JPH04213305A - Solid catalyst for polymerization of olefin and polymerization of olefin - Google Patents

Abstract

PURPOSE:To obtain the title catalyst which can give a polymer of excellent particle properties at high polymerization activity by prepolymerizing an olefin in a suspension or a vapor phase containing a particulate carrier, two specified transition metal compounds and an organoaluminumoxy compound. CONSTITUTION:The title catalyst is obtained by prepolymerizing an olefin in a suspension or a vapor phase containing a particulate carrier, transition metal compound containing ligands each having a cycloalkadienyl skeleton which are not combined with each other, a transition metal compound containing at least two ligands each having a cycloalkadienyl skeleton at least two of which are bonded to each other through (substituted) alkylene or (substituted) silylene, and an organoaluminumoxy compound. When this catalyst is used in a suspension polymerization process or a vapor phase polymerization process even when it contains a reduced amount of the lost component, it can give a spherical olefin polymer of excellent particle properties with high polymerization activity.

Description

[Detailed description of the invention]

0001

TECHNICAL FIELD OF THE INVENTION The present invention relates to a solid catalyst for olefin polymerization and a method for polymerizing olefins using this catalyst. An olefin that, when applied to the polymerization method, can produce a spherical olefin polymer with high polymerization activity and excellent particle properties even if the amount of organoaluminumoxy compound used is reduced, and also provides a polymer with excellent melt tension. This invention relates to a solid catalyst for polymerization and a method for polymerizing olefins using this catalyst.

0002

TECHNICAL BACKGROUND OF THE INVENTION Conventionally, titanium-based catalysts consisting of titanium compounds and organic aluminum compounds or vanadium compounds have been used as catalysts for producing α-olefin polymers, such as ethylene polymers or ethylene/α-olefin copolymers. A vanadium-based catalyst consisting of aluminum and an organoaluminum compound is known.

[0003] In recent years, a new Ziegler type olefin polymerization catalyst consisting of a zirconium compound and aluminoxane has been developed as a catalyst capable of producing ethylene/α-olefin copolymers with high polymerization activity. A method for producing an ethylene/α-olefin copolymer using the method has been proposed.

For example, JP-A-58-19309 describes the following formula (cyclopentadienyl)2MeRHal (wherein R is cyclopentadienyl, C1 to C6 alkyl or halogen, and Me is a transition metal and Hal is a halogen) and a transition metal compound represented by the following formula Al2OR4(Al(R)-O)n (wherein, R is methyl or ethyl, and n is 4 to 20
is the number of ) or the following formula

[0005]

[Chemical formula 1]

(wherein R is methyl or ethyl,
n is a number from 4 to 20. ) in the presence of a catalyst consisting of a cyclic aluminoxane represented by ethylene and C3
-5 of one or more α-olefins of ~C12
Methods for polymerization at temperatures between 0°C and 200°C are described.

[0007] Japanese Patent Application Laid-open No. 19309/1983 describes the following formula:

[0008]

[Case 2]

(In the formula, n is 2 to 40, and R is C1 to
It is C8 alkyl. ) and the following formula:

0010

[Chemical formula 3]

A method for producing a cyclic aluminoxane represented by the formula (wherein the definitions of R and n are the same as in the above formula) is described, and also for example, methylaluminoxane produced by the same method A method for polymerizing polyolefins by mixing titanium or zirconium with a bis(cyclopentadienyl) compound is described.

[0012] Japanese Patent Application Laid-open No. 60-35005 describes the following formula:

[0013]

[C4]

(wherein R1 is C1-C10 alkyl, R0 is R1 or is combined with -O-
represents. ) is first reacted with a magnesium compound, then the reaction product is chlorinated, and further treated with a Ti, V, Zr or Cr compound to produce a polymerization catalyst for olefins. has been done.

JP-A-60-35006 discloses that mono-, di- or tri-cyclopentadienyl of two or more different transition metals or a derivative thereof (a) and alumoxane (aluminoxane) (b) Example 1 describes the production of polyethylene by polymerizing ethylene and propylene using bis(pentamethylcyclopentadienyl)zirconium dimethyl and alumoxane as catalysts. There is. In addition, in Example 2, ethylene and propylene were polymerized using bis(pentamethylcyclopentadienyl)zirconium dichloride, bis(methylcyclopentadienyl)zirconium dichloride, and alumoxane as catalysts to copolymerize polyethylene and ethylene-propylene. It has been described to obtain polymer blends with coalescence.

JP-A No. 60-35007 discloses that ethylene is used alone or together with an α-olefin having 3 or more carbon atoms together with metallocene and the following formula:

[0017]

[C5]

(wherein R is an alkyl group having 1 to 5 carbon atoms, and n is an integer of 1 to about 20) or a cyclic alumoxane represented by the following formula:

[0019]

[C6]

A method is described in which polymerization is carried out in the presence of a linear aluminoxane represented by the formula (wherein the definitions of R and n are the same as in the above formula).

Furthermore, JP-A-60-35008 discloses that polyethylene or ethylene and C3 to C1 using a catalyst system containing at least two types of metallocene and alumoxane are disclosed.
The preparation of copolymers of 0 with α-olefins is described.

Catalysts formed from transition metal compounds and aluminoxane proposed in these prior art are as follows:
Although this catalyst has superior polymerization activity, especially ethylene polymerization activity, compared to catalysts formed from transition metal compounds and organoaluminum compounds that were known before the appearance of this catalyst,
Most of them are soluble in the reaction system, and in most cases, the production process is limited to a solution polymerization system, and when attempting to produce a polymer with a high molecular weight, the viscosity of the solution containing the polymer increases significantly, resulting in reduced productivity. There are problems in that the bulk density of the polymer obtained after the post-polymerization treatment is low, and it is difficult to produce a spherical olefin polymer with excellent particle properties.

On the other hand, at least one component of the transition metal compound and aluminoxane is silica, alumina,
Attempts have also been made to polymerize olefins in suspension polymerization systems or gas phase polymerization systems using catalysts supported on porous inorganic oxide supports such as silica and alumina.

For example, the above-mentioned Japanese Patent Application Laid-Open Nos. 60-35006, 60-35007, and 60-60
Publication No. 35008 describes that a catalyst in which a transition metal compound and aluminoxane are supported on silica, alumina, silica/alumina, etc. can be used.

[0025] In JP-A-60-106808 and JP-A-60-106809, a highly active catalyst component containing a titanium compound and/or a zirconium compound soluble in a hydrocarbon solvent and a filler are disclosed. By copolymerizing ethylene or ethylene and α-olefin in the presence of the product obtained by contact treatment in advance, the organoaluminum compound, and a filler that has an affinity for polyolefin, the polyethylene polymer and filler are copolymerized. A method for making a composition is described.

JP-A-61-31404 discloses that in the presence of a mixed catalyst consisting of a product obtained by reacting trialkylaluminum and water in the presence of silicon dioxide or aluminum oxide and a transition metal compound, , a method for polymerizing or copolymerizing ethylene or ethylene and an α-olefin is described.

Furthermore, JP-A-61-276805 discloses that a reaction mixture obtained by reacting a zirconium compound, aluminoxane, and trialkylaluminum is further reacted with an inorganic oxide having a surface hydroxyl group such as silica. The polymerization of olefins is described in the presence of a catalyst consisting of a reaction mixture of

Furthermore, JP-A-61-108610 and JP-A-61-296008 disclose that a transition metal compound such as metallocene and an aluminoxane are supported on a carrier such as an inorganic oxide in the presence of a catalyst. , a method for polymerizing olefins is described.

