JPS6389505A - Olefin polymerization method - Google Patents

Abstract

PURPOSE:To polymerize an olefin in excellent polymerization activity even in a decreased amount of an aluminoxane used, by using a catalyst comprising a specified supported solid catalyst component, an aluminoxane and a specified organoaluminum compound. CONSTITUTION:An olefin is (co)polymerized in the presence of a catalyst formed from a solid catalyst component (A) formed by allowing an inorganic carrier (e.g., SiO2 or Al2O3) to support a Group IV B transition metal compound [e.g., bis(cyclopentadienyl)zirconium dichloride], an aluminoxane (B) [e.g., a compound of formula I or II (wherein R is methyl or the like and m is an integer >=2)] and an organoaluminum compound (c) having a hydrocarbon group other than an n-alkyl group (e.g., triisopropylaluminum). When olefin polymerization, especially, ethylene polymerization or copolymerization of ethylene with an alpha-olefin according to the above process is performed by a slurry polymerization or vapor-phase polymerization process, the catalytic activity is high even in a decreased amount of the aluminoxane used and no adhesion of polymer to the reactor occurs. When this process is applied to the copolymerization of at least two olefins, a copolymer of a narrow MW distribution and a narrow composition distribution can be obtained.

Description

[Detailed description of the invention] [Industrial application field] The present invention relates to a method for polymerizing olefins.

In particular, the present invention relates to a method for polymerizing olefins with excellent polymerization activity even when using a small amount of aluminoxane. More specifically, the present invention relates to a method for polymerizing olefins that allows production of spherical polymers with good particle size distribution and excellent bulk specific gravity when slurry polymerization or gas phase polymerization is employed. The present invention also relates to a method for polymerizing an olefin copolymer having a narrow molecular weight distribution and a narrow composition distribution with excellent polymerization activity when applied to the copolymerization of two or more types of olefins.

[Conventional technology]

Conventionally, methods for producing α-olefin polymers, particularly ethylene polymers or ethylene/α-olefin copolymers, have been carried out using titanium-based catalysts made of titanium compounds and organoaluminum compounds, or vanadium-based catalysts made of vanadium compounds and organoaluminium compounds. A method of copolymerizing ethylene or ethylene and an α-olefin in the presence of is known. Generally, ethylene/α-olefin copolymers obtained with titanium-based catalysts have a wide molecular weight distribution and composition distribution, and are poor in transparency, surface non-adhesion, and mechanical properties. In addition, ethylene/α-olefin copolymers obtained using vanadium catalysts have narrower molecular weight and composition distributions (and significantly lower transparency, surface non-adhesiveness, and mechanical properties) than those obtained using titanium catalysts. Although improved, these properties are still insufficient for applications requiring these properties, and there is a need for α-olefin polymers, especially ethylene/α-olefin copolymers, which have further improved these properties.

On the other hand, a catalyst consisting of a zirconium compound and an aluminoxane has recently been proposed as a new Ziegler type olefin polymerization catalyst.

JP-A No. 58-19309 discloses the following formula 4% [where R is cyclopentadienyl, C1 to C6 alkyl, halogen, Me is a transition metal, Ha
i! is a halogen] and the transition metal-containing compound represented by the following formula % formula %) [where R is methyl or ethyl and 7 is 4-20
ethylene and C5 in the presence of a catalyst consisting of a flocculent aluminoxane represented by A method is described in which one or more α-olefins of ~C+Z are polymerized at temperatures of 150°C to 200°C. The publication states that in order to adjust the density of the polyethylene obtained, the polymerization of ethylene should be carried out in the presence of small amounts of up to 10% by weight of somewhat long-chain α-olefins or mixtures. .

JP-A-59-95292 describes a linear aluminoxane represented by the following formula, [where 7 is 2 to 40 and R is C0 to C8] and a linear aluminoxane represented by the following formula [where 1 and R
The definitions are the same as above] is described. The publication states that when olefin polymerization is carried out by mixing, for example, methylaluminoxane and a titanium or zirconium bis(cyclopentagenyl) compound produced by the same production method, the 25 per hour
It is stated that more than 1 million g of polyethylene can be obtained.

