JPS63260903A - Polymerization of olefin - Google Patents

Abstract

PURPOSE:To produce an olefin (co)polymer having narrow distributions of the molecular weight and the composition, and a large bulk specific gravity and excellent in powder property, by (co)polymerizing an olefin in the presence of a specific catalyst. CONSTITUTION:A catalyst (b) is obtained by blending a solid catalyst component (i) which consists of a compound of a transition metal of the Group IV B of the periodic table on a carrier in an amount of 0.5-500mg atoms for 100g of the carrier, which carrier is finely divided particles having a particle diameter of 5-200mum which have been calcined at 150-1,000 deg.C, and may be an inorganic carrier comprising preferably SiO2 and/or Al2O3 as a main ingredient or an organic carrier (e.g., PE having a weight-average molecular weight of 1,000-10,000,000), an aluminoxane (ii) of formula I-II (wherein R is a hydrocarbon group, for example CH3 or C2H5; and m is 2 or more) in an amount of 5-50,000mg atoms per 100g of said carrier in terms of Al, and 5-80%, for a total of Al of the components (ii) or (iii), an organoaluminum compound (iii) of formula III or IV (wherein R<1-3> are each a hydrocarbon group; R<4> is R<1>, alkoxy, or aryloxy; 0<m, n<3). One or more olefins (a) are (co)polymerized in the presence of the component (b).

Description

[Detailed description of the invention] [Industrial application field] The present invention relates to an olefin polymerization method.

In detail, it relates to a method that can polymerize olefins with excellent polymerization activity even when the amount of aluminoxane used is reduced, and can produce olefin polymers with large molecular weights. More specifically, it is possible to produce an olefin polymer with a narrow molecular weight distribution, high bulk specific gravity, and excellent powder properties, and when applied to the copolymerization of two or more types of olefins, the molecular weight distribution and This invention relates to a method for polymerizing an olefin copolymer having a narrow composition distribution with excellent polymerization activity.

[Prior Art] Conventionally, methods for producing α-olefin polymers, particularly ethylene polymers or ethylene/α-olefin copolymers, have involved using a titanium-based catalyst consisting of a titanium compound and an organoaluminum compound or a vanadium compound and an organoaluminum compound. A method is known in which ethylene or ethylene and α-olefin are copolymerized in the presence of a vanadium-based catalyst consisting of: In general, ethylene/α-olefin copolymers obtained using 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, the ethylene/α-olefin copolymer obtained using a vanadium-based catalyst has a narrower molecular weight distribution and composition distribution than that obtained using a titanium-based catalyst, and has considerably improved transparency, surface non-adhesion, and mechanical properties. However, these properties are still insufficient for applications requiring improved performance, and there is a need for α-olefin polymers, particularly ethylene/α-olefin copolymers, that have improved performance.

On the other hand, as a new Ziegler type olefin polymerization catalyst,
Catalysts consisting of zirconium compounds and aluminoxane have recently been proposed.

JP-A No. 58-19309 describes the following formula % formula % [where R is cyclopentadienyl, 01 to C6 alkyl, halogen, Me is a transition metal, Ha
l is a halogen] and a transition metal-containing compound represented by the following formula %) [where R is methyl or ethyl and n is 4 to 2
In the presence of a catalyst consisting of a linear aluminoxane represented by the number 0] or a cyclic aluminoxane represented by the following formula [where R and n are the same as above], ethylene and A method is described in which one or more C1-C12 α-olefins are polymerized at temperatures of 150°C to 200°C.

The publication states that in order to adjust the density of the resulting polyethylene, 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 No. 59-95292 discloses linear aluminoxanes represented by the following formula (% formula % is alkyl) and cyclic aluminoxanes represented by the following formula (where n and R have the same definitions as above). The invention related to the production method of aluminoxane was awarded to J.
e is listed. The same publication states that when olefin polymerization is carried out by mixing, for example, methylaluminoxane produced by the same production method with a titanium or zirconium bis(cyclopentagenyl) compound, It is stated that more than 25 million g of polyethylene can be obtained per hour.

JP-A No. 60-35005 describes the following formula [where,
R1 is 01-C2° alkyl, and Ro is R1 or combined to represent 10-] is first reacted with a magnesium compound, then the reaction product is chlorinated, and Ti, ■, Zr
Alternatively, a method for producing an olefin polymerization catalyst by treating with a Cr compound is disclosed. The publication states that the above catalyst is particularly suitable for copolymerizing a mixture of ethylene and 02C12α-olefin.

JP-A No. 60-35006 discloses that mono-, di- or l-dicyclopentadienyl of two or more different transition metals or a derivative thereof (Jl) and aluminium oxide are used as a catalyst system for producing a reactor blend polymer. xan) (b)
combinations are disclosed. In Example 1 of the same publication, ethylene and propylene were polymerized using bis(pentamethylcyclopentadienyl)zirconium dimethyl and aluminoxane as catalysts, and the number average molecular weight was 15,300.
．． It is disclosed that a polyethylene having a weight average molecular weight of 36.400 and a propylene content of 3.4% was obtained. In addition, in Example 2, bis(pentamethylcyclopentadienyl) zirconium dichloride, bis(
Ethylene and propylene are polymerized using zirconium dichloride and aluminoxane as a catalyst, and a toluene-soluble portion containing a number average molecular weight of 2,200, a weight average molecular weight of 11.900, and a propylene component of 30 mol% is produced. Number average molecule ff12 consisting of an average molecular weight of 3,000, a weight average molecular weight of 7.400 and a toluene insoluble portion containing a propylene component of 4.8 mol%
,000, a weight average molecular weight of 8,300, and a blend of polyethylene and ethylene-propylene copolymer containing a propylene component of 7.1 mol%. Similarly, in Example 3, an L- Blends of LDP E and ethylene-propylene copolymers are described.

JP-A-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 n is defined above] According to the description in the publication, the polymer obtained by this method is about 500 It has a weight average molecular weight of ~1.4 million and a molecular weight distribution of 1°5 to 4.0.

Furthermore, JP-A-60-35008 discloses that by using a catalyst system containing at least two types of metallocene and aluminoxane, polyethylene or ethylene having a wide molecular weight distribution and α-olefin of C1 to C3° can be combined. It is described that copolymers are prepared. The publication states that the above copolymer has a molecular weight distribution (MIJ/Mn) 2
-50.

Furthermore, a method for polymerizing olefins using a catalyst formed from a transition metal compound and a mixed organoaluminum compound consisting of an aluminoxane and an organoaluminum compound is disclosed in JP-A-60-260602 and JP-A-60.
It is proposed in Japanese Patent No. 130604, 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.

Catalysts formed from transition metal compounds and aluminoxane proposed in these prior art exhibit significantly superior polymerization activity compared to catalyst systems formed from conventionally known transition metal compounds and organoaluminum compounds. However, most of the catalyst systems proposed for these are soluble in the reaction system, and solution polymerization systems are often adopted, and in addition to the significantly high solution viscosity of the polymerization system, The bulk specific gravity of the resulting polymer obtained by the treatment was small, making it difficult to obtain a polymer with excellent powder properties.

On the other hand, suspension polymerization or gas phase polymerization is carried out using a catalyst in which one or both of the transition metal compound and aluminoxane are supported on a porous inorganic oxide support such as silica, silica-alumina, or alumina. Attempts have also been made to carry out the polymerization of olefins in systems.

For example, JP-A-60-35006, JP-A-60-35007 and JP-A-60-3 cited above.
No. 5008 describes the use of a catalyst in which a transition metal compound and aluminoxane are supported on silica, silica-alumina, alumina, or the like.

JP-A-60-106808 and JP-A-61-106809 disclose that a highly active catalyst component containing titanium and/or zirconium soluble in a hydrocarbon solvent is contacted with a filler in advance. A composition consisting of a polyethylene polymer and a filler is produced by copolymerizing ethylene or ethylene and an α-olefin in the presence of the obtained product, an organoaluminium compound, and a filler having an affinity for polyolefins. A method is proposed.

JP-A No. 61-31404 discloses that ethylene or A method of polymerizing or copolymerizing ethylene and α-olefin has been proposed.

Furthermore, JP-A No. 61-276805 discloses a reaction mixture obtained by reacting a zirconium compound and aluminoxane with a trialkylaluminium, which is further reacted with an inorganic oxide containing a surface hydroxyl group such as silica. A method has been proposed in which olefins are polymerized in the presence of a catalyst consisting of.

Furthermore, in JP-A-61-108610 and JP-A-61-296008, olefins are prepared in the presence of a catalyst in which a transition metal compound such as a metallocene and an aluminoxane are supported on a support such as an inorganic oxide. A method of polymerization has been proposed.