However, when an olefin is polymerized or copolymerized in a suspension polymerization system or a gas phase polymerization system using the solid catalyst component supported on a carrier described in these documents, the polymerization activity is lower than that in the solution polymerization system. The bulk specific gravity of the resulting polymer was not sufficiently satisfactory.

[0030]

[Object of the Invention] The present invention has been made in view of the prior art as described above, and it is possible to avoid using large amounts of organoaluminumoxy compounds even when applied to suspension polymerization or gas phase polymerization. In addition to providing a solid catalyst for olefin polymerization that can produce a spherical olefin polymer with high polymerization activity, excellent particle properties, and excellent melt tension, it is also possible to use a catalyst with such good properties. The purpose is to polymerize olefins.

[0031]

[Summary of the Invention] The first solid catalyst for olefin polymerization according to the present invention comprises [A] a particulate carrier and [B] a transition metal compound containing a ligand having a cycloalkadienyl skeleton that is not bonded to each other. (hereinafter referred to as a non-bridge type transition metal compound), and a ligand containing at least two or more [C]cycloalkadienyl skeletons and having at least two cycloalkadienyl skeletons. A suspension containing a transition metal compound bonded via an alkylene group, substituted alkylene group, silylene group or substituted silylene group (hereinafter referred to as a bridge type transition metal compound) and [D] an organoaluminumoxy compound. It is characterized by being formed by prepolymerizing olefins in a cloudy liquid or gas phase.

Further, the second solid catalyst for olefin polymerization according to the present invention comprises the above-mentioned component [A], component [B], component [C], [D] organoaluminumoxy compound, and [ E] It is characterized by being formed from an organoaluminum compound.

Furthermore, the method for polymerizing olefins according to the present invention is characterized in that olefins are polymerized or copolymerized in the presence of the solid catalyst for olefin polymerization as described above.

When olefin polymerization is carried out in the presence of the solid catalyst for olefin polymerization according to the present invention, the particle properties are excellent;
Furthermore, an olefin polymer having excellent melt tension and high polymerization activity can be obtained.

[0035]

DETAILED DESCRIPTION OF THE INVENTION The solid catalyst for olefin polymerization according to the present invention and the method for polymerizing olefins using this catalyst will be specifically described below.

FIG. 1 shows an explanatory diagram of the solid catalyst for olefin polymerization according to the present invention. In addition, in the present invention, the word "polymerization" is sometimes used to include not only homopolymerization but also copolymerization, and the word "polymer" includes not only homopolymers but also copolymers. It is sometimes used with this meaning.

[0037] The particulate carrier [A] according to the present invention has an average particle diameter of usually 1 to 300 μm, preferably 10 to 200 μm.
A particulate inorganic carrier or a particulate organic carrier in the m range is used.

[0038] As such a particulate inorganic carrier, an oxide is preferable, and specifically, SiO2, Al2O3
, MgO, ZrO2, TiO2 or a mixture thereof.

Among these, SiO2, Al2O3
A carrier containing as a main component at least one component selected from the group consisting of MgO and MgO is preferred. In addition, as the particulate organic carrier, particulate organic polymers, for example, particulate polymers of polyolefins such as polyethylene, polypropylene, poly-1-butene, poly-4-methyl-1-pentene, and particulates such as polystyrene, etc. Polymers and the like are used.

The [B] non-bridge type transition metal compound used in the present invention has the following formula M1 L1X (wherein, M
1 is a transition metal, L1 is a ligand that coordinates to the transition metal, at least one L1 is a ligand having a cycloalkadienyl skeleton, and L1 is a ligand other than a ligand having a cycloalkadienyl skeleton. L1 is a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group, an aryloxy group, a halogen, or hydrogen, and x is the valence of the transition metal. ).

In the above formula, M1 is a transition metal, specifically preferably zirconium, titanium, hafnium, chromium, vanadium,
Among these, zirconium and hafnium are particularly preferred.

Examples of the ligand having a cycloalkadienyl skeleton include a cyclopentadienyl group, a methylcyclopentadienyl group, an ethylcyclopentadienyl group, an n-butylcyclopentadienyl group, and a dimethylcyclopentadienyl group. Examples include an enyl group, an alkyl-substituted cyclopentadienyl group such as a pentamethylcyclopentadienyl group, an indenyl group, and a fluorenyl group.

One or more, preferably two, such ligands having a cycloalkadienyl skeleton are coordinated to the transition metal M1. Ligands other than those having a cycloalkadienyl skeleton have 1 to 12 carbon atoms.
hydrocarbon group, alkoxy group, aryloxy group, halogen or hydrogen.

Examples of hydrocarbon groups having 1 to 12 carbon atoms include alkyl groups, cycloalkyl groups, aryl groups, and aralkyl groups. Specifically, examples of alkyl groups include methyl groups and ethyl groups. , propyl group, isopropyl group, butyl group, etc.; cycloalkyl groups include cyclopentyl group, cyclohexyl group; aryl groups include phenyl group, tolyl group, etc.; aralkyl groups include: Examples include benzyl group and neophyll group.

Examples of the alkoxy group include a methoxy group, ethoxy group, and butoxy group, and examples of the aryloxy group include a phenoxy group.

[0046] Examples of halogen include fluorine, chlorine, bromine,
Examples include iodine. Such a transition metal compound containing a ligand having a non-bridged cycloalkadienyl skeleton [B] used in the present invention, for example, when the valence of the transition metal is 4, more specifically, The following formula R2k R3l R4mR5n M1 (wherein, M1
is zirconium, titanium, hafnium or vanadium, R2 is a group having a cycloalkadienyl skeleton, R3, R4 and R5 are a group having a cycloalkadienyl skeleton, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, an aryloxy group, a halogen atom, or hydrogen, k is an integer of 1 or more, and k+l+m+n=4).

Hereinafter, M1 is zirconium [B]
Specific examples of non-bridge type transition metal compounds containing a ligand having a cycloalkadienyl skeleton are shown below. Bis (cyclopentadienyl) zirconium monochloride monohydride, bis (cyclopentadienyl) zirconium monobromide monohydride, bis (cyclopentadienyl) methyl zirconium hydride, bis (cyclopentadienyl) ethyl zirconium hydride, bis ( cyclopentadienyl)
Phenylzirconium hydride, bis(cyclopentadienyl)benzylzirconium hydride, bis(cyclopentadienyl)neopentylzirconium hydride, bis(methylcyclopentadienyl)zirconium monochloride hydride, bis(indenyl)zirconium monochloride monohydride, Screw(
Cyclopentadienyl)zirconium dichloride, bis(cyclopentadienyl)zirconium dibromide, bis(cyclopentadienyl)methylzirconium monochloride, bis(cyclopentadienyl)ethylzirconium monochloride, bis(cyclopentadienyl) Cyclohexylzirconium monochloride, bis(cyclopentadienyl)phenylzirconium monochloride, bis(cyclopentadienyl)benzylzirconium monochloride, bis(methylcyclopentadienyl)zirconium dichloride, bis(dimethylcyclopentadienyl)zirconium dichloride , bis(n-butylcyclopentadienyl)zirconium dichloride, bis(indenyl)zirconium dichloride, bis(indenyl)
Zirconium dibromide, bis(cyclopentadienyl)zirconium dimethyl, bis(cyclopentadienyl)zirconium diphenyl, bis(cyclopentadienyl)zirconium dibenzyl, bis(cyclopentadienyl)zirconium methoxychloride, bis(cyclopentadienyl) dienyl) zirconium ethoxy chloride, bis(
Methylcyclopentadienyl)zirconium ethoxychloride, bis(cyclopentadienyl)zirconium phenoxychloride, bis(fluorenyl)zirconium dichloride.

