzing trialkylaluminum, and among these, R is particularly preferable. A methylaluminoxane which is a methyl group and n is 5 or more is preferably used.

The inorganic oxide used in the present invention includes:
_{SiO 2, Al 2 O 3,} CaO, Na 2 O, K 2 O, MgO, MnO, TiO 2,
Various oxides such as ZrO ₂ and those having cavities inside, those with relatively large pores and large surface area can be preferably used, and hollow inorganic oxides, oxide gels, etc. can also be used,
Usually, those having a diameter of about 1 μm to 0.1 mm can be preferably used. Of these, those containing silica gel or alumina are preferable because the amounts of the transition metal compound and aluminoxane supported can be increased.

The inorganic oxide is usually used after being calcined and dried before supporting the transition metal compound and the aluminoxane, but it may be an anhydride or may have adsorbed water of 10% by weight or less. Aluminoxanes are considered to be insoluble by reacting with the hydroxyl groups on the surface of these inorganic oxides, so the concentration of hydroxyl groups on the surface decreases when baked at high temperature, and the amount of aluminoxane supported on the surface of the aluminoxane decreases, thus reducing the amount of aluminoxane per catalyst. This is not preferable because the working level will decrease.

On the other hand, there is a method in which adsorbed water is contained in these inorganic oxides in order to increase the supported amount of aluminoxane. However, when the adsorbed water having 10% by weight or more of adsorbed water is used, the aluminoxane is adsorbed. Since it is only insolubilized with water and supported, it is not preferable because it is dissolved in the toluene solution when reacted with the organoaluminum compound in the toluene solution.

According to the present invention, a transition metal compound is brought into contact with a solid catalyst component obtained by reacting an aluminoxane with an inorganic oxide, or the solid catalyst component is treated with water and / or oxygen. It is possible to obtain an olefin polymerization solid catalyst component which is not dissolved in a toluene solution even when it is reacted with an organoaluminum compound in a toluene solution.

As a method for treating an inorganic oxide used as a carrier with an aluminoxane, it is preferable to first sufficiently react the inorganic oxide containing adsorbed water with an aluminoxane at a temperature higher than room temperature. After the substance is dispersed, it can be effectively supported by treating it at a predetermined temperature for a predetermined time.

Specifically, the reaction temperature is preferably 50 ° C. or higher. If the reaction temperature is lower than 50 ° C., the reaction time becomes long, and many components are unreacted and dissolved in the toluene solution when reacted with the organic aluminum in the toluene solution. Therefore, it is not preferable. The high temperature side is not particularly limited, but is usually 200 ° C or lower. The reaction time is not particularly limited, but is usually 1 hour or more and 150 hours or less. After loading, the unreacted aluminoxane solution is separated. The separation method is not particularly limited, and the supernatant may be separated after solid-liquid separation by standing or the like. If necessary, a solid catalyst component can be obtained by washing with a solvent such as a hydrocarbon compound to remove unsupported aluminoxane.

Examples of the transition metal compound used in the present invention include the compounds described in the above-mentioned documents. In addition, the transition metal compound represented by the general formula (Chemical formula 7) or (Chemical formula 8) is also used. It is illustrated.

Examples of the unsaturated hydrocarbon residue represented by A and B include monocyclic or polycyclic groups having conjugated π electrons having 5 to 50 carbon atoms, and specific examples thereof include cyclopetadienyl. Alternatively, a part or all of hydrogen thereof is replaced with a hydrocarbon residue having 1 to 10 carbon atoms (wherein the hydrocarbon residue may have a structure in which the terminal is again bound to the cyclopentadiene ring). ), Or a polycyclic aromatic hydrocarbon residue such as indenyl or fluorenyl, or one in which a part or all of the hydrogen thereof is replaced with a hydrocarbon residue having 1 to 10 carbon atoms. Also,
Nitrogen atom bonded to M, an oxygen atom, a silicon atom, examples of ligand containing phosphorus atom or a sulfur atom COR ', NR' _2, O
R ', OSiR' ₃ , SiR ' ₃ , GeR' ₃ , PR ' ₂ , POR' ₂ , SR ', S
Examples thereof include ligands represented by OR 'and SO ₂ R' (R 'is hydrogen or a hydrocarbon having 1 to 20 carbon atoms or a residue in which some of them are substituted with heteroatoms). These may be the same as or different from each other.