JP-A No. 60-35005 describes the following formula [where,
RI is C1~self. alkyl, RO is RI or combined to represent -0-] is first reacted with a magnesium compound, and then the reaction product is chlorinated and further treated with TiXV, Zr or Cr. A method for producing a polymerization catalyst for olefins is disclosed. The publication states that the above catalyst is particularly suitable for copolymerizing a mixture of ethylene and C3-C+Z α-olefin.

JP-A No. 60-35006 discloses that two or more different transition metal mono-, di-, or tri-cyclopentadienyl or derivatives thereof (a) and alumoxane ( Aluminoxane) (b) combinations are disclosed.

In Example 1 of the same publication, ethylene and propylene were polymerized using bis(pentamethylcyclopentagenyl)zirconium dimethyl and alumoxane as catalysts, with a number average molecular weight of 15,300 and a weight average molecular weight of ff 136,40.
It is disclosed that polyethylene containing 0 and 3.4% propylene components was obtained. In addition, in Example 2, ethylene and propylene were polymerized using bis(pentamethylcyclopentagenyl)zirconium dichloride, bis(methylcyclopentagenyl)zirconium dichloride, and alumoxane as catalysts, and the number average molecular weight was 2.
．． 200, weight average molecular weight L 1 , 900 and 3
Toluene soluble portion containing 0 mol% propylene component and number average molecular weight 3,000, weight average molecular! 7.400
and a toluene-insoluble portion containing 4.8 mol% propylene component, number average molecular weight 2,000, weight average molecular i
A blend of polyethylene and ethylene-propylene copolymer having a t8,300 and a propylene component of 7.1 mol% was obtained. Similarly, Example 3 has a molecular weight distribution (!iIn/Mfl) of 4.57 and a propylene component of 2.
LLD consisting of a soluble portion of 0.6 mol% and an insoluble portion with a molecular weight distribution of 3.04 and a propylene component of 2.9 mol%.
Blends of PE and ethylene-propylene copolymers are described.

JP-A No. 60-35007 discloses that ethylene alone or together with an α-olefin having 3 or more carbon atoms is used with metallocene and the following formula [where R is an alkyl group having 1 to 5 carbon atoms, and 7 is 1 to ca. is an integer of 20] or a linear alumoxane represented by the following formula % [wherein the definitions of R and are the same as above]. The method is described. According to the description in the same publication, the polymer obtained by this method has a molecular weight of about 500 to about 140.
It has a weight average molecular weight of 1,000,000 and a molecular weight distribution of 1.5 to 4.0.

In addition, JP-A-60-35008 discloses a copolymer of polyethylene having a wide molecular weight distribution or ethylene and an α-olefin of C1 to CIO by using a catalyst system containing at least two metallocenes and an alumoxane. It is described that a combination is produced. The publication describes that the above copolymer has a molecular weight distribution (L/Mn) of 2 to 50.

Catalysts formed from these transition metal compounds and aluminoxane have significantly superior polymerization activity compared to conventionally known catalyst systems; however, these catalyst systems are soluble in the reaction system, and the resulting polymer It has been difficult to obtain a polymer with low bulk specific gravity and excellent powder properties.

On the other hand, there is also a method using a catalyst formed from a solid catalyst component in which the transition metal compound is supported on a porous inorganic oxide support such as silica, silica-alumina, or alumina, and aluminoxane, as described in Japanese Patent Laid-Open No. 60-35006. It has also been proposed in JP-A-60-35007, JP-A-60-35008, and even JP-A-61-3.
1404, JP-A No. 61-108610, and JP-A No. 60-106808 have also proposed a method using a solid catalyst component supported on a similar porous inorganic oxide carrier. In many of the methods described in these prior art techniques, the polymerization activity decreases due to the use of supported solid components, and the resulting polymers have insufficient powder properties such as bulk specific gravity.

Further, a method of polymerizing olefins using a catalyst formed from a transition metal compound and a mixed organoaluminum compound consisting of an aluminoxasane and an organoaluminum compound is disclosed in JP-A-60-260602 and JP-A-60-130604. This method has been proposed in a publication, and it is stated that the polymerization activity per unit transition metal is improved by adding an organoaluminum compound. However, all of these methods have the problem that the amount of aluminoxane used is large and the activity per aluminoxane is still low.