In the above-mentioned zirconium compounds, transition metal compounds in which zirconium metal is replaced with titanium metal, hafnium metal, or vanadium metal can also be used.

The bridge type transition metal compound [C] used in the present invention has the following formula M2 L2X (wherein M2 is a transition metal, L2 is a ligand that coordinates to the transition metal, and at least Two L2 are ligands having a cycloalkadienyl skeleton and are bonded via an alkylene group, a substituted alkylene group, a silylene group, or a substituted silylene group, and are not ligands having a cycloalkadienyl skeleton. L2 is a hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group, an aryloxy group, a halogen, or hydrogen, and x is the valence of the transition metal.

In the above formula, M2 is a transition metal, specifically preferably zirconium, titanium, hafnium, chromium, vanadium,
Among these, zirconium and hafnium are particularly preferred.

Examples of the ligand having a cycloalkadienyl skeleton include a cyclopentadienyl group, a methylcyclopentadienyl group, an ethylcyclopentadienyl group, an n-butylcyclopentadienyl group, and a dimethylcyclopentadienyl group. enyl group, alkyl-substituted cyclopentadienyl group such as pentamethylcyclopentadienyl group, indenyl group, 4,5,6,7-tetrahydroindenyl group,
Examples include fluorenyl groups.

The ligands other than the ligand having a cycloalkadienyl skeleton are a hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group, an aryloxy group, a halogen, or hydrogen. Examples of hydrocarbon groups having 1 to 12 carbon atoms include alkyl groups, cycloalkyl groups, aryl groups, and aralkyl groups. Specifically, examples of alkyl groups include methyl groups, ethyl groups, and propyl groups. , isopropyl group, butyl group, etc., cycloalkyl groups include cyclopentyl group, cyclohexyl group, etc., aryl groups include phenyl group, tolyl group, etc., and aralkyl groups include benzyl group, Examples include a neophyll group.

Examples of the alkoxy group include a methoxy group, ethoxy group, and butoxy group, and examples of the aryloxy group include a phenoxy group. Examples of the halogen include fluorine, chlorine, bromine, and iodine.

[0054] Such a bridge type transition metal compound containing a ligand having a cycloalkadienyl skeleton [C] used in the present invention is more specifically is the following formula R2'R3'
R4'R5'M2 (wherein M2 is zirconium, titanium, hafnium, vanadium, etc., and at least two of R2', R3', R4' and R5', that is, R2' and R3
' is a group having a cycloalkadienyl skeleton, and the groups having two cycloalkadienyl skeletons are alkylene groups such as ethylene and propylene, isopropylidene,
They are bonded via a substituted alkylene group such as diphenylmethylene, a silylene group, a substituted silylene group such as dimethylsilylene, and R4' and R5' are a group having a cycloalkadienyl skeleton, an alkyl group, a cycloalkyl group, an aryl group, etc. group, aralkyl group, alkoxy group, aryloxy group, halogen atom, or hydrogen. ).

Hereinafter, M2 is zirconium [C]
containing at least two or more ligands having a cycloalkadienyl skeleton of Specific examples of bridge-type transition metal compounds that are bonded to each other are shown below. Ethylenebis(indenyl)
Dimethylzirconium, ethylenebis(indenyl)diethylzirconium, ethylenebis(indenyl)diphenylzirconium, ethylenebis(indenyl)methylzirconium monochloride, ethylenebis(indenyl)ethylzirconium monochloride, ethylenebis(indenyl)diethylzirconium
indenyl)methylzirconium monobromide, ethylenebis(indenyl)zirconium dichloride, ethylenebis(indenyl)zirconium dibromide, ethylenebis(4,5,6,7-tetrahydro-1-indenyl)dimethylzirconium, ethylenebis(4,5 ,6
,7-tetrahydro-1-indenyl)methylzirconium monochloride, ethylenebis(4,5,6,7-tetrahydro-1-indenyl)zirconium dichloride, ethylenebis(4,5,6,7-tetrahydro-1-
indenyl) zirconium dibromide, ethylene bis(
4-Methyl-1-indenyl) zirconium dichloride, ethylene bis(5-methyl-1-indenyl) zirconium dichloride, ethylene bis(6-methyl-1-indenyl) zirconium dichloride, ethylene bis(7
-methyl-1-indenyl) zirconium dichloride,
Ethylenebis(5-methoxy-1-indenyl)zirconium dichloride, ethylenebis(2,3-dimethyl-
1-indenyl) zirconium dichloride, ethylenebis(4,7-dimethyl-1-indenyl)zirconium dichloride, ethylenebis(4,7-dimethoxy-1-
indenyl) zirconium dichloride, isopropylidene (cyclopentadienyl-fluorenyl) zirconium dichloride, isopropylidene (cyclopentadienyl-2,7-di-t-butylfluoronyl) zirconium dichloride, isopropylidene (cyclopentadienyl-methylcyclopenta dienyl)zirconium dichloride, dimethylsilylenebis(cyclopentadienyl)zirconium dichloride, dimethylsilylenebis(methylcyclopentadienyl)zirconium dichloride, dimethylsilylenebis(dimethylcyclopentadienyl)zirconium dichloride, dimethylsilylenebis(trimethylcyclo) pentadienyl) zirconium dichloride,
Dimethylsilylenebis(indenyl)zirconium dichloride and transition metal compounds in which zirconium metal is replaced with titanium metal, hafnium metal, or vanadium metal in the above-mentioned zirconium compounds can also be used.

The organoaluminumoxy compound [D] used in the present invention may be a conventionally known aluminoxane, or may be a benzene-insoluble organoaluminumoxy compound discovered by the present inventors. good.

The above aluminoxane can be produced, for example, by the following method. (1) Compounds containing adsorbed water or salts containing crystal water, such as magnesium chloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate, ceric chloride hydrate, etc. A method of adding an organoaluminum compound such as trialkylaluminum to a suspension in a hydrocarbon medium, causing a reaction, and recovering a hydrocarbon solution. (2) A method in which water, ice, or steam is directly applied to an organoaluminum compound such as trialkylaluminium in a medium such as benzene, toluene, ethyl ether, or tetrahydrofuran to recover it as a hydrocarbon solution.

Note that the aluminoxane may contain a small amount of an organic metal component. Alternatively, the solvent or unreacted organoaluminum compound may be removed by distillation from the recovered aluminoxane solution, and then redissolved in the solvent.

[0059] Specifically, the organoaluminum compounds used in producing the aluminoxane solution include trimethylaluminum, triethylaluminum,
Tripropylaluminium, triisopropylaluminium, tri-n-butylaluminum, triisobutylaluminum, trisec-butylaluminum, tri-t
ert- trialkylaluminum such as butylaluminum, tripentylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum, tricyclohexylaluminum, tricyclooctylaluminum; dimethylaluminum chloride, diethylaluminium chloride, diethylaluminum bromide, diisobutylaluminum chloride Dialkyl aluminum hydrides such as dialkyl aluminum halides, diethylaluminum hydride, and diisobutyl aluminum hydride; dialkyl aluminum alkoxides such as dimethyl aluminum methoxide and diethylaluminum ethoxide; and dialkyl aluminum aryoxides such as diethyl aluminum phenoxide.