However, even if olefins are polymerized or copolymerized in a suspension polymerization system or a gas phase polymerization system using the carrier-supported solid catalyst component proposed in these prior art, the polymerization activity is lower than that in the solution polymerization system described above. There is no catalyst that fully exhibits the original characteristics of a catalyst consisting of a transition metal compound catalyst component and an aluminoxane catalyst component, and the powder properties such as the bulk specific gravity of the produced polymer are significantly reduced. It was also insufficient.

[Problems to be Solved by the Invention] An object of the present invention is to solve an olefin copolymer having a narrow molecular weight distribution and a narrow molecular weight distribution and a narrow composition distribution when applied to the copolymerization of two or more types of olefins. The object of the present invention is to provide a method capable of producing an ethylene/α-olefin copolymer having a narrow distribution and composition distribution with high polymerization activity per aluminoxane.

A further object of the present invention is to provide an olefin polymerization method that can provide an olefin polymer having a high bulk density and powdery properties, and which also has high polymerization activity.

[Means for Solving the Problems] According to the present invention, [^] a solid catalyst component in which a transition metal compound of group B of the periodic table is supported on a particulate carrier, [B] aluminoxane, and [C] General formula [N or general formula [II1] R'+a
^1 (OR2): +, -m
[l]1<3n^l[0siR,
'], -n [II] [wherein, R1,
R2 and R3 represent a hydrocarbon group, R4 represents a hydrocarbon group, an alkoxy group, or an aryloxy group, and O<m
An organoaluminum compound represented by O<3 and a positive number of O<n<3; be done.

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 solid catalyst component [A] used in the method of the present invention is a solid catalyst component in which at least 1% of a transition metal compound of group B of the periodic table is supported on a fine particle carrier; It is particularly preferable to use a solid component supported with a group transition metal compound and an aluminoxane component [B] because an olefin polymer having a large bulk specific gravity and excellent powder properties can be obtained with excellent polymerization activity.

The carrier constituting the solid catalyst component [A] is a particulate carrier, and either an inorganic particulate carrier or an organic particulate carrier can be used.

Specifically, the inorganic fine particle carrier is SiO2, AI
20 s, M g O, Z r O2, TiO*, B
2O3, Ca01ZnO, ThO2, etc. or mixtures thereof such as Si02-MgO, Si02-A
I2O3, S i 02 T i 02, S i
02 VzOs, 5iO2-Cr20i, S i 0
x-T i 02-M g○ etc. can be printed as an example. These inorganic fine particle carriers usually have a molecular weight of 150 to 100
It is used after firing at 0°C2, preferably 200 to 800°C. Among these, S i O2 and A l 2
A carrier containing at least one component selected from the group consisting of No. 03 as a main component is preferred. Note that the inorganic fine particle carrier contains a small amount of Na2C○1, K, CO, Ca C
O3, MgC01, Na 2 CO4, A 12 (
7S 04)! , BaSO4, KNO3, Mg
(NO3):, A l (N0z) 3, Na2O, K
It may contain carbonates, sulfates, nitrates, and oxide components such as 2O and Li2O. Although the properties of the carrier vary depending on its type and manufacturing method, the carrier preferably used in the present invention has a particle size of 5 to 200 μm, preferably 10 to 150 μm, more preferably 20 to 100 μm.
It is μm.

Specifically, the 1f1 particle carrier includes polyolefins such as polyethylene, polypropylene, poly1-butene, poly4-methyl-1-pentene, and polyolefins obtained by copolymerizing monomers used as raw materials for these compounds. Alternatively, various polyesters, polyamides, polyvinyl chloride, polymethyl methacrylate, polymethyl acrylate, borisdylene, and other various natural polymers and various monomer compounds can be exemplified. Although the properties of the carrier vary depending on its type and manufacturing method, the carrier preferably used in the present invention has a particle size of 5 to 200 μm, preferably 10 to 15071 m, and more preferably 20 to 100 B m.

The molecular weight of these carriers is acceptable as long as the molecular weight is such that these compounds can exist as solid substances. For example, taking polyethylene as an example, it is approximately 1,000 to 10,000
It is possible to use polyethylene with a weight average molecular weight in the range of ,000.

The fine particle carrier may be subjected to a preliminary contact treatment with a compound such as an organoaluminum compound, an aluminoxane compound, or a halogen-containing silane compound prior to supporting the transition metal compound of Group 1 VB of the periodic table. .

Specific examples of the organoaluminum compound include trialkylaluminum such as trimethylaluminum, triethylaluminum, tri-n-butylaluminum, and triisobutylaluminum, alkenylaluminum such as isoprenylaluminum, dimethylaluminum methoxide, and diethylaluminum ethoxide. , dialkylaluminum alkoxides such as dibutylaluminum butoxide and diisobutylaluminum methoxide, and alkylaluminum sesquialkoxides such as methylaluminum sesquimethoxide and ethylaluminum sesquiethoxide, as well as R' 2.5A 1 (
OR'''), dialkylaluminum halides such as dimethylaluminum chloride, diethylaluminium chloride, dimethylaluminum bromide, methylaluminum sesquichloride, ethyl Examples include alkyl aluminum sesquihalides such as aluminum sesquichloride, partially halogenated alkyl aluminums such as alkyl aluminum cybarides such as methyl aluminum dichloride, and ethyl aluminum dichloride.These organoaluminum compounds include trialkyl Aluminum, dialkylaluminum chloride, and dialkylaluminum alkoxide are preferred, and trimethylaluminum, triethylaluminum, triisobutylaluminum, dimethylaluminum chloride, diethylaluminum chloride, and diisobutylaluminum methoxide are particularly preferred.

In addition, as an aluminoxane compound that can be used for the preliminary contact treatment of the particulate carrier, the general formula [II[[
] and - General formula IV ]R'R' Preferably a methyl group or an ethyl group, particularly preferably a methyl group.
It is a halogen atom such as chlorine or bromine, and R6 is the hydrocarbon group exemplified for R5 or the above halogen. Also, a
is usually 1 to 80, preferably 1 to 3o,
b is usually 0 to 80, preferably 0 to 3°, and a+b is usually 4 to 100, preferably 8 to 5
It is 0. Moreover, -m formula [II [II] and t may be combined in a block manner, or may be combined regularly or irregularly at random.

Further, as a halogen-containing silane compound that can be used for the preliminary contact treatment of the fine particle carrier, examples of the halogen-containing silane compound have the general formula [V] 5iXcR'dOR" [V
A halogen-containing silane compound represented by ](]4-c-cl is preferred, where X is C1 or Br, and R' and R'' are hydrogen atoms, alkyl groups having 1 to 12 carbon atoms, aryl groups, or 3 carbon atoms. -12 cycloalkyl group, C is a number from 1 to 4, d is a number from 0 to 4, and C0d is a number from 1 to 4.

More specifically, for example, silicon tetrachloride, silicon tetrabromide, silane trichloride, methyl silane trichloride, ethyl silane trichloride, propyl silane trichloride, phenyl silane trichloride, cyclohexyl silane trichloride, silane tribromide, and trichloride. ethylsilane dichloride, dimethylsilane dichloride, methylsilane dichloride,
Examples include phenylsilane dichloride, methoxysilane trichloride, ethoxysilane trichloride, propoxysilane trichloride, phenoxysilane trichloride, ethoxysilane tribromide, methoxysilane dichloride, dimethoxysilane dichloride, and silanol trichloride. A halogen-containing silane compound consisting of a mixture of these compounds and a compound selected from these compounds is used, and silicon tetrachloride, trichloride silane, and trichloromethylsilane are particularly preferred.

Other compounds that can be used in the preliminary contact treatment of the particulate carrier include organoboron, organomagnesium, organozinc, organolithium, and the like.

The proportion of the organometallic compound or the silane compound used in the preliminary contact treatment of the particulate carrier with the organometallic compound or the silane compound is the proportion of the metal constituting the organometallic compound or the silane compound per 1 g of the particulate carrier. The range is from 0.01 to 50 milligram atoms, preferably from 0.05 to 30 milligram atoms, particularly preferably from 0.1 to 20 milligram atoms.

Adding the particulate carrier dispersed in an inert medium and at least one of the above organic compound or the above silane compound,
at a temperature of 0 to 120°C, preferably 10 to 100°C, more preferably 20 to 90°C for 10 minutes to 1
This can be carried out by treating under normal pressure, reduced pressure or increased pressure for 0 hours, preferably 20 minutes to 5 hours, more preferably 30 minutes to 3 hours.

The transition metal of group IVB of the periodic table in catalyst component [A] is selected from the group consisting of titanium, zirconium, and hafnium. Titanium and zirconium are preferred as the transition metal in catalyst component [A], and zirconium is particularly preferred.

