JPH09157321A - Polymerization catalyst and method for producing polyolefin using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To make it possible to reduce the adhesion to reaction vessel walls to allow the stable production by using a catalyst for the polymerization of an olefin made up of a transition metal compound, an organic aluminum oxy compound, and an organometallic compound. SOLUTION: The transition metal compound (A) is represented by formulae I to III wherein R<1> to R<10> denote each a C1-20 hydrocarbon, alkylsilyl, part alkylgermil group; R<11> denotes a C1-20 alkylene, alkylgermilene or alkylsilylene; Q denotes H, a C1-20 hydrocarbon, alkoxy, alyloxy, siloxy or halogen group; Y denotes and electron donor lrgand made up of O, S, NR<12> , and PR<12> in which R<12> denotes H, a C1-20 hydrocarbon, a halogenated alkyl or a halogen aryl group, Me denotes a Groups/3-6 transition metal; and (p) is 0 or 1. As the component (B), generally an aluminoxane compound is used. The organic aluminum oxy compound (C) is, foe example, an alkyl lithium. The molar proportions of the components are such that 1/5<A/B<1/10,000 and 1/100<A/C<1/100,000.

Description

Detailed Description of the Invention

[0001]

[0001] The present invention relates to an olefin polymerization catalyst and a method for producing a polyolefin using the catalyst. More specifically, the present invention relates to an olefin polymerization catalyst capable of producing a polyolefin having good powder properties and a high bulk density with high activity without adhering to a reactor wall, and a method for producing a polyolefin using the same.

[0002]

2. Description of the Related Art Recently, processes for producing polyethylene or ethylene-α-olefin copolymers using a metallocene compound and methylaluminoxane as catalysts have been developed. For example, JP-A-58-19309 discloses that ethylene using biscyclopentadienyl zirconium dichloride and linear or cyclic methylaluminoxane alone or ethylene and α having 3 to 12 carbon atoms is used.
-Methods for producing copolymers with olefins have been proposed. This method is a catalyst system having a large activity per unit amount of transition metal and excellent copolymerizability, but it is necessary to use a large amount of expensive methylalumoxane, which is problematic from an industrial viewpoint.

In order to solve this problem, a catalyst system which maintains high activity even when the amount of aluminoxane used as a catalyst component is reduced has been studied. For example, JP-A-60-
JP-A-260602 proposes a method for producing a polyolefin using a catalyst characterized by using an organoaluminum compound in addition to a metallocene compound and an aluminoxane. JP-A-63-168409 discloses a metallocene compound. A method for producing a polyolefin using a solid catalyst having a metallocene compound supported on a carrier at the same time as producing a carrier by contacting the carrier with an organomagnesium compound is disclosed. However, these catalyst systems were able to reduce the amount of aluminoxane used while maintaining high activity, but it was difficult to achieve stable industrial production because the produced polymer adhered to the reactor wall.

To improve this, in the above organoaluminum compound coexisting catalyst system, a metallocene compound or methylaluminoxane is being supported on a certain solid carrier. For example, Japanese Patent Laid-Open No. 61-29600
8, JP-A-63-280703, JP-A-63-2280
4, JP-A-63-51405, JP-A-63-5140
7, JP-A-63-54403, JP-A-63-6101
0, JP-A-63-248803, JP-A-4-10080
8, JP-A-3-74412, JP-A-3-709, JP-A-4-7306, etc., a solid catalyst in which a metallocene compound and methylaluminoxane are supported on a porous inorganic metal oxide such as silica, alumina, or silica-alumina. A method for polymerizing olefins using is disclosed.

In parallel with these, Japanese Patent Application Laid-Open No. 1-25900
4. JP-A-1-259005 discloses a method using a catalyst in which a special metallocene compound having an alkoxysilane group as a substituent of a cyclopentadienyl ligand is supported on a porous inorganic metal oxide carrier such as silica. Has been proposed. JP-A-1-207303, JP-A-61-314
04, JP-A-4-224808 describes a method in which an organoaluminum compound is brought into contact with undehydrated silica or the like, and a catalyst in which a metallocene compound is supported on a carrier thereof is used. Also, Japanese Patent Application Laid-Open Nos.
Japanese Patent No. 211405 discloses a method using a catalyst in which a metallocene compound and an aluminoxane are supported on a spherical magnesium chloride carrier.

Further, Japanese Patent Application Laid-Open Nos. Hei 3-210307 and Hei 3-
No. 66710 proposes a method using a catalyst obtained by co-milling a metallocene compound and an aluminoxane with a solid magnesium compound. Also, JP-A-63-1992
No. 06 describes a method using a catalyst in which a metallocene compound is supported on solidified methylaluminoxane. However, although the supported catalysts described in these prior arts have improved adaptability to the slurry polymerization method or the gas phase polymerization method, they are insufficient for stable operation in preventing the adhesion of the polymer to the reactor wall. Met.

[0007]

DISCLOSURE OF THE INVENTION The present invention provides a highly active polyolefin having high powder properties and high bulk density even when the amount of expensive methylaluminoxane used is small. An object of the present invention is to provide an olefin polymerization catalyst that can be produced without the adhesion of olefins, and to produce a polyolefin using this catalyst.