[Problem that the invention seeks to solve]

The present inventors have developed an olefin copolymer with excellent powder properties, a narrow molecular weight distribution, and a narrow molecular weight distribution and composition distribution when applied to the copolymerization of two or more types of olefins.
As a result of studying a method for producing ethylene polymers or ethylene/α-olefin copolymers with particularly excellent powder properties and narrow molecular weight and composition distributions with excellent polymerization activity even when using a small amount of aluminoxane, we found that (A ) It has been found that the above-mentioned promise can be achieved by using a catalyst formed from a specific carrier-supported solid catalyst component, [B] aluminoxane, and (C) a specific organoaluminum compound, and the present invention provides Reached.

[Means and effects for solving the problems] According to the present invention, (A) a solid catalyst component in which a transition metal compound of Group IVB of the periodic table is supported on an inorganic carrier, (B) an aluminoxane, and C] An organoaluminum compound having a hydrocarbon group other than an n-alkyl group. A method for polymerizing an olefin is provided, which comprises polymerizing or copolymerizing an olefin in the presence of a catalyst formed from the following.

The present invention will be explained in detail below.

In the present invention, the term "polymerization" may be used to include not only homopolymerization but also copolymerization, and the term "polymer" may be used to include not only homopolymers but also copolymers. .

The catalyst used in the present invention has three catalyst components (A)
, (B) and (C).

The catalyst component (A) used in the method of the present invention is a solid catalyst component in which a transition metal compound of group IVB of the periodic table is supported on an inorganic carrier.

The transition metal of group IVB of the periodic table in the catalyst component (A) is selected from the group consisting of titanium, zirconium and hafnium. As the transition metal in the catalyst component (A), titanium and zirconium are preferred, and zirconium is particularly preferred.

As a catalyst component (Al), a zirconium compound having a group having a conjugated π electron as a ligand can be mentioned as a transition metal of Group 1B of the periodic table.

A zirconium compound having the above group having conjugated π electrons as a ligand is, for example, the following formula (1) % formula % (1) [Here, R' represents a cycloalkagenyl group, and R''
, R'' and R4 are cycloalkagenyl groups,
1≧1.1+4 +, +
, = 4]. Examples of the cycloalkagenyl group include a cyclopentadienyl group, a methylcyclopentadienyl group, an ethylcyclopencadienyl group, a dimethylcyclopentadienyl group, an indenyl group, and a tetrahydroindenyl group. Rf, R3
Examples of the alkyl group for R4 include a methyl group, ethyl group, propyl group, isopropyl group, butyl group, etc.; examples of the aryl group include a phenyl group, tolyl group, etc.; Examples of the group include a benzyl group and a neophyl group, and examples of the halogen atom include fluorine, chlorine, and bromine.

Examples of the zirconium compound include the following compounds.

Bis(cyclopentagenyl)zirconium monochloride monohydride, Bis(cyclopentagenyl)zirconium monopromide monohydride, Bis(cyclopentagenyl)methylzirconium hydride, Bis(cyclopentagenyl)ethylzirconium hydride, Bis (cyclopentagenyl) phenylzirconium hydride, bis(cyclopentagenyl)benzylzirconium hydride, bis(cyclopentagenyl) neopentylzirconium hydride, bis(methylcyclopentagenyl)zirconium monochloride hydride, bis(indenyl) Zirconium monochloride monohydride, Bis(cyclopentagenyl)zirconium dichloride, Bis(cyclopentagenyl)zirconium dichloride, Bis(cyclopentagenyl)methylzirconium monochloride, Bis(cyclopentagenyl)ethylzirconium monochloride, Bis(cyclopentagenyl)cyclohexylzirconium monochloride, Bis(cyclopentagenyl)phenylzirconium monochloride, Bis(cyclopentagenyl)benzylzirconium monochloride, Bis(methylcyclopentagenyl)zirconium dichloride, Bis(indenyl) ) Zirconium dichloride, Bis(indenyl)zirconium dibromide, Bis(cyclopentajenyl)zirconium diphenyl, Bis(cyclopentagenyl)zirconium dibenzyl, Bis(cyclopentagenyl)methoxyzirconium chloride, Bis(cyclopentagenyl) ) butoxyzirconium chloride, bis(cyclopentagenyl)2-ethylhexoxyzirconium chloride, bis(cyclopentagenyl)methylzirconium ethoxide, bis(cyclopentagenyl)methylzirconium butoxide, bis(cyclopentagenyl) Ethylzirconium ethoxide, Bis(cyclopentagenyl)phenylzirconium ethoxide, Bis(cyclopentagenyl)benzylzirconium ethoxide, Bis(methylcyclopentagenyl)ethoxyzirconium chloride, Bis(indenyl)nidoxyzirconium chloride, Bis(cyclopentagenyl)ethoxyzirconium, bis(cyclopentagenyl)butoxyzirconium, bis(cyclopentagenyl)2-ethylhexylzirconium.