Among these, trialkylaluminum is particularly preferred. In addition, as this organoaluminum compound, isoprenyl aluminum represented by the following general formula (i-C4H9) You can also use

[0061] The organoaluminum compound as described above is
Used alone or in combination. Solvents used for aluminoxane solutions include aromatic hydrocarbons such as benzene, toluene, xylene, cumene, and cymene; aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, hexadecane, and octadecane; Alicyclic hydrocarbons such as cyclopentane, cyclohexane, cyclooctane, and methylcyclopentane; petroleum distillates such as gasoline, kerosene, and light oil; and halides of the above-mentioned aromatic hydrocarbons, aliphatic hydrocarbons, and alicyclic hydrocarbons, especially Examples include hydrocarbon solvents such as chlorinated compounds, brominated compounds, and the like. In addition, ethers such as ethyl ether and tetrahydrofuran can also be used. Among these solvents, aromatic hydrocarbons are particularly preferred.

Furthermore, the benzene-insoluble organoaluminumoxy compound used in the present invention has an Al content that dissolves in benzene at 60° C. in terms of Al atoms of 10% or less, preferably 5% or less, particularly preferably 2% or less. , insoluble or sparingly soluble in benzene.

The solubility of such an organoaluminumoxy compound in benzene is as follows:
After suspending in 0 ml of benzene, the mixture was stirred at 60°C for 6 hours, and then filtered while hot at 60°C using a jacketed G-5 glass filter. The amount of Al atoms present in the total filtrate after washing four times with 50 ml of benzene at
(x%).

Furthermore, when the above-mentioned benzene-insoluble organoaluminumoxy compound is analyzed by infrared spectroscopy (IR), the absorbance (D
1220) and the absorbance near 1260 cm-1 (
D1260), the ratio (D1260/D1220) is 0
．． 09 or less, preferably 0.08 or less, particularly preferably in the range of 0.04 to 0.07.

Incidentally, infrared spectroscopic analysis of the organoaluminumoxy compound is carried out as follows. First, in a nitrogen box, an organoaluminumoxy compound and Nujol are ground in an agate mortar to form a paste.

Next, the paste-like sample was treated with KBr.
The sample is placed between plates and the IR spectrum is measured using IR-810 manufactured by JASCO Corporation under a nitrogen atmosphere. Figure 2 shows the IR spectrum of the organoaluminumoxy compound used in the present invention.
Shown below.

From the IR spectrum thus obtained, D1260/D1220 is determined.
The 0/D1220 value is determined as follows. (a) Connect the maximum points near 1280 cm-1 and 1240 cm-1, and define this as the baseline L1. (b) Transmittance of absorption minimum point near 1260 cm-1 (T
%), draw a perpendicular line from this minimum point to the wavenumber axis (horizontal axis), read the transmittance (T0 %) at the intersection of this perpendicular line and baseline L1, and calculate the absorbance near 1260 cm-1 (D1260=log Calculate T0/T). (c) Similarly, around 1280cm-1 and 1180cm-1
Connect nearby maximum points and use this as the baseline L2. (d) Transmittance of absorption minimum point near 1220 cm-1 (T
'%), draw a perpendicular line from this minimum point to the wave number axis (horizontal axis), read the transmittance (T0'%) at the intersection of this perpendicular line and baseline L2, and read the absorbance (D1220) near 1220 cm-1. = log T0'/T'). (e) Calculate D1260/D1220 from these values.

FIG. 3 shows an IR spectrum of a conventionally known benzene-soluble organoaluminumoxy compound. As can be seen from FIG. 3, the D1260/D1220 value of the benzene-soluble organoaluminumoxy compound is approximately between 0.10 and 0.13, and the benzene-insoluble organoaluminumoxy compound used in the present invention has a D1260/D1220 value of approximately 0.10 to 0.13. The D1260/D1220 value is clearly different from conventionally known benzene-soluble organoaluminumoxy compounds.

The above benzene-insoluble organoaluminumoxy compound has the following formula:

[0070]

[C7]

It is presumed to have an alkyloxyaluminum unit represented by the following formula (wherein R1 is a hydrocarbon group having 1 to 12 carbon atoms). In the above alkyloxyaluminum unit, R1 specifically represents a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-
Examples include butyl group, isobutyl group, pentyl group, hexyl group, octyl group, decyl group, cyclohexyl group, and cyclooctyl group. Among these, methyl group and ethyl group are preferred, and methyl group is particularly preferred.

This benzene-insoluble organoaluminumoxy compound has the following formula:

[0073]

[Chemical formula 8]

In addition to the alkyloxyaluminum unit [i] represented by (wherein R1 is a hydrocarbon group having 1 to 12 carbon atoms), the following formula

[0075]

[Chemical formula 9]

(In the formula, R2 is a hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or a C 6 to 2
0 aryloxy group, hydroxyl group, halogen or hydrogen. Further, R2 and R1 in the alkyloxyaluminum unit [i] represent mutually different groups. ) may contain an oxyaluminum unit [ii] represented by

In that case, the content of the alkyloxyaluminum unit [i] is 30 mol% or more, preferably 50 mol%
As mentioned above, an organoaluminumoxy compound having an alkyloxyaluminum unit in a proportion of 70 mol % or more is particularly preferred.

Next, a method for producing the benzene-insoluble organoaluminumoxy compound as described above will be specifically explained. This benzene-insoluble organoaluminumoxy compound is obtained by contacting a solution of aluminoxane with water or an active hydrogen-containing compound.

As the active hydrogen-containing compound, alcohols such as methanol, ethanol, n-propanol and isopropal, diols such as ethylene glycol and hydroquinone, and organic acids such as acetic acid and propionic acid are used. Among these, alcohols and diols are preferred, and alcohols are particularly preferred.

Water or an active hydrogen-containing compound to be brought into contact with the aluminoxane solution may be dissolved or dispersed in a hydrocarbon solvent such as benzene, toluene or hexane, an ether solvent such as tetrahydrofuran, an amine solvent such as triethylamine, or , can be used in vapor or solid state. In addition, as water, crystallized water of salts such as magnesium chloride, magnesium sulfate, aluminum sulfate, copper sulfate, nickel sulfate, iron sulfate, and cerous chloride, or adsorbed on inorganic compounds or polymers such as silica, alumina, and aluminum hydroxide. Adsorbed water or the like can also be used.

The contact reaction between the aluminoxane solution and water or the active hydrogen-containing compound is usually carried out in a solvent, for example a hydrocarbon solvent. Solvents used in this case include aromatic hydrocarbons such as benzene, toluene, xylene, cumene, and cymene; aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, hexadecane, and octadecane; cyclopentane, cyclohexane, etc. , alicyclic hydrocarbons such as cyclooctane and methylcyclohexane; hydrocarbon solvents such as petroleum fractions such as gasoline, kerosene, and light oil; or halides of the above-mentioned aromatic hydrocarbons, aliphatic hydrocarbons, and alicyclic hydrocarbons, especially ,
It is also possible to use halogenated hydrocarbons such as chlorides and bromides, and ethers such as ethyl ether and tetrahydrofuran.

Among these media, aromatic hydrocarbons are particularly preferred. The water or active hydrogen-containing compound used in the catalytic reaction is used in an amount of 0.1 to 5 mol, preferably 0.2 to 3 mol, based on the Al atoms in the aluminoxane solution. It is desirable that the concentration in the reaction system is usually in the range of 1 x 10-3 to 5 gram atoms/liter, preferably 1 x 10-2 to 3 gram atoms/liter, in terms of aluminum atoms. The concentration of water in the system is usually 2 x 10-4 to 5 mol/liter, preferably 2 x 10-3 to 3 mol/liter.