[0008]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, have finally found a olefin polymerization catalyst and a method for producing a polyolefin which meet the purpose, and have reached the present invention. . That is, the olefin polymerization catalyst according to the present invention comprises: (A) a compound represented by the general formula (1):

Embedded image General formula (2)

Embedded image Alternatively, the general formula (3)

[Chemical 6] [In the formula, R ^{1 to} R ¹⁰ are hydrogen, a hydrocarbon group having 1 to 20 carbon atoms, an alkylsilyl group or an alkylgermyl group, which may be the same or different, and R ¹¹ is 1 to 20 carbon atoms. Is an alkylene group, alkylgermylene or alkylsilylene, each Q is hydrogen, and has 1 to 20 carbon atoms.
Is a hydrocarbon group having, alkoxy, aryloxy, siloxy or halogen, which may be the same or different, and Y is —O—, —S—, —NR ¹² —, —PR ¹² —.
And R ¹² is hydrogen, a hydrocarbon group having 1 to 20 carbon atoms, an alkyl halide or an aryl halide. )
Is an electron donor ligand consisting of Me, a transition metal of Groups 3, 4, 5 and 6 of the Periodic Table, and p is 0 or 1. ] The transition metal compound represented by, (B) an organoaluminum oxy compound supported on a carrier, and (C)
An olefin polymerization catalyst comprising at least one organometallic compound selected from alkyllithium, dialkylmagnesium or dialkylzinc. , The olefin polymerization catalyst described above, which carries 5 × 10 ^{−4 to} 0.05 gram atom of an aluminum oxy compound per 1 gram of the carrier in terms of aluminum atoms,

The organometallic compound (C) is at least one of normal butyl lithium, sec-butyl lithium, butyl ethyl magnesium, dinormal hexyl magnesium diethyl zinc or dibutyl zinc.
An olefin polymerization catalyst according to any one of 1., a number of moles [A] in the transition metal compound of component (A), a number of moles of aluminum atoms [B] in the organoaluminum oxy compound of component (B), and a component ( C) When the number of moles of the organometallic compound is [C], 1/5 <[A] / [B] <1 / 10,000 1/100 <[A] / [C] <1 / 100,000 The olefin polymerization catalyst according to any one of 1 to 3, which is blended in a proportion, The component (A) transition metal compound, the component (B) according to
A process for producing a polyolefin-based polymer, which comprises polymerizing or copolymerizing an olefin in the presence of an olefin polymerization catalyst comprising an organoaluminum oxy compound and a component (C) an organometallic compound supported on a carrier, and a transition metal compound as a component (A) When the number of moles [A] of the component, the number of moles of aluminum atom in the organoaluminum oxy compound of the component (B) [B], and the number of moles of the component (C) organometallic compound [C], 1/5 < [A] / [B] <1 / 10,000 1/100 <[A] / [C] <1 / 100,000 The olefin polymerization catalyst was blended in a concentration of the transition metal compound in the polymerization system. as 10 ^-8 to 10 ^-2 mol / liter presence of method and reaction temperature -30 to 200 ° C. of the polyolefin-based polymer according to the polymerization or copolymerization of olefins, the olefin Pressure has solved the above problems by developing a process for producing a polyolefin polymer of performing or described at normal pressure ~50kgG / cm ^3.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The olefin polymerization catalyst according to the present invention and a method for producing a polyolefin using the catalyst will be specifically described below. The transition metal compound (A) used in the present invention is represented by the general formula (1), the general formula (2) or the general formula (3): wherein R ^{1 to} R ¹⁰ are hydrogen and have 1 to 20 carbon atoms. Alkyl, alkenyl, aryl,
Hydrocarbon groups such as araryl, aralkyl and alicyclic, alkylsilyl groups or alkylgermyl groups, which may be the same or different, and R
¹¹ is an alkylene group having 1 to 20 carbon atoms, alkylgermylene or alkylsilylene, and each Q is hydrogen, a hydrocarbon group having 1 to 20 carbon atoms, alkoxy, allyloxy, siloxy or halogen, which may be the same or different. Alternatively, Y is —O—, —S—, —NR ¹² —,
—PR ¹² —, R ¹² is hydrogen, a hydrocarbon group having 1 to 20 carbon atoms, an alkyl halide or an aryl halide. ) Is an electron donor ligand, Me is a transition metal of Groups 3, 4, 5 and 6 of the periodic table, p
Is 0 or 1. ] It is a transition metal compound represented by.

The hydrocarbon group in these compounds is, for example, methyl group, ethyl group, propyl group, butyl group, isobutyl group, t-butyl group, amyl group, isoamyl group, hexyl group, heptyl group, octyl group, nonyl group. , Alkyl groups such as decyl group and cetyl group, aryl groups such as phenyl group, trimethylsilyl group as the alkylsilyl group, and trimethylgermyl group as the alkylgermyl group. In the above formula, Me is a transition metal element of Groups 3, 4, 5 and 6 of the periodic table (according to the 1990 rules of the Inorganic Chemistry Nomenclature),
The transition metal element of Group 4 of the periodic table, that is, titanium, zirconium, or hafnium is preferable, and zirconium or hafnium is particularly preferable.

Examples of the ligand of the compound having these substituents include a cyclopentadienyl group, a methylcyclopentadienyl group, an ethylcyclopentadienyl group,
alkyl-substituted cyclopentadienyl groups such as n-butylcyclopentadienyl group, t-butylcyclopentadienyl group, trimethylsilylcyclopentadienyl group, dimethylcyclopentadienyl group or pentamethylcyclopentadienyl group; Examples include an indenyl group and a fluorenyl group having or not having the same substituent.