Furthermore, mention is made of zirconium compounds in which the ligand is a polydentate compound in which at least two groups selected from the group consisting of an indenyl group, a substituted indenyl group, and a partially hydrogenated product thereof are bonded via a lower alkylene group. be able to. Examples of the zirconium compound include the following compounds.

Ethylenebis(indenyl)dimethylzirconium, Ethylenebis(indenyl)diethylzirconium, Ethylenebis(indenyl)diphenylzirconium, Ethylenebis(indenyl)methylzirconium monochloride, Ethylenebis(indenyl)ethylzirconium monochloride, Ethylenebis(indenyl)methyl Zirconium monopromide, 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-l-indenyl)zirconium dichloride, ethylenebis(4,5,6,7-tetrahydro-1-indenyl) ) Zirconium dibromide, Ethylenebis(4-methyl-1-indenyl)zirconium dichloride, Ethylenebis(5-methyl-1-indenyl)zirconium dichloride, Ethylenebis(6-methyl-1-indenyl)zirconium dichloride, Ethylenebis( 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-simethoxy1-indenyl)
Zirconium dichloride.

In the catalyst component (A), the transition metal compound of group IVB of the periodic table may be previously treated with an organic aluminum compound such as trimethylaluminum, dimethylaluminum chloride, methylaluminum dichloride, etc. before being supported.

In the catalyst component (A), a transition metal compound belonging to group (I) of the periodic table is supported on an inorganic carrier. The inorganic carrier is preferably an inorganic oxide, specifically SiO□, A i!
,0. , MgO, ZrO, , Ti0z, B2O3, C
aO, ZnO1BaO, Th0z, etc. or mixtures thereof, e.g., SiO, -MgO1SiO2-A 1203
．． 5iO2-TiOz, 5iOz-VzOs, 5iO
Examples include 2-CrzO+, SiO, -TiO, and -MgO. Among these, Sin, and An
A carrier containing as a main component at least one component selected from the group consisting of zO* is preferred. Note that the above inorganic oxide contains small amounts of Na, JO, KzCO*, Ca
C0+, MgCO5, NazSO4, Al2(S
on)s, Ba5Oa, KNO:l, MgCNaz
)z, A I CNOs')x, NazO, MgO, L
It may contain carbonate, sulfate, nitrate, or oxide components such as tzO.

The properties of the carrier vary depending on its type and manufacturing method, but the carrier preferably used in the present invention has a particle size of 10 to 30
0μ, preferably 20 to 200μ, specific surface area 50
from 1000 M/g, preferably from 100 to 700
rd/g, pore volume 0.3 to 3. Oa(/g
, preferably 0.5 to 2.5 aa/g. The temperature of the carrier is usually 150 to 1,000°C, preferably 20°C.
It is used after being fired at 0 to 800°C.

In the supporting reaction of the present invention, the mixing ratio (
transition metal/carrier) from 0.5 to 15%.

Preferably from 0.8 to 10% by weight, preferably from 0.8 to 7% by weight.

Examples of the supporting method of the present invention include the following method.

(11) After treating the support with an organic aluminum such as trimethylaluminum, dimethylaluminum chloride, or aluminoxane, or a halogen-containing silicon compound such as trichlorosilane, the support is treated with the group IVB transition metal compound of the periodic table in the presence of an inert solvent. How to mix.