Examples of the transition metal compound of group IVB of the periodic table in the catalyst component [A] include zirconium compounds having a group having conjugated π electrons as a ligand.

For example, the zirconium compound having the above-mentioned group having conjugated π electrons as a ligand has the following formula [W]R1kR2,R3III
R'nZr (1) [Here, R1 represents a cycloalkagenyl group or a substituent thereof, and R2, R3, and R4 are a cycloalkagenyl group, an aryl group, an alkyl group, a cycloalkyl group, an aralkyl group, or a halogen atom. ,
hydrogen, Or(", SRb, NR2°, or PR2d, R", Rb, R' and R4 are hydrocarbon groups such as alkyl groups, cycloalkyl groups, aryl groups, aralkyl groups, silyl groups, Two Ro and R' can also be linked to form a ring. k≧1, k+l+m+
When n=4, and R2 is a cycloalkagenyl group, R1 and R2 may be bonded through a lower alkylene group. ] It is a compound shown by. Examples of the cycloalkagenyl group include a cyclopentadienyl group, a methylcyclopentagenyl group, an ethylcyclopentagenyl group, a pentamethylcyclopentagenyl group, a dimethylcyclopentagenyl group, an indenyl group, and a tetrahydroindenyl group. Examples include a nyl group. As an alkyl group,
Examples include methyl group, ethyl group, propyl group, isopropyl group, butyl group, hexyl group, octyl group, 2-ethylhexyl group, decyl group, oleyl group, etc. As the aryl group, for example, phenyl group, etc. basis,
Examples of the aralkyl group include a benzyl group and a neophyl group. Examples of the cycloalkyl group include a cyclopentyl group, a cyclohexyl group, a cyclooctyl group, a norbornyl group, and a bicyclo group. Examples include nonyl groups and alkyl substituents of these groups, and examples of silyl groups include trimethylsilyl, triethylsilyl, phenyldimethylsilyl, and triphenylsilyl groups. Other examples of 6 halogen atoms include unsaturated aliphatic groups such as vinyl, allyl, propenyl, impropenyl, and 1-butenyl groups, and unsaturated alicyclic groups such as cyclohexenyl. Examples include fluorine, chlorine, and bromine, and examples of lower alkylene groups include lower alkylene groups such as methylene, ethylene, propylene, and butylene.

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)cyclohexylzirconium hydride, bis(cyclopentagenyl)phenylzirconium hydride, bis(cyclopentagenyl)benzylzirconium hydride, bis(cyclopentagenyl)neopentylzirconium hydride, bis(methylcyclo) Bis(indenyl)zirconium monochloride monohydride, Bis(indenyl)zirconium monochloride monohydride, Bis(cyclopentagenyl)zirconium dichloride, Bis(cyclopentagenyl)zirconium dibromide, 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(cyclopentagenyl)zirconium diphenyl, Bis(cyclopentagenyl)zirconium dibenzyl, Bis( cyclopentagenyl)methoxyzirconium chloride, bis(cyclopentagenyl)methoxyzirconium chloride, bis(cyclopentagenyl)ethoxyzirconium chloride, bis(cyclopentagenyl)butoxyzirconium chloride, bis(cyclopentagenyl)2 -Ethylhexoxyzirconium chloride, bis(cyclopentagenyl)methylzirconium ethoxide, and, bis(cyclopentagenyl)methylzirconium butoxide, bis(cyclopentagenyl)ethylzirconium ethoxide, bis(cyclopentagenyl) ) phenylzirconium ethoxide, bis(cyclopentagenyl)benzylzirconium ethoxide, bis(methylcyclopentagenyl)oxyzirconium chloride, 4bisindenylethoxyzirconium chloride, bis(cyclopentagenyl)ethoxyzirconium Chloride, Bis(cyclopentagenyl)butoxyzirconium chloride, Bis(cyclopentagenyl)2-ethylhexoxyzirconium chloride, Bis(cyclopentagenyl)phenoxyzirconium chloride, Bis(cyclopentagenyl)cyclohexoxyzirconium chloride , biscyclopentagenyl) phenylmethoxyzirconium chloride, bis(cyclopentagenyl)methylzirconium phenylmethoxide, bis(cyclopentagenyl)trimethylsiloxyzirconium chloride, bis(cyclopentagenyl)triphenylsiloxy Zirconium chloride, Bis(cyclopentagenyl)thiophenylzirconium chloride, Bis(cyclopentagenyl)thioethylzirconium chloride, Bis(cyclopentagenyl)bis(dimethylamide)
Zirconium, bis(cyclopentagenyl)diethylamide zirconium chloride, ethylenebis(indenyl)ethoxyzirconium chloride, ethylenebis(4,5,6,7-tetrahydro-1-indenyl)oxyzirconium chloride, ethylenebis(indenyl)ethoxyzirconium chloride ) dimethylzirconium, ethylenebis(indenyl)diethylzirconium, ethylenebis(indenyl)diphenylzirconium, ethylenebis(indenyl)dibenzylzirconium, ethylenebis(indenyl)methylzirconium monopromide, ethylenebis(indenyl)ethylzirconium monochloride, Ethylenebis(indenyl)benzylzirconium monochloride, Ethylenebis(indenyl)methylzirconium monochloride, Ethylenebis(indenyl)zirconium dichloride, Ethylenebis(indenyl)zirconium dichloride, Ethylenebis(4,5,6,7-tetrahydro-1) -indenyl)dimethylzirconium, ethylenebis(4,
5,6,7-tetra-1-indenyl)methylzirconium monochloride, ethylenebis(4,5,6,
7-titrahydro-1-indenyl) zirconium dichloride, ethylenebis(4,5,6,7-tetrahydro-1-indenyl)zirconium dichloride, 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-simethoxy-1-indenyl)
Zirconium dichloride, Ethylenebis(indenyl)zirconium dimethoxide, Ethylenebis(indenyl)zirconium jetoxide, Ethylenebis(indenyl)methoxyzirconium chloride, Ethylenebis(indenyl)ethoxyzirconium chloride, Ethylenebis(indenyl)methylzirconium ethoxide, Ethylene Bis(4,5,6,7-tetrahydro-1-indenyl)zirconium dimethoxide, ethylene bis(
4,5,6,7-TeI・Lahydro1=indenyl) zirconium jetoxide, ethylene bis(4,5,6,
7-titrapido-1-indenyl)methoxyzirconium chloride, ethylenebis(4,5,6,7-tetrahydro-1-indenyl)ethoxyzirconium chloride, ethylenebis(4,5,6,7-tetrahydro-1
-indenyl) methylzirconium ethoxide.

Examples of the titanium compound include the following compounds.

Bis(cyclopentagenyl)titanium monochloride monohalide, Bis(cyclopentagenyl)methyltitanium hydride, Bis(cyclopentagenyl)phenyltitanium chloride, Bis(cyclopentagenyl)benzyltitanium chloride, Bis(cyclopentagenyl)methyltitanium hydride genyl) titanium dichloride, bis(cyclopentagenyl) titanium dibenzyl, bis(cyclopentagenyl) ethoxytitanium chloride, bis(cyclopentagenyl) butoxytitanium chloride, bis(cyclopentagenyl) methyltitanium ethoxide , Bis(cyclopentagenyl) phenoxytitanium chloride, Bis(cyclopentagenyl)trimethylsiloxytitanium chloride, Bis(cyclopentagenyl)thiophenyltitanium chloride, Bis(cyclopentagenyl)bis(dimedylamide)
Titanium, bis(cyclopentagenyl)jetoxytitanium, ethylenebis(indenyl)titanium dichloride, ethylenebis(4,5,6,7-titrahydro]-indenyl)titanium dichloride.

Examples of the hafnium compound include the following compounds.

Bis(cyclopentagenyl) hafnium monochloride monohydride, bis(cyclopentagenyl) ethyl hafnium hydride, bis(cyclopentagenyl) phenyl hafnium chloride, bis(cyclopentagenyl) hafnium dichloride, bis(cyclopentagenyl) ethyl hafnium hydride hafnium dibenzyl, bis(cyclopentagenyl)-oxyhafnium chloride, bis(cyclopentagenyl)butoxyhafnium chloride, bis(cyclopentagenyl)methylhafnium ethoxide, bis(cyclopentagenyl) Phenoxyhafnium chloride, bis(cyclopentagenyl)thiophenylhafnium chloride, bis(cyclopentagenyl)bis(diethylamide)
Hafnium, ethylenebis(indenyl)hafnium dichloride, ethylenebis(4,5,6,7-tetrahydro-1-indenyl)hafnium dichloride.