In the compound represented by the above formula, R ¹¹
Is an alkylene group having 1 to 20 carbon atoms, alkylgermylene or alkylsilylene. Examples of the alkylene group include a methylene group, an ethylene group, a propylene group, an isopropylidene group, a cyclopentylidene group, a cyclohexylidene group, a tetrahydropyran-4-ylidene group, and a diphenylmethylene group. , Dimethylsilylene group, diphenylsilylene group and the like, and examples of the alkylgermylene group include
Examples thereof include a dimethylgermylene group and a diphenylgermylene group.

Q is hydrogen, a hydrocarbon group having 1 to 20 carbon atoms such as alkyl, alkenyl, aryl, araryl and aralkyl, alkoxy, allyloxy, siloxy or halogen, which may be the same or different.
Further, Y is —O—, —S—, —NR ¹² —, or —PR ¹² —. Here, R ¹² is hydrogen or a hydrocarbon group having 1 to 20 carbon atoms such as alkyl, alkenyl, aryl, araryl and aralkyl, or a halogenated alkyl or a halogenated aryl. Specifically, as a hydrocarbon group, a methyl group, an ethyl group, a propyl group, a butyl group, an isobutyl group, a t-butyl group, an amyl group, an isoamyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, Examples thereof include alkyl groups such as cetyl groups, phenyl groups, and benzyl groups. In this, -NR ¹² -, - PR
¹² -type ligands are preferred.

The transition metal compound represented by the general formula (1), the general formula (2) or the general formula (3) will be described below.
Illustrative examples of specific compounds in which is zirconium. As the transition metal compound represented by the general formula (1), bis (cyclopentadienyl) zirconium dichloride,
Bis (methylcyclopentadienyl) zirconium dichloride, bis (n-butylcyclopentadienyl) zirconium dichloride, bis (n-butylcyclopentadienyl) zirconium dimethyl, bis (1,3-dimethylcyclopentadienyl) zirconium Dichloride, bis (pentamethylcyclopentadienyl) zirconium dichloride, (cyclopentadienyl) (methylcyclopentadienyl) zirconium dichloride, (cyclopentadienyl) (n-butylcyclopentadienyl) zirconium dichloride, (cyclo Pentadienyl) (indenyl) zirconium dichloride, (Cyclopentadienyl) (fluorenyl) zirconium dichloride, Cyclopentadienylzirconium trichloride, Cyclopentadienyldichloride Benzalkonium trimethyl, pentamethylcyclopentadienyl zirconium trichloride, pentamethylcyclopentadienyl zirconium trimethyl like.

As the transition metal compound represented by the general formula (2), dimethylsilylenebis (methylcyclopentadienyl) zirconium dichloride, isopropylidenebis (methylcyclopentadienyl) zirconium dichloride, ethylenebis (indenyl) ) Zirconium dichloride, ethylenebis (4,5,6,7, -tetrahydro-1-indenyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (fluorenyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (indenyl) Zirconium dichloride, isopropylidene (t-butylcyclopentadienyl) (t-butylindenyl) Zirconium dichloride, isopropylidene (t-butylcyclopentadienyl) (t-butyl Ndeniru) zirconium dimethyl and the like.

As the transition metal compound represented by the general formula (3), ethylene (t-butylamide) (tetramethylcyclopentadienyl) zirconium dichloride, ethylene (methylamido) (tetramethylcyclopentadienyl) zirconium Dichloride, dimethylsilylene (t-butylamide) (tetramethylcyclopentadienyl) zirconium dichloride, dimethylsilylene (t-butylamide) (tetramethylcyclopentadienyl) zirconium dibenzyl, dimethylsilylene (benzylamide) (tetramethylcyclopenta) (Dienyl)
Examples thereof include zirconium dibenzyl and dimethylsilylene (phenylamide) (tetramethylcyclopentadienyl) zirconium dichloride.

Among the above zirconium compounds, transition metal compounds in which zirconium is changed to hafnium or titanium can be exemplified. The transition metal compound according to the present invention can be used alone or in combination of two or more of the above-mentioned transition metal compounds.

As the organoaluminum oxy compound in the component (B) used in the present invention, usually an aluminoxane compound is preferably used, but a modified aluminoxane can also be used as described later.

Typical examples of the above aluminoxane are represented by the general formula (4) (R ¹³ ) ₂ Al- [O-Al (R ¹³ )] _m- (R ¹³ ) ... (4) or the general formula (5) Organoaluminum compound represented by

Embedded image It is. [However, R ¹³ is hydrogen or carbon number 1-2.
0 hydrocarbon group, halogenated alkyl group or halogenated aryl group. Examples of the hydrocarbon group include a methyl group, an ethyl group, a propyl group, a butyl group, an isobutyl group and the like, and a methyl group and an isobutyl group are preferred. However, it may optionally contain a substituent such as a different hydrocarbon group listed above even in the same formula, for example, even if a repeating unit having a different hydrocarbon group is bonded in a block manner, They may be combined regularly or irregularly. m is 1 to 100, preferably 4 or more, particularly preferably 8 or more. A method for producing this type of compound is known, and examples thereof include a method of adding an organoaluminum compound to a hydrocarbon solvent suspension of a salt having water of crystallization (copper sulfate hydrate, aluminum sulfate hydrate), and a method for preparing a carbonized solution. A method in which solid, liquid or gaseous water is allowed to act on an organoaluminum compound in a hydrogen solvent is exemplified. In this case, as the aluminoxane, two or more compounds of the general formulas (4) and (5) may be mixed and used.