(2) A method in which the periodic table rVB group transition metal compound is treated with an organic aluminum such as trimethylaluminum or dimethylaluminum chloride, and then mixed with the carrier in the presence of an inert solvent.

(3) In the presence of an inert solvent, the carrier, the periodic table ■B
A method in which the group transition metal compound and the aluminoxane as the catalyst component [B] are mixed, the mixture is heated at room temperature or at an elevated temperature, and the solvent is removed using, for example, an evaporator under normal pressure or reduced pressure.

The catalyst component (A) thus obtained supports 0.01 to 3% by weight, preferably 0.03 to 1% by weight, of a transition metal of group IVB of the periodic table.

The catalyst component [B] used in the method of the present invention is aluminoxane. As aluminoxane used as a catalyst component, general formula (n) and general formula (Iil) R1Aj! →OAl h「0AIRt
The organoaluminum compound represented by (II) can be exemplified. In the 8-aluminoxane, R is a hydrocarbon group such as a methyl group, ethyl group, propyl group, butyl group, preferably a methyl group or an ethyl group, particularly preferably a methyl group, and m is 2 or more, preferably is an integer greater than or equal to 5. Examples of the method for producing the aluminoxane include the following method.

(1) Compounds containing adsorbed water, salts containing crystal water, such as magnesium chloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate, cerous chloride permanent hydrate, etc. A method in which trialkylaluminum is added to a hydrocarbon medium suspension and reacted.

(2) A method in which water is directly applied to trialkylaluminium in a medium such as benzene, toluene, ethyl ether, or tetrahydrofuran.

Among these methods, method (1) is preferably employed; however, the aluminoxane may contain a small amount of organometallic component.

The organoaluminum compound (C) used as a catalyst component in the method of the present invention is an organoaluminum compound having a hydrocarbon group other than an n-alkyl group. n
- Hydrocarbon groups other than alkyl groups include alkyl groups having a branched chain such as isoalkyl, cycloalkyl groups,
Examples include aryl groups. Specifically, the organoaluminum compounds include triisopropylaluminium, triisobutylaluminum, tri2-methylbutylaluminum, tri3-methylbutylaluminum, tri2-methylpentylaluminum, tri3-
Methylpentylaluminium, tri-4-methylpentylaluminium, tri-2-methylhexylaluminum,
trialkyl aluminum such as tri-3-methylhexylaluminum and tri-2-ethylhexylaluminum, tricycloalkylaluminum such as tricyclohexylaluminum, triarylaluminum such as triphenylaluminum, tritolylaluminum,
Examples include dialkyl aluminum hydride such as diisobutyl aluminum hydride, alkyl aluminum alkoxide such as isobutyl aluminum methoxide, isobutyl aluminum ethoxide, and isobutyl aluminum isopropoxide. Among these organoaluminum compounds, organoaluminum compounds having a branched alkyl group are preferred, and trialkylaluminum compounds are particularly preferred. Also preferred is isoprenylaluminum represented by the general formula %.

Note that there is no problem in adding a compound that forms the above-mentioned organoaluminum compound in the polymerization system, such as aluminum halide and alkyllithium or aluminum halide and alkylmagnesium.

In the method of the present invention, the olefin polymerization reaction is carried out in either a liquid phase polymerization method such as a slurry polymerization method or a solution polymerization method, or a gas phase polymerization method.

Further, prior to the polymerization of the olefin, preliminary polymerization can be performed using a small amount of the olefin.

Prepolymerization is carried out (1) in the absence of a solvent or (2) in an inert hydrocarbon medium. Among these methods, method (1) is preferred. At this time, the catalyst components (A) and [B]
are first mixed in an inert hydrocarbon medium, then at room temperature or at an elevated temperature, and the solvent is removed using, for example, an evaporator under normal pressure or reduced pressure to obtain a solid catalyst component. The molar ratio (A/
/ transition B metal atom) is 20 to 5000, preferably 2
5 to 2000, more preferably 30 to 1000
is within the range of Prepolymerization temperature is -20℃ to 70℃,
Preferably -10°C to 60°C, more preferably 0°C
to 50°C.