The ligand represented by A'or B'is
Monocyclic or polycyclic conjugated π-electrons with 5 to 50 carbon atoms
Groups with children, COR ', NR'₂, OR ', OSiR'₃, SiR '₃ ,
GeR ' ₃ , PR '₂, POR '₂ , SR ', SOR', SO₂R '(R' is hydrogen
Or a hydrocarbon having 1 to 20 carbon atoms or one of them
Transition represented by a residue in which one or more of the atoms are replaced by a hetero atom
The ligand bonded to the metal atom M is exemplified. these
May be the same or different from each other. Where A'and
And R'of B'has a structure bridged by R
is there.

The divalent group represented by R includes -O- and -S-.
, -SS-, -SO-, -SO _2- , -CO-, -NR "-, -PR"-, -PO
R "-, -OSiR" ₂ O- or a methylene group represented by the following general formula (Formula 9) or a part or all of the carbon atoms of the methylene group is substituted with a silicon atom, a germanium atom or a tin atom. Examples are silylene groups, germylene groups, and stannylene groups.

[0024]

[Image Omitted]-(R " ₂ C) n- (R" ₂ Si) m- (R " ₂ Ge) p- (R" ₂ Sn) q- (wherein R "is a hydrogen atom or a carbon atom number 1 2 R ″ may represent the same or different and n, m, p and q are integers of 0 to 4 and the following formula 1 ≦
It represents an integer satisfying n + m + p + q ≦ 4. )

X is a halogen atom such as fluorine, chlorine, bromine or iodine, or CR ' ₃ , CH ₂ SiR' ₂ , COR ', NR' ₂ , OR ',
OSiR ' ₃ , SiR' ₃ , GeR ' ₃ , PR' ₂ , POR ' ₂ , SR', SOR ',
SO ₂ R ′ (R ′ is hydrogen or a hydrocarbon having 1 to 20 carbon atoms or a residue in which some of them are substituted with a hetero atom) and the like can be exemplified.

The aluminoxane is used in an amount of 1 to 10000 mol times, usually 10 to 5000, relative to the above transition metal compound.
It is mole times.

The transition metal compound can be supported by dispersing the aluminoxane-supported carrier in a solution of the transition metal compound. The temperature for supporting the transition metal compound is not particularly limited, but is usually 0 ° C to
It is performed at 100 ° C.

What is important in the present invention is the catalytic treatment of the solid catalyst component obtained by the above-mentioned method with water and / or oxygen. Specifically, (1) a method in which a support obtained by catalytically reacting aluminoxane with an inorganic oxide is previously contacted with water and / or oxygen and then a transition metal compound is contacted. (2) In this method, a transition metal compound is brought into contact with the carrier and then water and / or oxygen is brought into contact therewith to obtain a solid catalyst component for olefin polymerization. Here, the term "contacting with water and / or oxygen" means that the above-mentioned carrier or the solid catalyst component for olefin polymerization is directly contacted with water vapor, oxygen or air, or the catalyst component is dispersed in a solvent. Examples thereof include a method in which a solvent containing water is added thereto, or a gas containing water vapor or oxygen is blown in to carry out contact treatment.

The solid catalyst component for olefin polymerization thus synthesized can be used as it is as a polymerization catalyst. Further, an organoaluminum compound can be used together during the polymerization.

As the organoaluminum compound used in combination with the above-mentioned solid catalyst component for olefin polymerization during the polymerization, trialkylaluminum having 2 to 3 alkyl residues having 1 to 12 carbon atoms, dialkylaluminum halide and the like can be used. Specifically, trimethyl aluminum, triethyl aluminum, tri-n-propyl aluminum, triisopropyl aluminum, tributyl aluminum,
Triisobutyl aluminum, tripentyl aluminum, trihexyl aluminum, triheptyl aluminum, trioctyl aluminum, tridecyl aluminum, isoprenyl aluminum, dimethyl aluminum hydride, diethyl aluminum hydride,
Examples thereof include dipropyl aluminum hydride, diisopropyl aluminum hydride, dibutyl aluminum hydride, dibutyl aluminum hydride, dimethyl aluminum chloride, diethyl aluminum chloride, dipropyl aluminum chloride, diisopropyl aluminum chloride, dibutyl aluminum chloride and dibutyl aluminum chloride.

In the present invention, olefins include propylene, butene-1, pentene-1, hexene-1, heptene.
-1, octene-1, nonene-1, decene-1, undecene-1,
Linear α such as dodecene-1, tridecene-1, tetradecene-1, pentadecene-1, hexadecene-1, octadecene-1
-In addition to olefins, 3-methylbutene-1,4-methylpentene-1,4,4-dimethylpentene-1 and other branched α-olefins, cyclopentene, cyclooctene norbornene and other cyclic olefins are exemplified, and these α- Not only olefins alone but also mixtures with one another or with small amounts of ethylene and dienes are indicated.