Examples of the organoaluminum compound used for producing aluminoxane include trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum, tri-n-butylaluminum, tri-iso-butylaluminum, tri-sec-butylaluminum. , Tri-tert-butylaluminum, tripentylaluminum, trihexylaluminum, trioctylaluminum, trialkylaluminum such as tricyclohexylaluminum, dimethylaluminum chloride, diethylaluminum chloride, dialkylaluminum halide such as di-iso-butylaluminum chloride, Dial such as dimethyl aluminum methoxide and diethyl aluminum ethoxide Le aluminum alkoxide is selected from among dialkyl aluminum Ally Loki Sid such as diethyl aluminum phenoxide. Among them, trialkylaluminums, particularly trimethylaluminum and tri-iso-butylaluminum are preferably selected.

As the hydrocarbon solvent used in the production of aluminoxane, aromatic hydrocarbons such as benzene, toluene and xylene, aliphatic hydrocarbons such as pentane, hexane, heptane, octane and decane, cyclopentane, Examples thereof include alicyclic hydrocarbons such as cyclohexane. Of these solvents, aromatic hydrocarbons are preferred. The catalyst of the present invention only needs to contain the organoaluminum oxy compound, and other components may be added or modified. Examples of the organoaluminum oxy compound to which an additive is added or a modified organoaluminum oxy compound include, for example, an aluminoxane compound in which the solubility in a solvent is reduced by adding water or heating, and a terminal with an active hydrogen-containing organic polar compound. Examples thereof include a modified aluminoxane compound and an aluminoxane compound to which an organic polar compound having no active hydrogen is added.

The carrier used as the component (B) is preferably porous fine particles and solid in the polymerization medium, such as an inorganic oxide, an inorganic chloride, an inorganic carbonate, an inorganic sulfate, or an organic substance. Selected from polymers. Examples of the inorganic oxide include SiO ₂ , Al ₂ O ₃ , MgO, ZrO.
Inorganic oxide of ₂ , TiO ₂ , CaO or SiO ₂ -A
_{l 2 O 3, SiO 2 -MgO} , SiO 2 -ZrO 2 Si
_{O 2 -TiO 2, SiO 2 -CaO} , Al 2 O 3 -Mg
_{O, Al 2 O 3 -ZrO 2} , Al 2 O 3 -TiO 2, A
_{l 2 O 3 -CaO, ZrO 2} -TiO 2, ZrO 2 -C
aO, ZrO ₂ —MgO, TiO ₂ —MgO and other complex oxides, inorganic chlorides such as magnesium chloride, inorganic carbonates such as magnesium carbonate, calcium carbonate and strontium carbonate, inorganics such as magnesium sulfate, calcium sulfate and barium sulfate An example is sulfate. Examples of the organic polymer carrier include fine particles of polyethylene, polypropylene, polystyrene and the like.

Among these, inorganic oxides, especially SiO
_It is desirable to be selected from ₂ , Al ₂ O ₃ and its composite oxide. The porous fine particles according to the present invention preferably have a specific surface area of 10 to 1000 m ² / g, more preferably 100 to 800 m ² / g, and particularly preferably 200 to 600 m ^2. / G range. Also, regarding the pore volume, 0.3 to 3 cc
/ G is preferable, and 0.5 to 2.5 is more preferable.
It is preferably in the range of cc / g, particularly preferably in the range of 1.0 to 2.0 cc / g.

A carrier, for example SiO which is the preferred carrier.
₂ , the amount of adsorbed water and the amount of surface hydroxyl groups of Al ₂ O ₃ or its composite oxide differ depending on the treatment conditions. As a preferable range thereof, the water content is 5% by weight or less, and the surface hydroxyl group content is
(Nm) ² or more. In order to control the water content and the amount of surface hydroxyl groups, it is possible to select the firing temperature and the firing time, and to carry out treatment with an organic aluminum compound or an organic boron compound.

The method of loading the organoaluminum oxy compound used in the present invention or a modified product thereof on a carrier is as follows:
After supporting an organoaluminum compound on a carrier, a method of reacting with water or an organic polar compound, a method of supporting a reaction product of an organoaluminum compound and water or an organic polar compound on a carrier, water or an organic compound on the carrier An example is a method of impregnating with a polar compound and then adding an organoaluminum compound to generate a reaction product on a carrier. However, the organoaluminum compound used for supporting is trialkylaluminum or aluminoxane when it reacts with water, and aluminoxane when it reacts with an organic polar compound. Among these methods, when reacting with water, the method is preferable, and the method is particularly preferable. When reacting with an organic polar compound, the method of is preferable, and the method of is particularly preferable.

The contact between the carrier and the organoaluminum oxy compound can be carried out in an inert hydrocarbon solvent. Specifically, aromatic hydrocarbons such as benzene, toluene and xylene, aliphatic hydrocarbons such as pentane, hexane, heptane, octane and decane, alicyclic hydrocarbons such as cyclopentane and cyclohexane can be used. Are preferably aromatic hydrocarbon solvents. The temperature at which the carrier and the organoaluminum oxy compound are brought into contact is usually -50 to 2
The reaction is carried out at 00 ° C, preferably at -20 to 100 ° C, more preferably at 0 to 50 ° C. The contact time is 0.05
It is about 200 to 200 hours, preferably about 0.2 to 20 hours.