The method of supporting the transition metal compound of group IVB of the periodic table on the fine particle carrier includes a method of supporting the group by reacting a functional group on the surface of the fine particle carrier with the transition metal compound, or a method of supporting the fine particle carrier with the above-mentioned organoaluminum compound,
A method of supporting by contacting with the transition metal compound after pre-contact treatment with an aluminoxane compound or a halogen-containing silane compound, or without pre-contact treatment, or the contact is carried out in an inert hydrocarbon medium. Then, the fine particle carrier is contacted with aluminoxane in an inert hydrocarbon medium, and then the medium is evaporated, or the aluminoxane is insoluble or difficult to support. A method in which a microparticle support carrying aluminoxane is prepared by adding a soluble solvent, and a transition metal compound is supported on this by contacting the support, or after the contact is carried out in an inert hydrocarbon medium, the carbonization process is carried out. Examples include a method in which the transition metal compound is supported by evaporating a hydrogen medium, or a method in which the transition metal compound is precipitated and supported on the fine particle carrier by adding an insoluble or slightly soluble solvent for the transition metal compound after the contact. can.

Catalyst component [B] is aluminoxane.

Examples of the aluminoxane used as the catalyst component [B] include organoaluminum compounds represented by the general formula [■] and the general formula [■]. In the aluminoxane, R is a methyl group,
Hydrocarbon groups such as ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, preferably methyl group, ethyl group, isobutyl group, particularly preferably methyl group; Preferably it is an integer of 5 or more. Further, the aluminoxane has the above general formula [■
] or [■], a part of R may be substituted with a halogen atom such as chlorine or bromine, and the halogenated aluminoxane may have a halogen content of 40% by weight or less,
The following method can be exemplified as a method for producing the aluminoxane.

(1) Compounds containing adsorbed water, salts containing water of crystallization, such as magnesium chloride hydrate, TIL acid cupric acid phase hydrate, aluminum acid hydrate, nickel sulfate hydrate, ceric chloride hydrate A method of adding trialkylaluminium to a suspension of a substance in a hydrocarbon medium and causing a reaction.

(2) A method in which water is allowed to directly act on trialkylaluminum in a medium such as benzene, l.luene, ethyl ether, or tetrahydrofuran.

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

For example, an organometallic compound component such as a halogen-containing organoaluminum compound or an organomagnesium compound may be present in addition to the above-mentioned trialkylaluminium.

In the present invention, the following method can be adopted as the form of supplying the aluminoxane [B] to the polymerization reaction system.

(1) A solid catalyst component that does not support aluminoxane is used as the solid catalyst component [A], and the solid catalyst component [A]
and a method of supplying aluminoxane [B] to a polymerization reaction system.

(2) As a solid catalyst component [A], a transition metal compound of Group 1 VB of the periodic table and an aluminoxane [
A method of using a solid catalyst component supporting B] and supplying the solid catalyst component to a polymerization reaction system.

(3) A method in which the solid catalyst component of (2) above is used as the solid catalyst component [A], and aluminoxane [B] is supplied to the polymerization reaction system together with the solid catalyst component [A].

As the solid catalyst component [A], a transition metal compound of Group 1 VB of the periodic table and aluminoxane [B
] The present applicant has disclosed Japanese Patent Application No. 61-311287 and Japanese Patent Application No. 61-31.
The following method (a) or tl) proposed in No. 1286 can be adopted.

(a) After forming an aluminoxane-supported particulate carrier by contacting a suspension of particulate carriers dispersed in a solution of aluminoxane with a solvent in which aluminoxane is insoluble or poorly soluble, the supported carrier is and period/body surface IVB
A solid catalyst for olefin polymerization can be produced by a method for producing a solid catalyst for olefin polymerization, which is characterized in that a solid component is formed by contacting a solution of a group of transition metal compounds.

More specifically, an insoluble or sparingly soluble solvent for aluminoxane is added to a suspension consisting of a solution of aluminoxane and a fine particle carrier, or a suspension consisting of a solution of aluminoxane and the carrier is added to the insoluble or sparingly soluble solvent. is added to precipitate aluminoxane, and in some cases, the solvent used for dissolving the aluminoxane is evaporated from the mixed suspension to promote the precipitation of aluminoxane, thereby forming an aluminoxane-supported fine particle carrier. get.

Next, a suspension consisting of the aluminoxane-supported support and an insoluble or poorly soluble solvent for aluminoxane is brought into contact with a solution of a transition metal compound of Group IVB of the periodic table, thereby converting the transition metal compound catalyst component into the aluminoxane. A solid catalyst for olefin polymerization is prepared by supporting it on a xane-supporting carrier.

In the step of contacting an insoluble or poorly soluble solvent for aluminoxane with a suspension consisting of a solution of the aluminoxane and a fine particle carrier, the solvent in which the aluminoxane is insoluble or poorly soluble with respect to 100 parts by weight of the aluminoxane solution. The proportion of is usually in the range of 10 to 10,000 parts by weight, preferably 100 to 1,000 parts by weight, and the temperature during contact is usually -100 to 300°C, preferably -
50 to 100°C1, preferably -30 to 5
The temperature is in the range of 0° C. and the contacting is usually carried out under stirring.

The aluminoxane solution is formed of at least aluminoxane and the solvent used to dissolve the aluminoxane described above. Methods for obtaining a solution of aluminoxane include simply mixing amphoteric compounds, or
Examples include a method of heating and mixing. The amount of solvent in the aluminoxane solution is from 0.1 to 50% per gram of aluminum in the aluminoxane.
1, preferably 0.2 to 101, more preferably 0
．． It is in the range of 3 to 2 g.

Further, the amount of the carrier in the suspension of the fine particle carrier dispersed in the aluminoxane solution is 1 to 500 g, preferably 10 to 2 g, per 11 of the aluminoxane solution.
00g, more preferably in the range of 20 to 100g.

In addition, in the contacting, the amount of the transition metal compound used per gram of aluminum in the solid aluminoxane suspension is from 0.0005 to 1 gram atom, preferably from 0.001 to 0.1 gram atom. , more preferably in the range of 0.002 to 0.04 gram atom.

In addition, the temperature during the contact is usually -50 to 200°C,
Preferably -20 to 100°C, more preferably -1
The temperature ranges from 0 to 50°C, and the contacting is usually carried out under stirring.

The solution of the transition metal compound is formed of at least the transition metal compound and the solvent used to dissolve the transition metal compound described above. Examples of methods for obtaining a solution of the transition metal compound include a method of simply mixing the compound again, a method of heating and mixing, and the like. The amount of solvent in the solution of the transition metal compound is from 1 to 5,001 Li, preferably from 2 to 200 Li per gram atom of the transition metal compound.
r, more preferably in the range of 3 to 1001.

The solid catalyst for olefin polymerization of the present invention also includes (b) a suspension of a fine particle carrier dispersed in a solution of aluminoxane and a transition metal of group IYB of the periodic table, and a solvent in which the aluminoxane is insoluble or poorly soluble; A solid catalyst for olefin polymerization can be produced by a method for producing a solid catalyst for olefin polymerization, which is characterized in that a solid component is formed by bringing the catalyst into contact with the catalyst.

For more information, see Aluminoxane and Periodic Table IV
By adding an insoluble or poorly soluble solvent of aluminoxane to a suspension consisting of a Group B transition metal compound and a fine particle carrier, or by adding aluminoxane and a transition metal compound of Group IVB of the periodic table to the insoluble or poorly soluble solvent. The aluminoxane and the transition metal compound are precipitated by adding a suspension consisting of aluminoxane and a fine particle carrier, and in some cases, the aluminoxane and the transition metal compound are precipitated by evaporating the solvent used to dissolve the aluminoxane from the mixed solution. A method for preparing a solid catalyst for olefin polymerization in which a transition metal compound and aluminoxane are supported on a fine particle carrier by promoting precipitation of the transition metal compound and/or the transition metal compound can be exemplified.

In the step of contacting a suspension consisting of a solution of the aluminoxane and a transition metal compound of group B of the periodic table and a fine particle carrier with a solvent in which the aluminoxane is insoluble or poorly soluble, The ratio of the solvent in which the aluminoxane is insoluble or poorly soluble to 100 parts by weight of the solution of the IYB group transition metal compound is usually 10 to 10,000 parts by weight, preferably 100 to 10 parts by weight.
00 parts by weight, and the temperature during contact is usually 100 parts by weight.
The temperature range is from 300°C to 300°C, preferably from 50°C to 100°C, more preferably from 30°C to 50°C, and the contacting is usually carried out under stirring.

The aluminoxane and transition metal compound solution is formed from at least the aluminoxane, the transition metal compound, and the solvent used to dissolve the aluminoxane described above. Examples of methods for obtaining the solution include a method of simply mixing the recompounds, a method of heating and mixing, and the like. The amount of solvent in the solution ranges from 0.1 to 501, preferably from 0.2 to 101, more preferably from 0.3 to 21, per gram atom of aluminum in the aluminoxane.