The treatment can be carried out either batchwise or continuously, and can be carried out under reduced pressure, normal pressure or increased pressure. In the prepolymerization, a molecular weight regulator such as hydrogen may be present, but the temperature should be at least 135°C.
The intrinsic viscosity [η] measured in decalin is 0.2 cu/
It is preferable to keep the amount to a level that allows production of a prepolymer of 1.5 to 20 dI/g, preferably 0.5 to 20 dI/g.

When carrying out the method of the present invention by a slurry polymerization method or a gas phase polymerization method, the proportion of the transition metal compound used is usually 10-8 to 10-8 as the concentration of the transition metal atoms in the polymerization reaction system.
2 gram atoms/β, preferably in the range from 10 −7 to 10 gram atoms/l.

Further, in the method of the present invention, the amount of aluminoxane used is 3 milligram atoms/l or less, preferably 0.1 to 2.5 milligram atoms/l, particularly preferably 0. It ranges from .2 to 2 milligram atoms/i.

In addition, the aluminoxane component (B) in the reaction system
and the aluminoxane component (B) relative to the total amount of aluminum atoms in the organoaluminum compound component (C).
The proportion of aluminum atoms in ) is usually 20 to 80%
, preferably 25 to 75%, particularly preferably 30%
Similarly, the proportion of aluminum atoms in the organoaluminum compound component (C) is usually 20% to 70%.
It ranges from 80% to 80%, preferably from 25 to 75%, particularly preferably from 30 to 70%. In the method of the present invention, the ratio of aluminum atoms in the total amount of the aluminoxane component [B] and organoaluminum compound component (C) to the transition metal atoms in the reaction system is usually 20 to 10,000, preferably 50 to 5,000. , particularly preferably in the range of 100 to 2000.

The method of the present invention is effective for producing olefin polymers, particularly ethylene polymers and co-conductors of ethylene and α-olefins. Examples of olefins that can be used in the present invention include ethylene and α to 20
-Olefins, such as propylene, 1-butene, 1-
hexene, 4-methyl-1-pentene, 1-octene,
Examples include 1-decene, needodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene.

Polyenes such as dienes can also be copolymerized if necessary.

In the process of the invention, the olefin polymerization is usually carried out in the gas phase or in the liquid phase, for example in the form of a slurry. In slurry polymerization, an inert hydrocarbon may be used as a solvent, or the olefin itself may be used as a solvent.

Specifically, the hydrocarbon medium includes butane, isobutane,
Aliphatic hydrocarbons such as pentane, hexane, octane, decane, dodecane, hexadecane, octadecane, alicyclic hydrocarbons such as cyclopenkune, methylcyclopenkune, cyclohexane, cyclooctane, benzene,
Examples include aromatic hydrocarbons such as toluene and xylene, petroleum fractions such as gasoline, kerosene, and light oil.

In the method of the present invention, when carrying out the slurry polymerization method, the polymerization temperature is usually -50 to 120°C, preferably O
The temperature ranges from 100°C to 100°C.

In the method of the present invention, when carrying out the gas phase polymerization method, the polymerization temperature is usually in the range of -50 to 120°C, preferably 20 to 100°C. Polymerization pressure is usually normal pressure to 100 kg/cn, preferably 2 to 50 kg/cn.
The polymerization is carried out in batch, semi-continuous, or semi-continuous manner.
It can be carried out in any continuous method. Furthermore, it is also possible to carry out the polymerization in two or more stages with different reaction conditions. Moreover, the molecular weight of the polymer can be adjusted by hydrogen and/or polymerization temperature.

〔Effect of the invention〕

It is said that the olefin polymerization of the present invention, especially when ethylene polymerization, slurry polymerization of ethylene and α-olefin, or gas phase polymerization is adopted, has high activity even when using less aluminoxane than conventional methods. It is characterized by the fact that no polymer adheres to the reactor, and when applied to the copolymerization of two or more olefins, it is possible to obtain an olefin copolymer with a narrow molecular weight distribution and composition distribution.

〔Example〕

Next, the method of the present invention will be specifically explained using examples.

In addition, in the examples and comparative examples, the MFR is at a temperature of 19
The measurement was carried out under the conditions of 0° C. and a load of 2.16 kg, and the measurement of the ~/total value was carried out as follows according to "Gel Permeation Chromatography" written by Takeuchi and published by Maruzen.