The amount of the organoaluminum oxy compound or the modified product of the organoaluminum oxy compound supported on the carrier is in the range of 5 × 10 ^{-4 to} 0.05 gram atom in terms of aluminum atom per 1 g of the carrier. It is preferable that the range is 5 × 10 ^{−3 to} 0.01 gram atom.

The organoaluminum oxy compound (B) supported on the carrier may be used as it is, but an inert hydrocarbon solvent such as aromatic hydrocarbons such as benzene, toluene and xylene, pentane, hexane, heptane and octane. It is preferable to wash with an aliphatic hydrocarbon such as decane and alicyclic hydrocarbon such as cyclopentane and cyclohexane before use. The washing temperature at that time is usually -50 to 200
° C, preferably 0 to 150 ° C, more preferably 50 to 1 ° C.
50 ° C.

As the organometallic compound (C) of the present invention, at least one selected from alkyllithium, dialkylmagnesium and dialkylzinc is used. Among the organometallic compounds (C), alkyl lithium includes methyl lithium, ethyl lithium, n-propyl lithium, n-butyl lithium, iso-butyl lithium, sec-butyl lithium, tert-butyl lithium, n-pentyl lithium, It is selected from iso-pentyllithium and neopentyllithium. Among these, n-butyl lithium and tert-butyl lithium are preferable. Further, as dialkyl magnesium, n-
It is selected from among butylethyl magnesium, di-sec-butyl magnesium, n-butyl-sec-butyl magnesium, di-tert-butyl magnesium, dineopentyl magnesium, di-n-hexyl magnesium. Among these, n-butylethyl magnesium, di-
It is preferably selected from sec-butyl magnesium and di-n-hexyl magnesium. Further, the dialkyl zinc is selected from diethyl zinc, di-n-propyl zinc, di-n-butyl zinc, di-n-hexyl zinc, and zinc neopentyl zinc. Of these, diethyl zinc is preferred.

Transition metal compound (A) used in the present invention
The contact between the organoaluminum oxy compound (B) and the organometallic compound (C) supported on the carrier may be carried out in the presence or absence of a monomer before the polymerization,
It may be introduced into the polymerization system without contact in advance. The order of contacting the transition metal compound (A) with the organoaluminum oxy compound (B) and the organometallic compound (C) supported on the carrier is arbitrarily selected, but (A) and (B) are mixed in advance. After that, a method of contacting with (C) or a method of previously mixing (A), (B) and (C) and then contacting with (C) again is preferable. When the transition metal compound (A), the organoaluminum oxy compound (B) and the organometallic compound (C) are pre-contacted with each other, the reactions are usually carried out in an inert solvent.

Examples of the solvent used at this time include aromatic hydrocarbons such as benzene, toluene and xylene, aliphatic hydrocarbons such as pentane, hexane, heptane, octane and decane, and alicyclic compounds such as cyclopentane and cyclohexane. Hydrocarbons can be used. The transition metal compound (A) used in the present invention, the contact ratio of the organoaluminum oxy compound (B) supported on the carrier, and the organometallic compound (C) are such that the number of moles of the transition metal compound (A) is [A], When the number of moles of aluminum atoms in the organoaluminum oxy compound (B) supported on the carrier is [B] and the number of moles of the transition metal compound (C) is [C], the value of [A] / [B] is , 1/5 to 1/10000, preferably 1/10 to 1
/ 2000, and the value of [A] / [C] is 1/10 to 1
/ 100,000, preferably 1/100 to 1/1000
It is preferably 0.

In the present invention, ethylene alone or propylene, 1-butene, 1-pentene, 1-
Heptene, 1-octene, 1-decene, 4-methyl-1
-Α-olefins such as pentene, cyclopentene,
Cycloolefins such as cyclohexene, and the dienes include butadiene, 1,5-hexadiene, 1,
It can be copolymerized with comonomers such as 4-hexadiene and 1,4-pentadiene. At the time of copolymerization, two or more kinds of these comonomers may be mixed and used for copolymerization with ethylene.

As the polymerization method in which the olefin polymerization catalyst of the present invention can be used, any of solution polymerization, slurry polymerization and gas phase polymerization is possible. Preferably, it is slurry polymerization or gas phase polymerization. Multi-stage polymerization is also possible. Alternatively, the polymerization reaction may be performed after the olefin is prepolymerized. The amount of the polymerization catalyst used in the method for producing a polyolefin according to the present invention need not be limited, but is usually 10 ⁻⁸ to 10 ⁻² mol in terms of the concentration of the transition metal compound in the polymerization reaction system.
/ L, preferably in the range of 10 ^-7 to 10 ^-3 mol / l. The olefin pressure of the reaction system can be used in a wide range, but it is preferably in the range of normal pressure to 50 kgG / cm ² , and the polymerization temperature can be used in a wide range.
In the range of 0 ° C to 200 ° C, preferably 0 ° C to 120 ° C
Range. The range of 50 to 90 ° C. is particularly preferable in consideration of productivity. The molecular weight at the time of polymerization can be adjusted by known means, for example, by selecting a temperature or introducing hydrogen.