The polymerization conditions are not particularly limited, and a solvent polymerization method using an inert medium, a bulk polymerization method substantially free of an inert medium, or a gas phase polymerization method can be used.
As the polymerization temperature and the polymerization pressure, general conditions used in a known method are used, and as the polymerization temperature, -100 to
It is common to carry out at 200 ° C. and a polymerization pressure of atmospheric pressure to 100 kg / cm ² -G.

[0033]

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

Example 1 Methylaluminoxane (manufactured by Tosoh Akzo, polymerization degree 1
6.2) 254 g was dissolved in 1500 ml of toluene and placed in a 4-liter flask, and silica gel (manufactured by Fuji Divison Co., HT
G30908 was dried under reduced pressure at room temperature for 4 hours, and the amount of adsorbed water was 8% by weight. 300 g) was dispersed and the temperature was raised with stirring to reflux for 8 hours. Then filter under a nitrogen stream,
Then, wash with 1000 ml of toluene three times to remove excess methylaluminoxane, and further wash with 1000 ml of n-hexane.
It was washed twice and dried under reduced pressure to obtain silica gel supporting aluminoxane.

Next, 17.8 g of diphenylmethylene (cyclopentadienyl-2,6-di-tert-butylfluorenyl) zirconium dichloride synthesized according to a conventional method was added to 400
It was dissolved in 1 ml of toluene, 432 g of silica gel supporting aluminoxane was suspended in 1 liter of toluene, and the mixture was stirred at room temperature for 2 hours. Then, the operation of filtering under a nitrogen stream and further washing with 1000 ml of toluene was repeated 5 times, and then dried under reduced pressure to obtain 425.4 g of a solid catalyst component (A).

Further, 104 g of the solid catalyst component (A) was washed three times with 2000 ml of toluene containing 0.54 g of water and dried under reduced pressure to obtain 92 g of the solid catalyst component (B). Solid catalyst component thus obtained
(B) 0.5 g and triisobutylaluminum 0.9 g are put in a 5 liter autoclave and 1.5 kg of propylene is added.
Polymerization was carried out at ℃ for 2 hours, unreacted propylene was purged, the polymer was taken out, dried and weighed to obtain 836 g of polymer. The bulk specific gravity of this polymer is 0.41 g / ml,
No polymer adhered to the polymerizer wall, and no fine powder passed through a 200-mesh standard sieve. According to ¹³ C-NMR, the syndiotactic pentad fraction was 0.81.
The intrinsic viscosity (hereinafter referred to as η) measured with a tetralin solution at 1.2 ° C is 1.21, 1,2,4-trichlorobenzene as the solvent G
The ratio of the weight average molecular weight to the number average molecular weight measured by PC (hereinafter referred to as MW / MN) was 2.5.

Comparative Example 1 Polymerization of propylene was carried out in the same manner as in Example 1 except that 0.5 g of the solid catalyst component (A) was used instead of the solid catalyst component (B) without washing with toluene containing water. Then, 1025 g of a polymer was obtained. The bulk specific gravity of this polymer was 0.38 g / ml, and no polymer adhered to the wall of the polymerization vessel, but 1.5% of fine powder passed through a 200-mesh standard sieve. Again ¹³
The syndiotactic pentad fraction is 0 according to C-NMR.
It was 81, η was 1.59, and MW / MN was 2.8.

Example 2 Diphenylmethylene (cyclopentadienyl-2,6-di-tert-butylfluorenyl) in the synthesis of solid catalyst components
A solid catalyst component (C) was obtained in the same manner as in Example 1 except that isopropenyl (cyclopentadienyl-1-fluorenyl) zirconium dichloride was used instead of zirconium dichloride. Further, 105 g of the solid catalyst component (C) was added to 1
It was washed 3 times with 2000 ml of toluene which had been blown in for a while, and dried under reduced pressure to obtain 98 g of a solid catalyst component (D).

Polymerization of propylene was carried out in the same manner as in Example 1 using 0.5 g of the thus obtained solid catalyst component (D) to obtain 321 g of a polymer. The bulk specific gravity of this polymer is
It is 0.38 g / ml, there is no adhesion of polymer on the polymerization vessel wall,
No fines passed through the 200 mesh standard sieve. Also
According to ¹³ C-NMR, the syndiotactic pentad fraction is
It was 0.82, η was 0.81 and MW / MN was 2.2.

Comparative Example 2 Polymerization of propylene was carried out in the same manner as in Example 2 except that 0.5 g of the solid catalyst component (C) was used instead of the solid catalyst component (D) without washing with air-blown toluene. Where 87
6 g of polymer was obtained. The bulk specific gravity of this polymer is 0.38 g /
There was no polymer attached to the wall of the polymerization vessel,
1.7% of the fines passed through a 200 mesh standard sieve.
According to ¹³ C-NMR, the syndiotactic pentad fraction was 0.82, η was 0.81 and MW / MN was 2.4.