(11 Using standard polystyrene with a known molecular weight (manufactured by Toyo Soda ■, monodispersed polystyrene), calculate the molecular weight M and its G
P C (Get Permeation Chrom
The ato-graph) count is measured, and a correlation diagram calibration curve of the molecule IM and EV (Elution Volume) is created. The concentration at this time is 0.02 wt%.

(2) Obtain a GPC chromatograph of the sample by GPC measurement, calculate the number average molecular weight h and weight average molecular weight ~ in terms of polystyrene according to the above (1), and determine the FJhJ/& value. The sample preparation conditions and GPC measurement conditions at that time are as follows.

[Sample preparation]

(a) A sample is divided into an Erlenmeyer flask together with a 0-dichlorobenzene solvent so that the concentration of O is 1 wt%.

(b) Heat the Erlenmeyer flask to 140°C and apply the filtrate to GPC for about 30 minutes.

(GPC measurement conditions) It was conducted under the following conditions.

(a) Equipment Manufactured by Wat6r5 (150C-AL
C/GPC) (b) Column manufactured by Toyo Soda (GMH
Type) (c) Sample amount 400μ! (d) Temperature: 140°C (e) Flow rate: 1 m/+ail To measure the amount of n-decane soluble portion in the copolymer (the smaller the amount of soluble portion, the narrower the composition distribution), approximately 3 g of the copolymer was −
The solution was added to decane 450- and dissolved at 145°C, cooled to 23°C, removed the n-decane insoluble part by filtration, and recovered the n-decane soluble part from the filtrate.

Example 1 Aluminoxane name LliJ Into a 400-ml flask that was sufficiently purged with nitrogen,
(Sot) 3.14Hz 037g and toluene 125-
After cooling to 0° C., 500 mmol of trimethylaluminum II diluted with 125 toluene was added dropwise. Next, the temperature was raised to 40°C, and the reaction was continued at that temperature for 10 hours.

After the reaction, solid-liquid separation was performed by filtration, and toluene was further removed from the filtrate to obtain 13 g of white solid aluminoxane. The molecular weight determined by freezing point depression in benzene was 930, and the m value shown in catalyst component (B) was 14.

Zirconium i, 1 Silica (average particle size 70 μ, specific surface area 260 m/g, pore volume 1.65
3.8 g of aa/g) calcined at 300°C for 4 hours and a toluene solution of aluminoxane (A j! 0.
49 mol/1)51.5- was added and stirred at room temperature for 10 minutes. Thereafter, toluene was removed using an evaporator at room temperature to obtain a solid product. To this solid product was added a toluene solution of bis(cyclopentagenyl)zirconium dichloride (ZrO, 04 ml 1 ol/l') 1
．． 911t1 was added and toluene was removed again using an evaporator at room temperature to reduce the Zr content to 0°54-t.
% catalyst component was obtained. Furthermore, a mixed gas of ethylene and nitrogen (30 ff each) was added to the catalyst component thus obtained.
A solid catalyst component in which 0.86 g of ethylene was polymerized per 1 g of catalyst was obtained by flowing the mixture at room temperature for 30 minutes.

900 d of hexane and 100 d of 1-hexene were charged into 22 stainless steel autorapes which had been sufficiently purged with nitrogen.
The temperature was raised to 5°C. Thereafter, 1 mmol of triisobutylaluminum and 0.015 mg of a zirconium catalyst prepolymerized with ethylene were charged in terms of zirconium atoms. Furthermore, the temperature was raised to 60°C, and ethylene was subsequently introduced to initiate polymerization. Total pressure is 7kg/cn! −
Ethylene was continuously supplied to maintain the gauge, and polymerization was carried out at 70°C for 2 hours. After the polymerization was completed, the polymer slurry was added to a large excess of methanol, filtered, and dried under reduced pressure at 80° C. for 12 hours. As a result, M F R0,16g
/ 10m1n, density 0.916 g/aA, &/R
Poly?n2.98, bulk density 0.33g/cJ, room temperature n-decane soluble portion II 0.31wt%? -101°2g was obtained.