The polymer or copolymer produced by using the olefin polymerization catalyst of the present invention has a characteristic that a resin having a wide range of molecular weight can be produced. That is, by selecting the metallocene species, the polymerization temperature, or adjusting the amount of hydrogen introduced during the polymerization, JIS K-7210. "The flow test method for thermoplastics", Table 14, condition 14 (190
C., load 21.6 kgf: hereinafter referred to as HLMFR. ), A melt flow rate of 0.0001 g / 10 min from a high molecular weight compound to condition 4 (190 ° C., load 2.16 k)
gf: Hereinafter referred to as MFR. It is possible to manufacture a low molecular weight compound having a melt flow rate of 1) of 10,000 g / 10 min. Further, the polymer or copolymer in the present invention is in the form of particles having an average particle size of about 200 to 800 μm, and its bulk density is as high as 0.30 to 0.45 g / cc,
It is characterized by its excellent powder properties. Further, the polymer or copolymer produced by using the catalyst of the present invention has a low content of catalyst component residue that adversely affects practical properties. In addition, the copolymer produced using the olefin polymerization catalyst of the present invention has essentially excellent randomness and a narrow composition distribution.
Therefore, the obtained copolymer resin has excellent properties such as excellent transparency, a small amount of extractable components, and excellent low-temperature heat sealability.

[0036]

Next, the present invention will be described specifically with reference to examples. Regarding the melt flow rate, according to JIS K-7210, MFR was measured under the condition 4 in Table 1 and HLMFR was measured under the condition 14 in Table 1. (Example 1) [Preparation of aluminoxane] 75 liters of dry toluene was added to a reactor of 200 liters which was sufficiently replaced with nitrogen, and 3.75 of Al ₂ (SO ₄ ) ₃ .14H ₂ O was added thereto.
KG was suspended. After cooling to −20 ° C., 45 mol of trimethylaluminum (40.5 liter of 1.11 mol / liter toluene solution) was added over 1 hour, and 80
The temperature was raised to ° C and the mixture was stirred for 12 hours. Then, the aluminum sulfate compound was removed under a nitrogen atmosphere to give 0.35 mol.
/ Liter methylaluminoxane in toluene 1
05 liters were collected.

[Support of aluminoxane on carrier] Toluene (5) was added to a 200-liter reactor sufficiently replaced with nitrogen.
0 l and 3.0 kg of silica (Davison 952 calcined at 300 ° C. for 4 hours) were added, and to the suspension, the above methylaluminoxane [0.35M (Al atom conversion) toluene solution, methyl group / aluminum atom = 1 was added. .30] 74
L was added, and the mixture was stirred at room temperature for 30 minutes. Thereafter, the solvent was distilled off under reduced pressure. 100 L of heptane was added, and the mixture was stirred at 80 ° C for 4 hours. Then, it was washed twice with 50 liters of heptane at 80 ° C., and further washed 3 times with 30 liters of hexane at room temperature to obtain a solid component.

[Polymerization] Fully nitrogen-substituted internal volume 290
Isobutane was supplied to a 1 liter loop polymerization reactor, and after filling the polymerization reactor with isobutane, the temperature was raised to 70 ° C. while stirring. Then, ethylene was added at a partial pressure of 10
The hydrogen was supplied so as to be kg / cm ^2, and hydrogen was supplied so that the hydrogen concentration in the polymerization reactor was 2 × 10 ⁻⁵ (weight ratio) with respect to ethylene. Further, a hexane solution of bis (n-butylcyclopentadienyl) zirconium dichloride (0.2 g / liter) was 330 ml / hr, the prepared solid catalyst component was 2.0 g / hr,
A hexane solution of n-butyllithium (1.6 mol / liter) was continuously supplied at a rate of 74 ml / hr to initiate polymerization. Isobutane, a polymerization solvent, was added to 5
While continuously feeding at a rate of 1.5 kg / hr, the polymerization conditions of the polymerization reactor were ethylene partial pressure of 10 kg / cm ² , polymerization temperature of 70 ° C., residence time of 1 hour, and linear velocity of the polymer slurry in the polymerization reactor. It was maintained at 6 m / sec. The liquid composition in the polymerization reactor was ethylene 7.6 mol%, isobutane 91.
It was 5 mol%.

As a result, under the above conditions, 15.4 kg / hr
Polyethylene is produced at a ratio of MFR of this polymer
Is 0.7 g / 10 min, the ratio of HLMFR to MFR (HLMFR / MFR) is 15.8, and the density is 0.94.
It was 61 g / cm ³ . The bulk density of the obtained polymer was 0.40 g / cm ³ , and the average particle size was 320 μm. After 100 hours of polymerization under the above polymerization conditions, when the polymerization reactor was opened, there was no adhesion of the polymer to the polymerization reactor wall and the stirring impeller.

(Embodiment 2) Inner volume 2 fully replaced with nitrogen
Isobutane was supplied to a 90-liter loop polymerization reactor. After filling the polymerization reactor with isobutane, the temperature was raised to 70 ° C. while stirring. Then, ethylene was added at a partial pressure of 1
It was supplied so as to be 0 kg / cm ² . Further, 1-hexene was supplied so that the concentration of 1-hexene in the polymerization reactor was 0.33 (molar ratio) with respect to ethylene, and hydrogen was supplied with respect to ethylene in the polymerization reactor. It was supplied so as to be 2 × 10 ⁻⁵ (weight ratio). Further, a hexane solution of bis (n-butylcyclopentadienyl) zirconium dichloride (0.2 g / liter) was added to the mixture.
0 ml / hr, 2.0 g / hr of the solid catalyst component prepared above, and 74 ml / hr of a hexane solution of n-butyllithium (1.6 mol / liter).
Polymerization was initiated by continuously supplying the mixture at a rate of. While continuously supplying iso-butane as a polymerization solvent at a rate of 51.5 kg / hr, the polymerization conditions of the polymerization reactor were as follows: ethylene partial pressure 10 kg / cm ² , polymerization temperature 70 ° C., residence time 1 hour, polymerization The linear velocity of the polymer slurry in the reactor is 6 m /
sec. The liquid composition in the polymerization reactor was 7.5 mol% ethylene, 2.5 mol% 1-hexene, and 89.3 mol% iso-butane.