The quantitative ratio of the aluminoxane and the transition metal compound in the solution is 0.0005 to 1, preferably 0.001 to 0.1, per 1 gram atom of aluminum in the aluminoxane. is 0.002
For example, the range is from 0.04 to 0.04.

Further, the amount of the fine particle carrier in the suspension of the aluminoxane and transition metal compound solution is 1 to 500 g, preferably 10 to 200 g, more preferably 20 to 100 g per solution II. range.

Also, the temperature during the contact is usually -100 to 300°C.
, preferably -50 to 100°C, more preferably -
The temperature range is from 30 to 50°C, and the contacting is usually carried out under stirring.

The solid catalyst for olefin polymerization of the present invention can also be produced by (a) contacting a suspension of fine particle carriers dispersed in an insoluble or slightly soluble solvent of aluminoxane with a solution of aluminoxane; After forming a suspension of the supported fine particle carrier, the supported fine particle carrier and the periodic table
A method for producing a solid catalyst for olefin polymerization, characterized in that a solid component is formed by contacting the catalyst with a solution of a Group B transition metal compound.

Specifically, by adding a solution of aluminoxane to a suspension of fine particle carriers dispersed in a solvent in which aluminoxane is insoluble or poorly soluble, or by adding a solution of aluminoxane to a solution of aluminoxane in a solvent in which aluminoxane is insoluble or poorly soluble. The aluminoxane is precipitated by adding a suspension consisting of a particulate carrier, and in some cases, the solvent used to dissolve the aluminoxane is removed by distillation from the mixed suspension to separate the aluminoxane and/or transition. Precipitation of the metal compound is promoted to obtain an aluminoxane-supported fine particle carrier. Next, a suspension consisting of the aluminoxane-supporting carrier and an insoluble or slightly soluble solvent for aluminoxane is brought into contact with a solution of a transition metal compound of Group II/B of the periodic table, thereby converting the transition metal compound catalyst component into the aluminum. A solid catalyst for olefin polymerization is prepared by supporting the nooxane on a carrier.

In a suspension formed from an insoluble or poorly soluble solvent for the aluminoxane and a fine particle carrier, the amount of the carrier is usually 1 to 500 g, preferably 10 to 20 g, more preferably 20 to 100 g per 11 of the solvent. range. Further, the contact between the suspension and the aluminoxane solution is usually carried out at -100 to 300°C, preferably -50 to 100°C, more preferably -30°C.
The temperature range is from 50°C to 50°C. Further, the contact is usually carried out under stirring. The amount of the aluminoxane solution during the contacting is usually in the range of 100 to 1000 parts by weight, preferably 10 to 100 parts by weight, based on 100 parts by weight of the suspension.

The aluminoxane solution used for the contact is formed of at least aluminoxane and the solvent used to dissolve the aluminoxane described above. Examples of methods for obtaining the solution include a method of simply mixing both compounds, or a method of heating and mixing. The amount of solvent in the solution is from 0.1 to 501, preferably from 0.2 to 10 per gram atom of aluminum in the aluminoxane.
1, more preferably in the range of 0.3 to 21.

In addition, aluminoxane-supported fine particle carrier and periodic table IV
For contacting with a solution of a Group B transition metal compound, 0.0005 to 1 gram atom of the Group IVB transition metal compound, preferably 0.0001 to 0. .1 gram atom, more preferably in the range of 0.002 to 0.04 gram atom.

In addition, the temperature during the contact is usually -50 to 200°C,
Preferably -20 to 100°C, more preferably -1
The contacting is usually carried out under stirring.

The solution of the transition metal compound is formed of at least the transition metal compound and the solvent used to dissolve the transition metal compound described above. Examples of methods for obtaining a solution of the transition metal compound include a method of simply mixing both compounds, or a method of heating and mixing them. The amount of solvent in the solution of the transition metal compound is from 1 to 5001.0% per gram atom of the transition metal compound. Preferably 2 to 2001
, more preferably in the range of 3 to 1001 (d)
By contacting a suspension of fine particle carriers dispersed in a solvent in which aluminoxane is insoluble or poorly soluble with a solution of aluminoxane and a transition metal compound of group IVB of the periodic table, aluminoxane and a transition metal compound of group IVB of the periodic table are brought into contact. It can be produced by a method for producing a solid catalyst for olefin polymerization, which is characterized by forming a solid component in which a group transition metal compound is supported on a particulate carrier.

Specifically, by adding a solution of aluminoxane and a transition metal compound of group IYB of the periodic table to a suspension of fine particle carriers dispersed in a solvent in which aluminoxane is insoluble or poorly soluble, or by adding a solution of aluminoxane and a transition metal compound of group IYB of the periodic table, or to a solution of aluminoxane. Aluminoxane and transition metal compounds are precipitated by adding a suspension consisting of an insoluble or poorly soluble solvent for aluminoxane and a fine particle carrier, and in some cases, the solvent used to dissolve the aluminoxane and transition metal compounds is added. A method for preparing a solid catalyst for olefin polymerization in which a transition metal compound and aluminoxane are supported on a fine particle carrier by promoting precipitation of the aluminoxane and/or transition metal compound by distillation removal from the mixed suspension. can be exemplified.

In a suspension formed from an insoluble or poorly soluble solvent for the aluminoxane and a fine particle carrier, the amount of the carrier is usually 1 to 500 g, preferably 10 g per 11 of the solvent.
The amount ranges from 20 to 200 g, more preferably from 20 to 100 g. Further, the contact between the suspension and the solution of the aluminoxane and the transition metal compound of group IVB of the periodic table is usually carried out at -100 to 300°C, preferably -
50 to 100°C, more preferably -30 to 50°C
It is carried out in the range of °C. Further, the contact is usually carried out under stirring. The amount of the solution of aluminoxane and the transition metal compound during the contact is usually 1 to 1000 parts by weight, preferably 10 to 1 part by weight, per 100 parts by weight of the suspension.
00 parts by weight.

The solution of aluminoxane and the transition metal compound used for the contact is formed by at least the aluminoxane, the transition metal compound, and the solvent used to dissolve the aluminoxane described above. Examples of methods for obtaining the solution include a method of simply mixing the amphoteric materials, or a method of heating and mixing. The amount of solvent in the solution is 0.1 per gram atom of aluminum in the aluminoxane.
It ranges from 0.2 to 501, preferably from 0.2 to 101, more preferably from 0.3 to 21.

The concentration of the transition metal compound in the solution is 0.0005 to 1 gram atom of the transition metal compound per gram atom of aluminum, preferably 0.0001 to 0.1 gram atom.
Gram atoms, more preferably 0.002 to 0.04
It is in the gram atom range.

Further, the contact is usually -50 to 200°C, preferably -
20 to 100°C, more preferably -10 to 50°C
℃ range, and the contacting is usually carried out under stirring.

As a soluble solvent for group IVB transition metal compounds of the periodic table,
Examples include aromatic hydrocarbons such as benzene, toluene, ethylbenzene, propylbenzene, butylbenzene, and xylene, and halogen-containing hydrocarbons such as chlorobenzene, dichloroethane, and tane.

Examples of insoluble or poorly soluble solvents for transition metal compounds of group IVB of the periodic table include pentane, hexane, decane,
Aliphatic or alicyclic hydrocarbons such as dodecane, kerosene, and cyclohexane can be mentioned.

Examples of solvents for aluminoxane include aromatic hydrocarbons such as benzene, toluene, ethylbenzene, propylbenzene, butylbenzene, and xylene.

Insoluble or poorly soluble solvents for aluminoxane include pentane, hexane, decane, dodecane, kerosene,
Mention may be made of straight or branched aliphatic hydrocarbons such as cyclohexane and cycloaliphatic hydrocarbons such as cyclohexane, norbornane, ethylcyclohexane.

As the insoluble or slightly soluble solvent for aluminoxane, it is preferable to use a solvent having a higher boiling point than the solvent used to obtain the aluminoxane solution.

The solid catalyst component [A] prepared by the above method contains a transition metal compound in an amount of 0.5 to 500 milligram atoms, preferably 1 to 200 milligram atoms, more preferably 3 to 50 milligram atoms, as transition metal atoms per 100 g of particulate carrier. Contains. The solid catalyst component [B] is
The aluminoxane contains from 50 to 50,000 milligram atoms, preferably from 50 to 10,000 milligram atoms, more preferably from 100 to 4,000 milligram atoms as aluminum atoms per 100 g of the particulate organic compound carrier. In the solid catalyst component [A], the atomic ratio of aluminum to transition metal (A17M
) is in the range of 1 to 1000, preferably 6 to 600, more preferably 15 to 300. In the solid catalyst component [A], the solid catalyst has an average particle size of 5 to 200 μm, preferably 10 to 150 μm, and more preferably 20 to 100 μm.