[0083] The aluminoxane solution may be brought into contact with water or an active hydrogen-containing compound in the following manner. (1) A method of bringing a solution of aluminoxane into contact with water or a hydrocarbon solvent containing an active hydrogen-containing compound. (2) A method of bringing aluminoxane and steam into contact by, for example, blowing water or steam of an active hydrogen-containing compound into a solution of aluminoxane. (3) A method in which a solution of aluminoxane is brought into direct contact with water, ice, or an active hydrogen-containing compound. (4) A solution of aluminoxane is mixed with a hydrocarbon suspension of an adsorbed water-containing compound, a hydrocarbon suspension of a crystal water-containing compound, or a hydrocarbon suspension of a compound to which an active hydrogen-containing compound has been adsorbed, and the aluminoxane is A method of contacting adsorbed water or crystallized water with water.

[0084] The aluminoxane solution as described above may contain other components as long as they do not adversely affect the reaction between the aluminoxane and water or the active hydrogen-containing compound.

[0085] The contact reaction between the aluminoxane solution and water or an active hydrogen-containing compound is usually carried out at -50 to 150°C.
, preferably 0 to 120°C, more preferably 20 to 10
It is carried out at a temperature of 0°C. The reaction time varies greatly depending on the reaction temperature, but is usually about 0.5 to 300 hours, preferably about 1 to 150 hours.

The benzene-insoluble organoaluminumoxy compound can also be directly obtained by bringing the above-mentioned organoaluminum into contact with water. In this case, water is used in an amount such that the amount of organic aluminum atoms dissolved in the reaction system is 20% or less based on the total organic aluminum atoms.

The water to be brought into contact with the organoaluminum compound may be a hydrocarbon solvent such as benzene, toluene or hexane,
It can be used by dissolving or dispersing it in an ether solvent such as tetrahydrofuran, an amine solvent such as triethylamine, or in the form of water vapor or ice. Also, as water, crystallized water of salts such as magnesium chloride, magnesium sulfate, aluminum sulfate, copper sulfate, nickel sulfate, iron sulfate, and cerous chloride, or adsorbed on inorganic compounds or polymers such as silica, alumina, and aluminum hydroxide. Adsorbed water or the like can also be used.

The contact reaction between the organoaluminum compound and water is usually carried out in a hydrocarbon solvent. Hydrocarbon solvents used in this case include aromatic hydrocarbons such as benzene, toluene, xylene, cumene, and cymene, pentane, hexane, heptane, octane, decane, dodecane,
Aliphatic hydrocarbons such as hexadecane and octadecane, alicyclic hydrocarbons such as cyclopentane, cyclohexane, cyclooctane, and methylcyclohexane, petroleum fractions such as gasoline, kerosene, and light oil, or the above-mentioned aromatic hydrocarbons,
Examples include hydrocarbon solvents such as halides of aliphatic hydrocarbons and alicyclic hydrocarbons, especially chlorinated and brominated compounds. In addition, ethers such as ethyl ether tetrahydrofuran can also be used. Among these media, aromatic hydrocarbons are particularly preferred.

The concentration of the organoaluminum compound in the reaction system is usually 1 x 10-3 to 5 in terms of aluminum atoms.
The concentration of water in the reaction system is usually 1 x 10-3 to 5 mol/liter, preferably 1 x 10-2 to 3 mol/liter. A concentration of 1×10 −2 to 3 mol/liter is desirable. At this time, it is desirable that the amount of organic aluminum atoms dissolved in the reaction system is 20% or less, preferably 10% or less, and more preferably 0 to 5% based on the total organic aluminum atoms.

[0090] Specific methods for bringing the organoaluminum compound into contact with water include the following methods. (1) A method in which a hydrocarbon solution of organoaluminum is brought into contact with a hydrocarbon solvent containing water. (2) A method of bringing organic aluminum and water vapor into contact, such as by blowing water vapor into a hydrocarbon solution of organic aluminum. (3) A method of mixing a hydrocarbon solution of an organoaluminum and a hydrocarbon suspension of an adsorbed water-containing compound or a crystal water-containing compound, and bringing the organoaluminum into contact with the adsorbed water or crystal water. (4) A method of bringing an organic aluminum hydrocarbon solution into contact with ice.

The hydrocarbon solution of organoaluminum as described above may contain other components as long as they do not adversely affect the reaction between organoaluminum and water. The contact reaction between an organoaluminum compound and water is usually -100
It is carried out at a temperature of -150°C, preferably -70 to 100°C, more preferably -50 to 80°C. The reaction time also varies greatly depending on the reaction temperature, but is usually 1 to 20
0 hours, preferably about 2 to 100 hours.

[0092] As the organoaluminum compound [E] used in the present invention, for example, the following formula R6n AlX3-n (wherein R6 is a hydrocarbon group having 1 to 12 carbon atoms,
X is halogen or hydrogen, and n is 1 to 3).

In the above formula, R6 has 1 to 12 carbon atoms.
Hydrocarbon groups such as alkyl groups, cycloalkyl groups, or aryl groups, specifically methyl, ethyl, n-propyl, isopropyl, isobutyl, pentyl, hexyl, octyl groups. , cyclopentyl group, cyclohexyl group, phenyl group, tolyl group, etc.

[0094] Specifically, the following compounds are used as such organoaluminum compounds. Trialkyl aluminum such as trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, trioctylaluminum, tri-2-ethylhexylaluminum; alkenylaluminum such as isoprenylaluminum; dimethylaluminum chloride, diethylaluminum chloride, diisopropylaluminium chloride, dialkylaluminum halides such as diisobutylaluminum chloride, dimethylaluminum bromide; alkylaluminum sesquihalides such as methylaluminum sesquichloride, ethylaluminum sesquichloride, isopropylaluminum sesquichloride, butylaluminum sesquichloride, ethylaluminum sesquibromide; methylaluminum dichloride, Alkylaluminum dihalides such as ethylaluminum dichloride, isopropylaluminum dichloride, and ethylaluminum dibromide; Alkylaluminum hydrides such as diethylaluminum hydride and diisobutylaluminum hydride; In addition, as the organoaluminum compound of component [E], the following formula R6n AlY3-n ( In the formula, R6 is the same as above, and Y is -OR7 group, -OSiR83 group, -OAlR92 group, -NR1
02 group, -SiR113 group or -N(R12)A
lR132 group, n is 1 to 2, R7, R
8, R9 and R13 are methyl group, ethyl group, isopropyl group, isobutyl group, cyclohexyl group, phenyl group, etc., and R10 is hydrogen, methyl group, ethyl group,
Examples are isopropyl group, phenyl group, trimethylsilyl group, etc., and R11 and R12 are methyl group, ethyl group, etc. ) can also be used.