As a result, under the above conditions, 17.2 kg / h
Polyethylene is produced at a ratio of r, and the MF of this polymer is
R is 3.5g / 10min, HLMFR and MFR
Ratio (HLMFR / MFR) is 15.4, density is 0.9
It was 220 g / cm ³ . The bulk density of the obtained polymer was 0.35 g / cm ³ , and the average particle size was 330 μm. After 100 hours of polymerization under the above polymerization conditions, when the polymerization reactor was opened, there was no adhesion of the polymer to the polymerization reactor wall and the stirring impeller.

Example 3 Example 3 was repeated except that a hexane solution of n-butyllithium was replaced with a heptane solution of butylethylmagnesium (1.2 mol / liter) and was continuously supplied at a rate of 100 ml / hr. 1
The same operation as described above was performed. As a result, under the above conditions, 16.
Polyethylene was produced at a rate of 6 kg / hr, and the MFR of this polymer was 0.8 g / 10 min.
C., the ratio of HLMFR to MFR (HLMFR / MFR) was 15.6, and the density was 0.9466 g / cm ³ . The bulk density of the obtained polymer was 0.38 g / cm ³ , and the average particle size was 390 μm. After 100 hours of polymerization under the above polymerization conditions, when the polymerization reactor was opened, there was no adhesion of the polymer to the polymerization reactor wall and the stirring impeller.

Example 4 Example 4 was repeated except that a heptane solution of butylethylmagnesium (1.2 mol / liter) was used in place of the hexane solution of n-butyllithium, and the solution was continuously supplied at a rate of 100 ml / hr. Two
The same operation as described above was performed. As a result, under the above conditions, 18.
Polyethylene was produced at a rate of 0 kg / hr, the MFR of this polymer was 3.7 g / 10 min, and HLMF
The ratio of R and MFR (HLMFR / MFR) was 15.9, and the density was 0.9218 g / cm ³ . The obtained polymer has a bulk density of 0.37 g / cm ³ and an average particle size of 35.
It was 0 μm. After 100 hours of polymerization under the above polymerization conditions, when the polymerization reactor was opened, there was no adhesion of the polymer to the polymerization reactor wall and the stirring impeller.

(Example 5) Instead of the hexane solution of n-butyl lithium, a hexane solution of diethyl zinc (0.5
mol / l), and 235 ml / hr
The same operation as in Example 1 was performed except that the mixture was continuously supplied at the ratio of. As a result, under the above conditions, 15.3 kg / hr
Polyethylene was produced at a rate of. MF of this polymer
R is 0.9g / 10min, HLMFR and MFR
Ratio (HLMFR / MFR) is 16.4, density is 0.9
It was 475 g / cm ³ . The bulk density of the obtained polymer was 0.35 g / cm ³ , and the average particle size was 310 μm. After 100 hours of polymerization under the above polymerization conditions, when the polymerization reactor was opened, there was no adhesion of the polymer to the polymerization reactor wall and the stirring impeller.

Example 6 Instead of the hexane solution of n-butyllithium, a hexane solution of diethyl zinc (0.5
mol / l), and 235 ml / hr
The same operation as in Example 2 was performed except that the mixture was continuously fed at the ratio of. As a result, under the above conditions, 16.0 kg / h
Polyethylene is produced at a ratio of r, and the MF of this polymer is
R is 4.3g / 10min, HLMFR and MFR
Ratio (HLMFR / MFR) is 15.6, density is 0.9
It was 211 g / cm ³ . The bulk density of the obtained polymer was 0.37 g / cm ³ , and the average particle size was 300 μm. After 100 hours of polymerization under the above polymerization conditions, when the polymerization reactor was opened, there was no adhesion of the polymer to the polymerization reactor wall and the stirring impeller.

Comparative Example 1 A hexane solution of tri-iso-butylaluminum (0.5 mol / liter) was used in place of the hexane solution of n-butyllithium.
The same operation as in Example 1 was performed except that the solution was continuously supplied at a rate of 5 ml / hr. As a result, polyethylene was produced at a rate of 28 kg / hr under the above conditions. The MFR of this polymer is 0.8 g / 10 min, H
The ratio of LMFR and MFR (HLMFR / MFR) is 16.
1, the density was 0.9458 g / cm ³ . The bulk density of the obtained polymer was 0.36 g / cm ³ , and the average particle size was 370 μm. Under the above polymerization conditions, a load was applied to the stirring pump after 30 hours, and the temperature control of the polymerization reactor became impossible, so the polymerization was stopped. When the polymerization reactor was opened, adhesion of a polymer having a thickness of 2 to 3 mm was observed on the polymerization reactor wall and the stirring impeller.