The organoaluminum compound [C1 is a compound of the general formula [II1 and the general formula 1111 R'mA l(OR''), -1 [
IIFR”nA I[ORiR1]*-n L I
II] In the formula E, R1, R" and R3 represent a hydrocarbon group, R' represents a hydrocarbon group, an alkoxy group or an aryloxy group, and represents 0 < m < 3.0 <n> 3] In the organoaluminum compounds represented by the general formula [I] and the general formula [II1, R'% [<2 and 1 is 1] Specifically, a methyl group, Ethyl group, rhopropyl group, isobutyl group, n-butyl group, t-butyl group, 5ec-butyl group, isobutyl group, rhohexyl &
, n-octyl group, linear or branched saturated or unsaturated aliphatic hydrocarbon group having 1 to 1 carbon atoms such as 2-ethyl hakama crystal, cyclohexane group, methylcyclopentyl group, methylcyclohexyl group Examples include carbon fi4 to 1 () jIFt cyclic carbocyclic water hydrocarbon groups such as groups, aromatic hydrocarbon groups having 6 to 16 carbon atoms such as nyl group, tolyl group, xylyl group, and naphthyl group. can. *, general formula [II1 or general formula t
In the organoaluminum compound represented by fll,
R'<3 is preferably a branched hydrocarbon group, particularly preferably a branched furkyl group, and a particularly preferred example of R2 is a methyl group. In addition, in the aluminum compound represented by the general formula 11N, [(rumor has it that specific examples include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, inbutyl group, etc.) having 1 to 10 carbon atoms. aliphatic hydrocarbon groups, m-ring water hydrocarbons having 4 to 10 carbon atoms such as cyclohexyl groups, methylcyclopentyl groups, and methylcyclohexyl groups, carbon atoms such as phenyl groups, tolyl groups, xylyl groups, and naphthyl groups. 6 to 1
6 aromatic hydrocarbon group, methquine group, ethoxy group, propoxide, butoxy group, isobutoxy group, cyclohexyl group, methylcyclopentyloxy group, alkoxine-IJi having 4 to 10 carbon atoms such as methylcyclohexyloxy group, phenoxy group, Examples include Tolyloxy Z&, Su7 Toxicai, and the like. Also, general formula 111
In this case, the seagull has a temperature of 0, preferably 1≦S2.
It represents a positive number of 5, particularly preferably -=2. In general formula 111), ■ represents a positive number of 0<n<3, preferably 1≦1≦2.5, and particularly preferably n=2.

Organoaluminum compound t represented by the general formula [II1
Specifically, cJ includes diethylaluminum methoxide, avylaluminum methoxy, diisobutylaluminum nodoxy, l/, diisobutylaluminum ethoxide, bis-2-methylbunalaluminum methoxide, bis-3-methylbunalaluminum methoxy. do, bis3-methylbunal aluminum methoxide,
Bis-2-methylpentylaluminum methoxide, bis-3-methylpentylaluminum ethoxide, bis-4-
Dialkyl aluminum alkoxides such as methylpentylaluminium propoxide, bis-2-methylhexylaluminum butoxide, bis-3-methylhexylaluminum cyclohexyl oxide, dicycloalkylaluminum alkoxides such as bis-2-ethylhexylaluminum phenoxide, dicyclohexylaluminum methoxide, diphenyl Aluminum methoxide, bis7lyl aluminum alkoxides such as bistryl aluminum methoxide, ethyl aluminum dimethoxide, isoprobylaluminum dimethoxide,
Isobutylaluminum diethquinde, 2-methylbutylaluminium rhamnomethoxide, 3-methylbutylaluminium rhamnomethoxide, 3-methylbunal aluminum methoxide, 2-methylbentylaluminium rhamnomethoxide, 3-methylbenchyl Aluminum rhamnomethoxide, 4
-Methylbentylaluminium rhamnomethoxide, 2-methylhexylaluminum zoproboxide, 3-methylhexylaluminum cyclohexyl oxide, 2-ethyl alkylaluminum dialkoxide, such as cyaluminum ν phenoxide, cyclohexylaluminum zoproboxide cycloalkylaluminum dialkoxides such as methoxide, cyclooctylaluminum noetoside,
7-aryl aluminum dial such as phenylaluminum nomethoxide, tolylaluminum jetoxide: J
oxide, theory in these organoaluminum compounds = 1
．． Alkylaluminum sesquialkoxide, which is No. 5, can be exemplified. Among these and aluminum compounds, is it dialkyl? Preferred are aluminum alkoxides, particularly diisoalkylaluminum alkoxides.

*, an organoaluminum compound represented by the general formula [II11] [CJ is specifically E t, *A 10-8
i+OMe),, 1soP raA l-0-8i+
OE t)3.1so13u2A l-0-8i40
Me),, 1soB u2A l-0-8i40 I
EL) 3.1so13utA I-0-8i40n-)
3u),, eisoBu, A1-0-8 i(0rrH
exyl)s, 1soOetylA l-0-81(
OEt)+, 1soB u*A io -8iMea,
iso B L12 A 10-8*Et,, 1so)
3 u2A lo -s iP h3, etc. can be exemplified.

The organoaluminum compound ICI is produced by combining these organoaluminum compounds 1. A compound that produces CI may be added.

In the method of the present invention, the catalyst is the solid catalyst component IA.
It is formed from I, the aluminoxane IB, I, and the organoaluminum compound IcI, but it may contain other constituents such as electron donors as optional components. The electron donor component may be supported on the solid catalyst component tA], or may be supplied to the polymerization reaction system together with the isoform component [AJ, the aluminoxane IB+, and the organoaluminum compound 1G]. Good too.

Electron donor and 1. So what about carboxylic acids, esters, ethers, ketones, aldehydes, alcohols, alcohols, and acids? Examples include oxygen-containing compounds such as amide compounds, compounds containing metal atoms such as aluminum and silicon, nitriles, amines, and phosphines. For example, the content of the electron donor is usually in the range of 0 to 1 mol, preferably (), 1 to), 6 mol per gram of the transition metal electron (M).

The method of the present invention is effective for producing olefin polymers, particularly ethylene polymers and copolymers of ethylene and a-olefins. α-olefins having from 2 to 20, such as ethylene, tetrapyrene, 1-butene,
1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1
-hexadecene, 1-octadecene, 1-eicosene and the like. Among these, polymerization of ethylene or copolymerization of ethylene and a-olefin having 3 to 10 carbon atoms is preferred.

In the method of the present invention, olefin polymerization is usually carried out by a gas phase polymerization method or a phaseless polymerization method such as a slurry dripping method. In stirring the slurry, an inert hydrocarbon may be used as the solvent, or the olefin itself may be used as the solvent.

Specifically, the hydrocarbon medium includes butane, isobutane,
Pentane, hexane, octane, decane, dodecane,
Examples include aliphatic hydrocarbons such as hexa-nadecane and octadecane, alicyclic groups such as cyclobencune, methylcyclobencune, cyclohexane and cyclooctane, R-hydrocarbons, petroleum fractions such as kerosene and gas oil.

The use of the transition metal compound when carrying out method 7j of the present invention in a liquid phase polymerization method such as a slurry polymerization method or a gas phase polymerization method is dependent on the concentration of the reduction and metal element f in the polymerization reaction system. usually in the range of 10-a to 10-2 gram atoms/1, preferably 10-a to 10-3 gram atoms/1.

Further, when carrying out the present invention by a liquid phase polymerization method or a gas phase polymerization method, the amount of aluminoxane used is 6 milligram atom/1 or less, preferably 3 milligram atom in terms of aluminum atoms in the reaction system. /l, more preferably from 0.01 to 2 milligram atoms/l, particularly preferably from 0.02 to 1 milligram atom/l. The amount of aluminum atoms used in the aluminum oxane compound component [CI total aluminum raw material 14'-luminoxane fraction 11-1] is usually 20 to 95%, preferably (- < is in the range of 40% and 92%, and similarly, the organoaluminum compound component [CI
The proportion of the transition (aluminum) bt f- used in the reaction system is usually in the range of 80% to 80%, preferably 8 to 30%.
The ratio of the aluminum raw material r~ of the total amount of the aluminum/oxane component [3] and the specific aluminum compound component [CI to the group atoms is usually 20 to 10,000, preferably 40 to 5,000, particularly IJf- or 60 to 5,000. 2 (l OO's @).

When the method) of the present invention is carried out by a liquid phase polymerization method such as the Suf'J-It method, the polymerization temperature is usually -50 to 12
0°C1 good A! L < is () or 100 'C17
) within the range of 6.