Example 2 The same procedure as in Example 1 was carried out except that the amount of prepolymerized ethylene was changed to 0.66 g per 1 g of catalyst.

In Example 1, 10001 nl of hexane was used as the solvent without using l-hexene, and the total pressure was 6 kg/ci-
The same procedure as in Example 1 was conducted except that ethylene was homopolymerized using a gauge. The results are shown in Table 2.

Comparative Example 1 The same procedure as in Example 2 was carried out except that triisobutylaluminum was not used in Example 2. The results are shown in Table 2.

Example 3 250 g of sodium chloride (Wako Pure Chemicals special grade) was charged into a 2β stainless steel autoclave that had been sufficiently purged with nitrogen.
It was dried under reduced pressure at 90°C for 1 hour. Thereafter, the system was cooled to 65° C. and replaced with ethylene. Subsequently, 1 mmol of triisobutylaluminum, 0.015 mg atom of the zirconium catalyst prepared in Example 1 in terms of zirconium atom, and 1-hexene 10- were introduced, and ethylene was further introduced to bring the total pressure to 8 kg/cni・gauge. Polymerization started as follows. After that, only ethylene was replenished, and the total pressure was 8
kg/cfl! - Polymerization was carried out at 70°C for 2 hours while maintaining the gauge. After polymerization, remove sodium chloride by washing with water.
After washing the remaining polymer with methanol, it was dried under reduced pressure at 80° C. overnight. M F R1,45g/10m
1n, density 0.925 g/cdSFihr/FJn
3.03, bulk density 0.31 g/aA, room temperature n-decane soluble portion ff1O, 46.8 g of polymer having 10%.

Example 4 In the polymerization of Example 3, 1-hexene was not used, and triisobutylaluminum and zirconium catalyst were used at 75°C.
Example 3 except that the polymerization was carried out at 80°C for 1 hour.
I did the same thing. The results are shown in Table 2.

Examples 5 to 8 Polymerization was carried out in the same manner as in Example 1 under the conditions listed in Table 1. The results are shown in Table 2.

Example 9 Zirconium A,'Alumina (average particle size 60 μ, specific surface area 290 rrr/g, pore volume 1
．． 05mZ/g) was calcined at 500℃ for 5 hours, 5.8g of dimethylaluminum monochloride toluene solution (AI!1mol/j!ri17-) and toluene 5〇- were added, and the mixture was heated at 80℃ for 2 hours. After that, solid-liquid separation was performed by filtration, and the solid portion was dissolved in 50ml of toluene.
1, and then add bis(cyclopentagenyl) to it.
Toluene solution of zirconium dichloride (Zr0.04
mol/l) 32- was added and heated at 80°C for 1 hour. A solid catalyst was obtained by performing solid-liquid separation by filtration again. The zirconium content in the solid catalyst is 0.27
It was wt%. This solid catalyst was 0.1 milligram in terms of zirconium atoms, and the toluene solution of the aluminoxane synthesized in Example 1 (A 10.49 m).

Add 1 #20 and 20 of toluene and stir at room temperature for 3
Stirred for 0 minutes. Thereafter, toluene was removed using an evaporator at room temperature. Furthermore, a mixed gas of ethylene and nitrogen (301% each) was added to the catalyst component thus obtained.
/hr, 451/hr) at room temperature for 30 minutes, the amount of ethylene per 1β of the catalyst was reduced to 0.
30g of polymerized solid catalyst component was obtained.

Sato-Ki Polymerization was carried out in the same manner as in Example 4. The results are shown in Table 2.

Comparative Example 2 The same procedure as in Example 9 was conducted except that triisobutylaluminum was not used. The results are shown in Table 2.

[Brief explanation of the drawing]

FIG. 1 is a flowchart showing one example of the preparation of a catalyst for olefin polymerization according to the present invention.

Claims (1)

[Claims] (1) [A] A solid catalyst component in which a transition metal compound of group IVB of the periodic table is supported on an inorganic carrier, [B] aluminoxane, and [C] an organic aluminum having a hydrocarbon group other than an n-alkyl group. A method for polymerizing olefins, comprising polymerizing or copolymerizing olefins in the presence of a catalyst formed from a compound.