(Comparative Example 2) A hexane solution of tri-n-butylaluminum (0.5 mol / liter) was used in place of the hexane solution of n-butyllithium, and was continuously supplied at a rate of 235 ml / hr. The same operation as in Example 1 was performed. As a result, under the above conditions, 2
Polyethylene was produced at a rate of 9 kg / hr. The MFR of this polymer is 0.7 g / 10 min, and the HLM
The ratio of FR and MFR (HLMFR / MFR) is 16.3,
The density was 0.9450 g / cm ³ . The obtained polymer has a bulk density of 0.42 g / cm ³ and an average particle size of 4
It was 20 μm. Under the above-mentioned polymerization conditions, when the polymerization reactor was opened after polymerization for 100 hours, adhesion of a polymer having a thickness of about 0.3 to 0.5 mm was observed on the wall of the polymerization reactor and the impeller for stirring.

[0048]

The present invention relates to a novel olefin polymerization catalyst comprising a metallocene compound, an organoaluminum oxy compound and an organometallic compound of lithium, magnesium or zinc, and a method for producing an olefin polymer using the same. However, it has a sufficient polymerization activity with a small amount of expensive methylaluminoxane, and has the ability to produce a polyolefin having an extremely wide range of molecular weight depending on the amount of hydrogen introduced at the time of polymerization. The catalyst of the present invention can be used in any of solution polymerization, slurry polymerization or gas phase polymerization, but the most important feature is that the conventional high-performance metallocene catalyst is the most problematic when used in the slurry method. It was possible to significantly reduce the adhesion to the reactor wall while maintaining the ability to produce a polymer having a high polymerization activity and a wide range of molecular weights, and the catalyst of the present invention was developed. As a result, the metallocene catalyst can be economically applied to slurry polymerization, and industrially stable production becomes possible.

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[Procedure amendment]

[Submission date] February 29, 1996

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] Brief description of drawings

[Correction method] Added

[Correction contents]

[Brief description of the drawings]

FIG. 1 is a flow chart of a catalyst.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Akihiro Hori Oita-shi, Oita Prefecture Nakanoshima 2 Nihon Polyolefin Co., Ltd. Oita Research Institute (72) Inventor Shigenobu Miyake Oita-shi Oita Prefecture Nakanozu 2 Japan Polioref Oita Laboratory, Inc. (72) Inventor Shintaro Inazawa Oita, Oita Prefecture Nakanoshima 2 Japan Polyolefin Co., Ltd. Oita Laboratory

Claims (7)

[Claims] 1. (A) General formula (1): General formula (2) Or the general formula (3): [In the formula, R ^{1 to} R ¹⁰ are hydrogen, a hydrocarbon group having 1 to 20 carbon atoms, an alkylsilyl group or an alkylgermyl group, which may be the same or different, and R ¹¹ is 1 to 20 carbon atoms. Is an alkylene group, alkylgermylene or alkylsilylene, each Q is hydrogen, and has 1 to 20 carbon atoms.
Is a hydrocarbon group having, alkoxy, aryloxy, siloxy or halogen, which may be the same or different, and Y is —O—, —S—, —NR ¹² —, —PR ¹² —.
And R ¹² is hydrogen, a hydrocarbon group having 1 to 20 carbon atoms, an alkyl halide or an aryl halide. )
Is an electron donor ligand consisting of Me, a transition metal of Groups 3, 4, 5 and 6 of the periodic table, and p is 0 or 1
It is. ] An olefin polymerization catalyst comprising a transition metal compound represented by the formula (B), and (B) an organoaluminumoxy compound supported on a carrier, and (C) at least one organometallic compound selected from alkyllithium, dialkylmagnesium or dialkylzinc. 2. The olefin polymerization catalyst according to claim 1, which carries 5 × 10 ^{−4 to} 0.05 gram atom of an aluminum oxy compound per 1 gram of the carrier in terms of aluminum atoms. 3. The organometallic compound (C) is at least one of normal butyl lithium, sec-butyl lithium, butyl ethyl magnesium, dinormal hexyl magnesium, diethyl zinc or dibutyl zinc. The olefin polymerization catalyst according to 1. 4. The number of moles [A] in the transition metal compound of component (A), the number of moles of aluminum atoms [B] in the organoaluminum oxy compound of component (B) and the organometallic compound of component (C). When the number of moles is [C], the compounding ratio is 1/5 <[A] / [B] <1 / 10,000 1/100 <[A] / [C] <1 / 100,000 Item 5. The olefin polymerization catalyst according to any one of Items 1 to 3. 5. The olefin in the presence of the olefin polymerization catalyst comprising the component (A) transition metal compound, the component (B) carrier-supported organoaluminum oxy compound and the component (C) organometallic compound according to claim 1. A method for producing a polyolefin-based polymer, which comprises polymerizing or copolymerizing. 6. The number of moles [A] in the transition metal compound of the component (A), the number of moles of aluminum atoms [B] in the organoaluminum oxy compound of the component (B) and the organometallic compound of the component (C). When the number of moles is [C], an olefin blended in a ratio of 1/5 <[A] / [B] <1 / 10,000 1/100 <[A] / [C] <1 / 100,000 The method for producing a polyolefin polymer according to claim 5, wherein the polymerization catalyst is used to polymerize or copolymerize an olefin in the presence of a transition metal compound concentration in the polymerization system of 10 ^-8 to 10 ^-2 mol / liter. 7. The method for producing a polyolefin polymer according to claim 5, wherein the reaction temperature is −30 to 200 ° C., and the partial pressure of the olefin is atmospheric pressure to 50 kgG / cm ³ .