[0095] Specifically, the following compounds are used as such organoaluminum compounds. (i) Compounds represented by R6n Al(OR7)3-n, such as dimethylaluminum methoxide, diethylaluminum ethoxide, diisobutylaluminum methoxide, etc. (ii) Compounds represented by R6n Al(OSi R83)3-n Compounds such as Et2Al(OSiMe3)(iso-Bu
)2 Al(OSiMe3)(iso-Bu)2
Al(OSi Et3) etc., (iii) R6n A
A compound represented by l(OAlR92)3-n, for example, Et2 AlOAlEt2 (iso-Bu)2 AlOAl(iso-Bu)2
etc., (iv) R6n Al(NR102)3-n
Compounds represented by Me2 AlNEt 2 Et2 AlNHMe Me2 AlNHEt Et2 AlN(SiMe3 )2 (iso-Bu)2 AlN(SiMe3)2 etc., (v) R6n Al(Si R113 )3-n
Compounds represented by, for example (iso-Bu)2AlSiMe3, etc.

00
96]

[Chemical formula 10]

[0097] As the organoaluminum compound as described above, the following formula, R63 Al, R6n Al (OR7)
Preferred examples include organoaluminum compounds represented by 3-n, R6n Al(OAlR92)3-n, where R6 is an isoalkyl group and n=
2 is particularly preferred. Two or more of these organoaluminum compounds can also be used in combination.

Specifically, the solid catalyst for olefin polymerization in the present invention can be prepared as follows. First, a particulate carrier [A], a non-bridge type transition metal compound [B], a bridge type transition metal compound [C], an organoaluminumoxy compound [D], and if necessary, an organoaluminum compound [E] The solid catalyst for olefin polymerization according to the present invention can be obtained by mixing them in an inert hydrocarbon solvent, introducing an olefin therein, and performing preliminary polymerization.

At this time, the mixing order can be arbitrarily selected, but it is preferable to mix and contact in the order of [A] → ([E]) → [D] → [B] → olefin → [C] → olefin, or [
A]→([E])→[D]→[B]+[C]→Olefin is mixed and contacted in this order.

In addition, a non-bridge type transition metal compound [B], a bridge type transition metal compound [C], an organoaluminumoxy compound [D] and, if necessary, an organoaluminum compound [B] are added to the particulate carrier [A]. E
The solid catalyst for olefin polymerization according to the present invention can also be obtained by supporting the catalyst, introducing an olefin in the absence of a solvent, and performing preliminary polymerization.

[0101] When mixing components [A] to [D], and optionally further component [E], component [B]
and component [C] in a total amount of usually 10-5 to 5 x 10-3 mol, preferably 5 x 10-3 mol per gram of component [A].
It is used in an amount of 5 to 10-3 mol, and the total concentration of component [B] and component [C] is about 10-4 to 2 x 10-2 mol/liter, preferably 2 x 10-4 to 10 -2 mol/liter range. In addition, component [B] and component [C
] When the total amount of component [B] is 100 mol%
is in an amount of 5 to 80 mol%, preferably 7 to 70 mol%,
More preferably, the amount is 10 to 60 mol%.

The atomic ratio (Al/transition metal) of the transition metal in component [B] and component [C] to aluminum in component [D] is usually 10 to 500, preferably 20 to 20.
It is 0. The atomic ratio (AlE/AlD) of aluminum atoms (AlE) of component [E] and aluminum atoms (AlD) of component [D], which are used as necessary, is usually 0.02 to 3, preferably 0.05 to 1. It is in the range of .5. The mixing temperature when mixing components [A] to [D] and, if necessary, further component [E] is usually -20 to
80°C, preferably 0-60°C, and the contact time is 1-60°C.
The duration is 200 minutes, preferably 5 to 120 minutes.

[0103] Olefin is prepolymerized in the presence of components [A] to [D] as described above and, if necessary, component [E]. During prepolymerization, the transition metal compound is
It is usually used in an amount of 10-4 to 2 x 10-2 mol/liter, preferably 5 x 10-4 to 10-2 mol/liter, and the prepolymerization temperature is -20 to 80°C, preferably 0 to 5
0°C, and the prepolymerization time was 0.5 to 100 hours.
Preferably it is about 1 to 50 hours.

The olefin used in the prepolymerization is selected from among the olefins used during polymerization, but ethylene is preferred. The solid catalyst for olefin polymerization of the present invention obtained as described above has about 5 x 10-6 to 5 x 10-4 gram atoms, preferably 10-5 to 3 x 10-4, per gram of component [A]. Gram atoms of transition metal atoms are supported, and about 10@-3 to 10@-1 gram atoms, preferably 2.times.10@-3 to 5.times.10@-2 gram atoms of aluminum atoms are supported.

Further, the amount of polymer produced by prepolymerization is desirably in the range of about 0.1 to 500 g, preferably 0.3 to 300 g, particularly preferably 1 to 100 g, per 1 g of the particulate carrier.

[0106] Specific examples of the inert hydrocarbon medium used in the preparation of the solid catalyst for olefin polymerization according to the present invention include fats such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene. group hydrocarbons; alicyclic hydrocarbons such as cyclopentane, cyclohexane, and methylcyclopentane; aromatic hydrocarbons such as benzene, toluene, and xylene;
Examples include halogenated hydrocarbons such as ethylene chloride, chlorobenzene, dichloromethane, and mixtures thereof.

[0107] When olefin polymerization is carried out using the solid catalyst for olefin polymerization in which olefins have been prepolymerized as described above, the transition metal compounds [B] and [C] are added in a proportion of transition metal atoms per liter of polymerization volume. Usually 10-8 to 10-3 gram atoms, preferably 10-
Preferably, amounts of 7 to 10-4 gram atoms are used. At this time, an organic aluminum compound or aluminoxane may be used as necessary. Examples of the organoaluminum compound used in this case include compounds similar to the organoaluminum compound [E] described above. The amount used is 0 to 50 per gram atom of transition metal atom.
It is desirable that the amount is 0 mol, preferably in the range of 5 to 200 mol.

Olefins that can be polymerized with such an olefin polymerization catalyst include ethylene and α-olefins having 3 to 20 carbon atoms, such as propylene, 1-butene, 1-pentene, 1-hexene, 4
-Methyl-1-pentene, 1-octene, 1-decene,
1-dodecene, 1-tetradecene, 1-hexadecene,
1-octadecene, 1-eicosene, cyclopentene,
Cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene, 2-methyl 1,4
,5,8-dimethano-1,2,3,4,4a,5,8,
Examples include 8a-octahydronaphthalene. Furthermore, styrene, vinylcyclohexane, diene, etc. can also be used.

In the present invention, polymerization can be carried out by either a liquid phase polymerization method such as suspension polymerization or a gas phase polymerization method. In the liquid phase polymerization method, the same inert hydrocarbon solvent used in the catalyst preparation method can be used, or the olefin itself can be used as the solvent.

[0110] The polymerization temperature of olefin using such an olefin polymerization catalyst is usually in the range of -50 to 150°C, preferably 0 to 100°C. The polymerization pressure is usually normal pressure to 100 kg/cm2, preferably normal pressure to 50 kg/cm2.
g/cm2, and the polymerization reaction can be carried out in any of the batch, semi-continuous, and continuous methods. Furthermore, it is also possible to carry out the polymerization in two or more stages with different reaction conditions. The molecular weight of the resulting olefin polymer can be controlled by the presence of hydrogen in the polymerization system or by changing the polymerization temperature.

In the present invention, the olefin polymerization catalyst may contain other components useful for olefin polymerization in addition to the above-mentioned components.

[0112]

Effects of the Invention The solid catalyst for olefin polymerization according to the present invention comprises a particulate carrier [A], a transition metal compound having a cycloalkadienyl skeleton, an organoaluminumoxy compound [D], and optionally [ E] When polymerizing olefins using an organoaluminum compound, [B] a non-bridge type transition metal compound and [C] a bridge type transition metal compound are used in combination. Therefore, the polymerization activity is excellent and the yield is excellent. The resulting polymer has excellent particle properties and melt tension.