When the method of the present invention is carried out by a gas phase polymerization method, the polymerization temperature is usually 120°C to 120°C, preferably 20 to 1°C.
) is in the range of 0°C.

The condition is 2 or SOk+r/am', and 1ζ can also be used in any of the run type, semi-continuous type, and continuous type.

Furthermore, it is also 611-ization to carry out the polymerization under two different reaction conditions.

In the h method of the present invention, when a free polymerization method or a gas phase polymerization method is adopted, -CT prior to olefin polymerization
Prepolymerization of the olefin is preferably carried out in the presence of a solid catalyst. The preliminary song is about the transition metallization inclusions of group fft3 of the AI periodic table in solid catalysts wty1? (by passing 71 to 1000 g of fh, preferably 5 to 51701, more preferably 10 to 200 g of olefin e1f).

Prediction! The olefins used in A1 are ethylene and a-olefins having 3 to 20 carbon atoms, such as propylene, 1-butene, 4-methyl-1-pentene, 1-
hexene, 1-octene, 1-decene, 1-dodecene,
Examples include 1-butrabusene, but
Ethylene is preferred.

The temperature of the spare garage is between -20°C and 7°C, preferably between -30°C and 60°C, more preferably below 0°C.
The temperature range is 50°C.

The treatment may be carried out either batchwise or continuously, and f, t+' can be carried out under normal pressure or under pressure.
I can do that. In the prepolymerization, a molecular weight agent such as hydrogen or an i84wJ agent may be present, but at least f
jl Intrinsic viscosity M7 J measured in decalin at 3b°C
:+f0.2dA/g or more, preferably 0.5-1
, 20 di/F! The amount of prepolymer that can be produced is limited.

Prepolymerization is carried out without solvent or in an inert hydrocarbon medium. Prepolymerization in an inert hydrocarbon medium is preferred from the viewpoint of operability. Examples of the inert hydrocarbon medium used in the prepolymerization include the solvents mentioned above as insoluble or soluble solvents for aluminoxane.

The concentration of the solid catalyst in the preliminary claw metal reaction system in pre-polymerization and (- is usually the concentration of transition metal atoms in the solid catalyst J O""6 to 1 gram atom/2, preferably 10
It ranges from -4 to 10''2 grams -/1.

1 Example 1 Next, the present invention will be concretely explained using examples.

Preparation of 1-methylaluminoxane 1 Stirring in 4001 which was sufficiently purged with nitrogen (the 'f' substitute is t)
XM7')X Near G::AL(SO+)s' 14Hz
0 37g and toluene 12! After cooling to 0° C., 125 mA of toluene containing 5 Oval of chill aluminum was added dropwise over 11 hours. Next C12
After one reaction in which the temperature was raised to 40°C over time and the reaction was continued at that temperature for 40 hours, the M liquid was separated by tr filtration.
Remove low boiling point substances from the separated liquid using an evaporator, add toluene to the remaining solid, and collect as a toluene solution 1
．． Ta.

The molecular weight determined from the q and α precipitation in benzene was 888, and therefore the degree of polymerization of this aluminoxane was 15.

Example 1] Preparation of solid catalyst 1 In a 300111 reactor equipped with a stirrer capable of reducing pressure to 11f, 10
A toluene solution of 67-1 containing the methyl 7-luminoxane corresponding to 0 mmol of AI atoms and polyethylene powder (manufactured by Mitsui Petrochemical Industries, Ltd., trade name: Min) 48 with an average particle size of 35 μ are added. , stir at room temperature.
0()+/l of fine gJ1n-decane for about 0.5 hours r11
Methylat and luminoxane were precipitated by adding 100 ml of methyl oxane to the reactor using a vacuum pump.
Toluene in the reactor was removed by raising the temperature inside the reactor to 45° C. over about 3 hours while reducing the pressure to torr, and methylaluminoxane was further precipitated. This reaction solution was filtered using a filter, the liquid phase was removed, and the solid was resuspended in n-decane. ! After adding a toluene solution of
Add 10 mmol of diisobutylaluminum methoxide to the hindlimb suspension after applying vacuum for 1 minute to remove toluene, mix at room temperature for 60 minutes, cool to -20°C, and filter the suspension. solid catalyst)
1g was produced.

The Zr content in the obtained solid catalyst was 10 mmol per 100 g of polyethylene used as a carrier, and 2.
2 mol, and the V average catalyst particle diameter determined by microscopic observation was about 40 μm.

[Pre-polymerization] 400mj! 100+ under nitrogen atmosphere in the reactor with stirring
After adding 1 jt of purified n-decane and the above solid catalyst in an amount equivalent to 0.1 mmol of Zr, ethylene was fed at a rate of 4 Nl/hour for 1 hour. During this time, the temperature was maintained at 2 (>°C). After the ethylene supply was completed, the system was replaced with nitrogen, washed once with purified hexane, and then reconstituted with hexane.
The mixture was suspended and stored in a catalyst bottle.

[fR-1 Add 250 ml of sodium chloride as a powder to a No. 8 21 autoclave that has been purged with nitrogen, and while heating it to 90°C, vacuum the autoclave so that the internal pressure becomes less than bOl infusion. The pressure was reduced to 11' using a pump for 2 hours.Then, the temperature of the autoclave was lowered to 75°C, and the interior of the autoclave was replaced with ethylene, after which the prepolymerized solid catalyst component was added to 0.0% in terms of zolconium atoms. 0
After adding 0.59 mmol, the autoclave was closed to 1.5 mm, and 508 mjl of hydrogen was added, and the autoclave was pressurized with ethylene so that the internal pressure was 8 kg/c@1 G.

Stirring 4'11 Increase speed to 300 rp++ and stir at 80°C.
Time polymerization was performed.

After the completion of the merging, the entire amount of polymer and sodium chloride in the autoclave was taken out and poured into about 11 g of water. Approximately 5
By stirring [Wl], almost all of the sodium chloride was dissolved in water, and only the polymer was floating on the water surface.The floating polymers of 1 and - were taken in equal numbers, and after washing with methanol No. 10, the urine was reduced at 80℃. It was dried overnight in a dryer. The yield of the obtained polymer was 103 g, and M F' R was 1,4
dg/eein, apparent bulk density is (), 45g/a
#Met.

Comparative Example 1 An experiment was conducted in the same manner as in Example 1 except that quibutylaluminium methoxide was not used in Example 1. The results are shown in Table 1.

Example Z 1 Preparation of solid catalyst: In a 400 ml reactor equipped with a stirrer capable of reducing pressure 0f, 10
Add 67 mjl of toluene solution containing the above methylaluminoxane corresponding to 0 mmol of A1 atoms and 4 □ of polyethylene powder with average particle size of 4 gL 35 μ'- (manufactured by Mitsui Petrochemical Industries, Ltd., trade name: Me-N), and let the mixture cool to room temperature. By adding purified n-decane from 100 companies over about 0.5 hours with stirring, methylaluminoxane was precipitated.Then, while reducing the pressure inside the reactor to 4 Lorr using a vacuum pump, the inside of the reactor was Toluene in the reactor was removed by raising the temperature to 45° C. over about 3 hours, and further methylaluminoxane was precipitated. This reaction solution was filtered using a filter, and after removing the liquid phase, the solid portion was resuspended in ■-decane. 5 L of toluene solution containing cyclophyte was added and mixed at room temperature for about 1 hour.
The pressure was reduced to R for 30 minutes, and the toluene was added to the VANJ cell 1. A solid catalyst for olefin polymerization was prepared by passing the cloudy hind limb liquid once.

1; 7. in the crushed solid catalyst. The r content is the polyethylene 100I used as a carrier (10 millimeters per hour, AI
The combined amount was 1.9 mol per 1()Og of polyethylene used as a carrier, and +LI6 was determined by microscopic observation.
The J catalyst particle diameter was about 4()μ pupil.

[Preliminary IIjI vehicle 1 4 (10 ml stirring a.
After adding 11jn-decane of 0(io+j!), 5() mmol of diisobutylaluminum methoxide, and the above solid catalyst in an amount corresponding to 0.1 mmol of Zr, 4NJ!/
Ethylene was fed for 1 hour at a rate of 1 hour. During this time, the temperature was maintained at 20°C. After the supply of ethylene is finished, the inside of the prefecture is replaced with nitrogen, then washed once with purified hexane, and +q +! ! The mixture was clouded and stored in a catalyst bottle.

Polymerization of Katylene was carried out in the same manner as in Example-1. .

Comparative Example 2 Noisobutylaluminum meth Asite was used in Example 2.1. Table 1 shows the results of 6 experiments conducted in the same manner as in Example 1, except that there were no cases.