Example 3 100 g of methylaluminoxane-supported silica gel obtained in the same manner as in Example 1 was washed 3 times with 2000 ml of toluene in which air was blown for 1 hour, and dried under reduced pressure to 250 m.
17.8 g of diphenylmethylene (cyclopentadienyl-2,6-di-tert-butylfluorenyl) zirconium dichloride was dissolved in 400 ml of toluene and stirred at room temperature for 2 hours. Then, the procedure of filtering under a nitrogen stream and further washing with 1000 ml of toluene was repeated 5 times and then dried under reduced pressure to obtain 96 g of a solid catalyst component (E).

0.5 g of the solid catalyst component (E) thus obtained and 0.9 g of triisobutylaluminum were placed in a 5 liter autoclave, 1.5 kg of propylene was added, and the mixture was polymerized at 60 ° C. for 2 hours. The polymer was taken out, dried and weighed to obtain 514 g of a polymer.
The bulk specific gravity of this polymer was 0.40 g / ml, no polymer adhered to the wall of the polymerization vessel, and no fine powder passed through a 200-mesh standard sieve. According to ¹³ C-NMR, the syndiotactic pentad fraction was 0.81, η was 1.25 and MW / MN.
Was 2.3.

Example 4 Methylaluminoxane (manufactured by Tosoh Akzo, polymerization degree 1
Solid catalyst component (F) was obtained in the same manner as in Example 2 except that 2 g of Aluminum Oxide C (containing 3% by weight of adsorbed water) manufactured by Japan Aerosil Co., Ltd. was added to 40 ml of a 20 wt% toluene solution of 6.2), instead of silica gel. Further, the solid catalyst component was washed 3 times with 2000 ml of toluene in which air was blown for 1 hour and dried under reduced pressure.
(G) 3.6g was obtained.

523 g of a polymer was obtained in the same manner as in Example 2 except that 0.5 g of this solid catalyst component (G) was used. The polymer had an η of 0.81, a bulk specific gravity of 0.34 g / ml, a syndiotactic pentad fraction of 0.83, and a MW / MN of 2.3. No polymer adhered to the wall of the polymerization vessel, and no fine powder passed through the 200-mesh standard sieve.

[0045]

EFFECTS OF THE INVENTION By carrying out the method of the present invention, it is possible to produce a poly α-olefin having a high activity and a large bulk specific gravity per catalyst with high productivity without producing fine powder, which is industrially extremely valuable. There is.

[Brief description of drawings]

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

Claims (1)

[Claims] 1. The following general formula (Formula 1) or (Formula 2) obtained by hydrolyzing a trialkylaluminum (wherein R is a hydrocarbon residue having 1 to 4 carbon atoms, and n is 1 to 1). An aluminoxane represented by the following formula: [Chemical 2] The solid catalyst component obtained by carrying by catalytic reaction with an inorganic oxide having anhydrous or 10% by weight or less of adsorbed water is added to the following general formula (Chemical formula 3) or (Chemical formula 4) (in the formulas, A and B). Is a monovalent or divalent unsaturated hydrocarbon residue, or M
Are the same or different ligands each containing a nitrogen atom, an oxygen atom, a silicon atom, a phosphorus atom or a sulfur atom bonded to, and A ′ and B ′ are the same or different monovalent or divalent bridged by R. A valent unsaturated hydrocarbon residue or a ligand containing a nitrogen atom, an oxygen atom, a phosphorus atom or a sulfur atom bonded to M, and R is a divalent nitrogen atom, an oxygen atom, a silicon atom or a phosphorus atom. Or, a residue containing a sulfur atom or a linear saturated hydrocarbon residue which may have a side chain or a part or all of the carbon atoms of the linear chain thereof is substituted with a silicon atom, a germanium atom or a tin atom. A residue, M is a metal atom selected from Group 4 or 5 of the periodic table, and X
Represents a transition metal compound represented by a halogen atom, a carbon atom, a nitrogen atom, an oxygen atom, a silicon atom, a boron atom, a phosphorus atom or a sulfur atom bonded to M), [Chemical 4] In producing a solid catalyst component for olefin polymerization which is brought into contact with the solid catalyst component obtained by reacting the aluminoxane with an inorganic oxide, or after contacting a transition metal compound with the solid catalyst component, water and And / or a method of producing a solid catalyst component for olefin polymerization, which comprises using a contact treatment with oxygen.