[0113] Furthermore, the solid catalyst for olefin polymerization according to the present invention can be used for olefin polymerization, particularly when used for suspension polymerization or gas phase polymerization, in which olefins could not be polymerized with high polymerization activity in the past. Olefins can be polymerized with high polymerization activity, and olefin polymers with excellent particle properties can be obtained.

[0114]

[Examples] The present invention will be explained below with reference to Examples, but the present invention is not limited to these Examples.

[0115] In this specification, melt tension (hereinafter referred to as
(sometimes referred to as MT) is measured as follows. Melt tension (MT) is determined by measuring the stress when a molten polymer is stretched at a constant speed. That is, the produced polymer powder or the polymer obtained by melting the powder in decane and precipitating it in a methanol/acetone (1/1) solution of 5 times or more the amount of decane was used as the measurement sample, and The test was carried out using an MT measuring machine under the following conditions: resin temperature of 190° C., extrusion speed of 10 mm/min, winding speed of 10 to 20 m/min, nozzle diameter of 2.09 mmφ, and nozzle length of 8 mm. When measuring melt tension, 0.1% by weight of 2,6-di-t-butyl para-cresol as a crosslinking stabilizer was mixed in advance with the ethylene copolymer.

[0116]

[Example 1] [Preparation of solid catalyst (zirconium catalyst)] In a 400 ml glass flask that was sufficiently purged with nitrogen, 1.38 g of silica (manufactured by Fuji Davison, F-948) calcined at 700°C for 6 hours was added. 20 ml of decane was added to make a suspension. 3.24 ml of a decane solution of triisobutylaluminum (Al; 1 mol/liter) was added to this suspension, and the mixture was stirred at room temperature for 30 minutes.

Next, in this suspension, 18.8 ml of a toluene solution of an organoaluminium oxy compound (Methylaluminoxane manufactured by Schering Co., Ltd. was dried and then redissolved in toluene, Al; 0.864 mol/liter) was added.
was added and further stirred at room temperature for 30 minutes.

Thereafter, 1.03 ml of a toluene solution of bis(cyclopentadienyl)zirconium dichloride (Zr; 0.0417 mol/liter) was added to this suspension, and after stirring for 10 minutes, 50 ml of decane was added. In addition, ethylene gas (normal pressure) was continuously introduced and the temperature was increased to 30℃ for 2 hours.
A time prepolymerization was carried out.

[0119] Thereafter, the Zr concentration of ethylene bis(indenyl) zirconium dichloride was reduced to 0.00172 mol/
100.5 ml of toluene solution was added and prepolymerization was further continued at 30° C. for 4 hours.

After this prepolymerization, the solvent was removed by decantation, and then hot washing (60 mL) with 250 ml of hexane was performed.
°C) three times, and then washed with 250 ml of hexane (room temperature).
was performed three times. By this operation, 9.5 mg atoms of zirconium, 0.66 g atoms of aluminum, and 1750 mg of polyethylene per 100 g of silica.
A solid catalyst containing g was obtained. [Polymerization] Sodium chloride (Wako Pure Chemicals special grade) 150 ml was placed in a stainless steel autoclave with an internal volume of 2 liters that was sufficiently purged with nitrogen.
g was charged and dried under reduced pressure at 90° C. for 1 hour. Thereafter, the pressure was returned to normal by introducing ethylene gas, and the inside of the system was set at 70°C. Next, 0.3 mmol of triisobutylaluminum and the above solid catalyst (0.00 mmol in terms of zirconium atom)
A premix of 3 milligram atoms) was charged to the autoclave.

Next, 50 Nml of hydrogen was introduced, and then ethylene was introduced at 70°C to bring the total pressure to 8 kg/cm2-G.
Polymerization started as follows. After that, only ethylene was supplied,
The total pressure was maintained at 8 kg/cm2-G, and polymerization was carried out at 85°C for 1 hour. After the polymerization was completed, the sodium chloride was removed by washing with water, the remaining polymer was washed with methanol, and then
It was dried under reduced pressure at °C overnight. As a result, the bulk specific gravity is 0.43g
/cm3, the MFR measured at 190°C under a load of 2.16 kg is 0.65 g/10 min, the melt tension (MT) is 10 g, and the average polymer particle size is 41
142 g of a polymer having a diameter of 0 μm was obtained.

[0122]

[Example 2] [Preparation of solid catalyst (zirconium catalyst)] 20 ml of decane was added to 1.12 g of the same silica as in Example 1 to form a suspension, and a decane solution of triisobutylaluminum (Al; 1 mol/ml) was added to the suspension. 2.8 ml) was added, and the mixture was stirred at room temperature for 35 minutes.

Next, a toluene solution of the same organoaluminumoxy compound as in Example 1 (Al;
0.864 mol/liter) was added thereto, and the mixture was further stirred at room temperature for 25 minutes.

Thereafter, 1.34 ml of a toluene solution of bis(cyclopentadienyl)zirconium dichloride (Zr; 0.0417 mol/liter) was added to this suspension, and after stirring for 30 minutes, 50 ml of decane was added. was added, ethylene gas (normal pressure) was introduced continuously, and the temperature was heated to 30°C.
Prepolymerization was carried out for 2 hours. Then, ethylene bis(
(indenyl) zirconium dichloride has a Zr concentration of 0.
00183 mol/liter toluene solution 71.3
ml was added and further prepolymerization was continued at 30° C. for 3.5 hours. The subsequent operations were carried out in the same manner as in Example 1 to obtain a solid catalyst containing 9.6 milligram atoms of zirconium, 0.66 grams of aluminum, and 2100 grams of polyethylene per 100 g of silica. [Polymerization] Conducted in the same manner as in Example 1, bulk specific gravity was 0.42 g/cm3
88 g of a polymer having an MFR of 0.60 g/10 min and an average polymer particle size of 380 μm was obtained.

[0125]

[Example 3] [Preparation of solid catalyst (zirconium catalyst)] 30 ml of decane was added to 3.0 g of the same silica as in Example 1 to form a suspension, and a decane solution of triisobutylaluminum (
7.45 ml of Al (1 mol/liter) was added thereto, and the mixture was stirred at room temperature for 25 minutes.

Next, a toluene solution of the same organoaluminumoxy compound as in Example 1 (Al;
2.13 mol/liter) was added thereto, and the mixture was further stirred at room temperature for 25 minutes.

Thereafter, 2.14 toluene solution of bis(methylcyclopentadienyl)zirconium dichloride (Zr; 0.0465 mol/liter) was added to this suspension.
After adding 100ml of decane and stirring for 5 minutes,
ml and continuously introduced ethylene gas (at normal pressure).
Prepolymerization was carried out at 25°C for 2.5 hours. After that, Zr of ethylenebis(indenyl)zirconium dichloride
166.4 ml of a toluene solution having a concentration of 0.0024 mol/liter was added, and the prepolymerization was further continued at 30° C. for 5 hours. The subsequent operations were carried out in the same manner as in Example 1 to obtain a solid catalyst containing 9.0 milligram atoms of zirconium, 0.55 grams of aluminum and 2000 grams of polyethylene per 100 grams of silica. [Polymerization] In the polymerization of Example 1, the amount of triisobutylaluminum used was 0.54 mmol, and the amount of ethylene was 6.5 k.
Polymerization was carried out in the same manner except that the catalyst component was pressurized into an autoclave pressurized to g/cm2-G. the result,
Bulk specific gravity is 0.41g/cm3, MFR is 0.5
8 g/10 min, melt tension (MT) of 13 g, and polymer average particle size of 400 μm.
I got it.