Example 3 [Preparation of solid catalyst! In a reactor with stirring + 1' rock bottom capable of vacuum rIf of 300■e, 1
i corresponding to 00 mmol of Δl atoms; I methyl °?
67 toluene solution containing luminoxane and 5
C) Add 2 g of silica (Devison Co., $952) calcined at 0°C for 121 hours, and add 100 g of purified silica at room temperature with stirring.
About 0 n-decane! Methylaluminoxane was precipitated by adding i5 hours.

Next, the pressure inside the reactor was reduced to 4 jorr using a vacuum pump, and the temperature inside the reactor was raised by 1 jorr to 35°C over a period of time to remove the toluene in the reactor and remove the methylaluminol. More xane was precipitated.

This reaction solution was filtered using a filter, the phaseless part was removed, and the solid part was suspended in 11-decane for 19 hours.
, 5 liters of toluene containing 2 mmol of bis(cyclopentagenyl)zirconium cyclophyte ￥8? & added. After mixing at room temperature for about 1 hour, the liquid phase was removed using a filter to prepare a solid catalyst for olefin polymerization.

The χr content in the obtained isocatalytic catalyst is per 100tr of silica used as a support. mmol, A1-containing mouse is 2.4 mol per 100 g of silica used as a carrier,
The average catalyst particle diameter determined by microscopic observation is approximately 40μ.
Met.

Solvent-free polymerization of P and ethylene was carried out in the same manner as in Example 2. The results are shown in Table 1.

Comparative Example 3 An experiment was conducted in the same manner as in Example 3 except that diisobutylaluminum methoxide was not used in Example 14 fl 3. The results are shown in Table 1.

1 Synthesis of aluminoxane 1 A12
(S()4)t or 14010: ('/gt) Rue''/125-1 and cooled to 0 °C) After 3J, trimethylaluminum SO diluted with toluene 1251 (
1st step 01 is 40 degrees C; this is good,
After the reaction was continued for 10 hours at that temperature, solid-liquid separation was performed by filtration, and toluene was removed from the furnace solution to obtain white solid aluminum sample 1. The molecular weight determined by coagulation and precipitation in benzene is <, 3: (0, m shown in catalyst component (1))
The value was 14.

1 solid catalyst rll? ! ! 1. Syria'/
('I' j6J grain size j/ 0 μ, ratio table 11'+f
A toluene solution of 52 g of methylaluminum monochloride (a, (A 1
．． 1 wool / 1. ) 26 ml and toluene 1 (1 batch) were added and heated at 80"C for 2 hours. Then, the l and M liquids were separated by tIJ filtration to obtain a catalyst component. This catalyst component was transferred into 50 al of toluene. ,
Furthermore, a toluene solution (7', rO
,04a+ol/l)4:(Add ml and incubate at 80℃ for 1
Time heat 1. In addition, solid-liquid separation was carried out by 111 and 74 for 9r.
Then, 19.6 ml of aluminoxane dissolved in toluene (Ag 1,0,'(wo doors/l)) was added to the obtained solid component.
and toluene 801 were added, and the mixture was stirred at room temperature for 30 minutes.

Thereafter, the mixture was stirred at room temperature for 30 minutes. Thereafter, by removing toluene with an evaporator at room temperature: /, rO, 08 wt%, Aj! A solid component of 10 wt% was obtained.

Prepolymerization and solventless polymerization of ethylene were carried out in the same manner as in Example 2, except that the scale of the 1'-preparation polymerization was changed to half the scale of Example 2.

Comparative Example 4 A substitute crop was prepared in the same manner as in Example 4 except that noisobutylaluminum methoxide was not used in Example 4I. The results are shown in Table 2.

Example 5 [Preparation of solid catalyst 1] Consisting of silica (Davison Co., Ltd. 1 $952) S calcined at 800° C. for 12) hours in a 400 o + I stirrer with sufficient nitrogen purging, and toluene 1 () OL61. 50 containing 2 mmol of aluminum/Oyasan in suspension
After adding a toluene solution of 1 at room temperature, the temperature of the mixture was raised to 10°C, and a reaction was carried out at 10°C for 21 hours. After the reaction was completed, the liquid portion was removed from the reaction solution using a filter, and the remaining solid portion was resuspended in 100 ml of toluene. 9. This suspension contains 038 mmol of bis(cyclopentadienyl)norconylamnocloid.
After the reaction was completed, the liquid part was removed from the suspension using a filter, and the remaining solid part was extracted with toluene. Solid catalyst component 1.AI was washed twice using
I got it. The amount of zirconium supported in the catalyst component IAI is 0.
゜61,% was 0,hi,t! i^1-body catalyst composition lA
Add toluene solution of aluminoxane (An!
1.0: (11101/'l) 4°/ml and 50ml of toluene were added and stirred at room temperature for 305 - 1ltl, then the toluene was removed with an evaporator at room temperature [-
Solid acid 5F carrying fluminoxane was obtained.

Example of polymerization of preliminary r+ and solvent-free polymerization of ethylene.
This was carried out according to method 2. The results are shown in Table-2.

Comparative Example 5 An experiment was conducted in the same manner as in Example 4, except that neuisobutylfluorinium methoxide was not used in Example 5. The results are shown in Table 2i.

Example 6 Preparation of 1 Solid Catalyst Component + AI 1 Silica calcined for 12 hours at 300" (Devison Co.! Il # 952): 4 Bi and A mixed suspension consisting of 50 ml of trichomerosifun was stirred at 50°C for 2 hours. After 6 reaction cycles, the liquid part was removed from the reaction solution using a filter, and the remaining solid part was removed. 50-1
I11 was suspended in toluene. This suspension contains bis(cyclopentadienyl)zirconyramnoclide of 01: (l) Toluene of 01 was added at 25°C, and the reaction was carried out under stirring at 50°C for 2 hours. After the reaction reached 0°, the liquid part was removed from the turbid liquid using a filter, and the remaining solid part was washed twice with toluene to obtain the solid catalyst component IAI. The amount of zirconium supported in the catalyst component tAl was 1.2 wt%. To 11 grams of the above solid catalyst component LA, a toluene solution of aluminoxane (Ag1.0: (wool/l) 4'
/ ml and toluene 501 and heated at room temperature: (()
After stirring in the dark, toluene was removed from an evaporator at room temperature and solid components of aluminoxane were removed.

Prepolymerization and melting of ethylene! & Follow the polymerization method in Example-2')! ,mL,ta. The results are shown in Table 2. Comparative Example +1 An experiment was conducted using the same method as in Example 4, except that diimbunal aluminum methoxide was not used in Example 6. 1". The results are shown in Table 2.

Example 'l The methylaluminum/oxane mixture used in the preparation of the solid catalyst of Example 2 was prepared from 100 mmol to 7 mmol of S(0 mmol), and the amount of aluminum methoxide added at 1.5 mmol was preliminarily added to 5 mmol of methylaluminum/oxane. ) A solid catalyst was prepared by the Jj method similar to Example 2 except that the amount was changed from mmol to 15 mmol, and the solid catalyst was prepared by the H method similar to Example 2.
8 stocks got tsuke ↑r. The experimental results are shown in Table J.

Comparative Example Same as Example 1, except that in Example 4, quintal aluminum methoxide was used and no aluminum methoxide was used.
The experiment lasted 7 hours due to repeated operations. The results are shown in kz (.

Example 8 The diisobutyl °rluminium meth-cyto used in Example 7 (isol axis), Δl-0-8il.:L
, except for 1 change r and z.
became.

Experimental results are shown below: Yukobo Shi9-1 Comparative Example 8 In Example 8 (iqoBu)2Al-0-8i11
．． .

The experiment was carried out using the same Nof method as in Example 8, except that 4F was not used. The results are shown in Table j1.

Table 2 [Effects of the Invention 1] The present invention provides an olefin polymerization method that has a relatively large olefin homopolymerization and co-polymerization activity, and has a large bulk specific gravity, uniform particle size, and fine powder. less,
Polymers and copolymers having a narrow molecule W and, in the case of co-intervention, a narrow composition 41 can be produced.

[Brief explanation of drawings]

Figure fjS1 and Figure 2 are 7L1-chart diagrams showing one example of catalyst preparation in olefin polymerization of 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 a fine particle carrier, [B] Aluminoxane, and [C] General formula [I] or General formula [II] R^1mAl (OR^2)_3_-m[I]R^3n
Al[OSiR_3^4]_3_-n[II] [wherein, R
^1, R^2 and R^3 represent hydrocarbon groups, R^4
represents a hydrocarbon group, an alkoxy group, or an aryloxy group, and represents a positive number of 0<m<3 and 0<n<3. A method for polymerizing olefins, which comprises polymerizing or copolymerizing.