[0128]

[Comparative Example 1] [Preparation of solid catalyst (zirconium catalyst)] 20 ml of decane was added to 3.05 g of the same silica as in Example 1 to make a suspension, and a decane solution of triisobutylaluminum (Al; 1 mol/ 7.61 ml) was added thereto, and the mixture was stirred at room temperature for 30 minutes.

Next, a toluene solution of the same organoaluminumoxy compound as in Example 1 (Al;
2.13 mol/liter) was added thereto, and the mixture was further stirred at room temperature for 30 minutes.

Thereafter, 10.9 of a toluene solution of bis(methylcyclopentadienyl)zirconium dichloride (Zr; 0.0465 mol/liter) was added to this suspension.
After adding 10 ml of decane and stirring for 30 minutes, add 10 ml of decane.
0 ml was added, ethylene gas (normal pressure) was continuously introduced, and prepolymerization was carried out at 30° C. for 3.5 hours. The subsequent operations were carried out in the same manner as in Example 1 to obtain a solid catalyst containing 12.0 milligram atoms of zirconium, 0.71 grams of aluminum, and 790 grams of polyethylene per 100 g of silica. [Polymerization] Polymerization was carried out in the same manner as in Example 3 except that 0.015 milligram atoms of the solid catalyst obtained above was used in terms of zirconium atoms, and the bulk specific gravity was 0.42 g/cm3 and the MFR was 0. 70 g of polymer were obtained with a melt tension of 3.5 g and a melt tension of 3.5 g.

[0131]

[Comparative Example 2] [Preparation of solid catalyst (zirconium catalyst)] 20 ml of decane was added to 1.16 g of the same silica as in Example 1 to make a suspension, and a decane solution of triisobutylaluminum (Al; 1 mol/ 4.05 ml) was added, and the mixture was stirred at room temperature for 30 minutes.

Next, a toluene solution of the same organoaluminumoxy compound as in Example 1 (Al;
2.13 mol/liter) was added thereto, and the mixture was further stirred at room temperature for 30 minutes.

After that, ethylene bis(
toluene solution of (indenyl) zirconium dichloride (
After adding 80.5 ml of Zr (0.0024 mol/liter) and stirring for 30 minutes, 50 ml of decane and 90 ml of toluene were further added, and ethylene gas (at normal pressure) was continuously introduced, and preheated at 30°C for 3 hours. Polymerization was carried out. The subsequent operations were carried out in the same manner as in Example 1, and 100 g of silica was used.
8.9 mg atom of zirconium, 0.56 g atom of aluminum and 1 g atom of polyethylene.
A solid catalyst containing 000g was obtained. [Polymerization] The polymerization was carried out in the same manner as in Example 3, and the bulk specific gravity was 0.36 g/
cm3, MFR is 0.44g/10min,
123 g of a polymer having an average particle size of 370 μm was obtained.

[0134]

[Example 4] [Polymerization] In the polymerization of Example 1, a mixed gas of ethylene and 1-butene (1-butene content: 3.9 mol%) was used instead of ethylene, and the amount of hydrogen added was 30 Nml. 0.75 mmol of triisobutylaluminum and 0.0075 mmol of the solid catalyst component prepared in Example 3 in terms of zirconium atom.
Using milligram atoms, polymerization temperature 80℃, total pressure 2.5
Polymerization was carried out in the same manner as in Example 1, except that the bulk specific gravity was 0.38 g/cm3, and the MFR was
is 0.82g/10min and melt tension (MT) is 9g
Polymer 1 with a density of 0.918 g/cm3
72g was obtained.

[0135]

[Example 5] [Preparation of solid catalyst (zirconium catalyst)] 25 ml of decane was added to 1.49 g of the same silica as in Example 1 to form a suspension, and a solution of triisobutylaluminum in decane (Al; 1 mol/ml) was added to the suspension. 3.72 ml) was added thereto, and the mixture was stirred at room temperature for 45 minutes.

Next, a toluene solution of the same organoaluminumoxy compound as in Example 1 (Al;
2.30 mol/liter) was added thereto, and the mixture was further stirred at room temperature for 45 minutes.

Thereafter, 2.13 toluene solution of bis(methylcyclopentadienyl)zirconium dichloride (Zr; 0.0465 mol/liter) was added to this suspension.
After adding 75 ml of decane and stirring for 10 minutes,
ml and continuously introduced ethylene gas (at normal pressure).
Prepolymerization was carried out at 30°C for 1.5 hours. After that, Zr of ethylenebis(indenyl)zirconium dichloride
51.9 ml of a toluene solution having a concentration of 0.00287 mol/liter was added, and the prepolymerization was further continued at 30° C. for 4 hours. The subsequent operations were carried out in the same manner as in Example 1 to obtain a solid catalyst containing 11.5 milligram atoms of zirconium, 0.71 grams of aluminum, and 1700 grams of polyethylene per 100 g of silica. [Polymerization] In the polymerization of Example 1, a mixed gas of ethylene and 1-butene (1-butene content: 4.4 mol%) was used instead of ethylene, the amount of hydrogen added was 30 Nml, and the amount of triisobutylaluminum was 0. Polymerization was carried out in the same manner as in Example 1, except that 0.005 milligram atoms of the solid catalyst component prepared above was used in terms of zirconium atoms, and the bulk specific gravity was 0.39 g/cm3, and the MFR was 0.5 mmol. 53
g/10 minutes, the melt tension (MT) is 12 g,
137 g of a polymer having a density of 0.917 g/cm3 was obtained.

[Brief explanation of the drawing]

FIG. 1 is an explanatory diagram of an olefin polymerization catalyst according to the present invention.

[Figure 2] I of benzene-insoluble aluminum oxy compound
This is the R spectrum.

[Figure 3] I of benzene-soluble aluminum oxy compound
This is the R spectrum.

Claims (6)

[Claims] Claim 1: [A] a particulate carrier; [B] a transition metal compound containing ligands having a cycloalkadienyl skeleton that are not bonded to each other; and [C] a coordination having a cycloalkadienyl skeleton. [ D] A solid catalyst for olefin polymerization, which is formed by prepolymerizing an olefin in a suspension or gas phase containing an organoaluminumoxy compound. [Claim 2] [A] a particulate carrier; [B] a transition metal compound containing ligands having a cycloalkadienyl skeleton that are not bonded to each other; and [C] a coordination having a cycloalkadienyl skeleton. [ A solid catalyst for olefin polymerization, which is formed by prepolymerizing an olefin in a suspension or gas phase containing D] an organoaluminumoxy compound and [E] an organoaluminum compound. . 3. A method for polymerizing olefins, which comprises polymerizing or copolymerizing olefins in the presence of the solid catalyst for olefin polymerization according to claim 1. 4. A method for polymerizing olefins, which comprises polymerizing or copolymerizing olefins in the presence of the solid catalyst for olefin polymerization according to claim 2. 5. A method for polymerizing olefins, which comprises polymerizing or copolymerizing olefins in the presence of the solid catalyst for olefin polymerization according to claim 1 and an organoaluminum compound. 6. A method for polymerizing olefins, which comprises polymerizing or copolymerizing olefins in the presence of the solid catalyst for olefin polymerization according to claim 2 and an organoaluminum compound.