JPH11269224A - Catalyst for olefinic polymer preparation and preparation of olefinic polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a catalyst capable of giving a polymer having little residual metal content with high activity and good efficiency by including a compd. of a group 8-10 transition metal in the periodic table; a clay, a clay mineral or an ion-exchangeable lamellar compd.; and a silane compd. SOLUTION: A polymerization catalyst contains (A) such a compd. of a group 8-10 transition metal in the periodic table as expressed by formula II, i.e., a complex compd., among compds. of formula I; (B) a clay such as montmorillonite or the like, a clay mineral, or an ion-exchangeable lamellar compd.; and (C) a silane compd. such as trialkylsilane chlorides, with contg. on the basis of 1 mole of the transition metal in component A, 0.1-100,000 moles of the hydroxyl group in component B and 0.1-100,000 moles of the Si atom in component C, or when component B is other than a clay or a clay mineral, with contg. on the basis of 1 g of component B, 0.000011 g of the transition metal in component A and 0.001-100 g of the Si atom in component C. In formula I, R<1> and R<4> are each a 1-20C aliphatic hydrocarbyl group or the like; R<2> and R<3> are each a 1-20C hydrocarbyl group; X and Y are each a halogen or the like; and M is a group 8-10 transition metal in the periodic table.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an olefin polymer production catalyst and a method for producing an olefin polymer, and more particularly, to a practical high molecular weight olefin polymer,
In particular, the present invention relates to a novel catalyst for efficiently and industrially producing polyethylene and a method for producing an olefin polymer using the catalyst.

[0002]

2. Description of the Related Art At present, Ziegler-based and metallocene-based catalysts are mainly used as catalysts for producing olefin polymers, and these catalysts are composed of metal elements belonging to Group 4 of the periodic table such as titanium and zirconium. Compounds are used as main catalyst components. In metallocene-based catalysts, catalysts comprising metallocene and aluminoxane are mainly used (JP-A-58-19309, JP-A-2-167307, etc.). A polymer having a very high polymerization activity and a narrow molecular weight distribution has been obtained.

[0003] On the other hand, recently, as a new system different from these, nickel and palladium, etc.
Systems using complexes of metals belonging to groups 10 to 10 have been developed. Heretofore, nickel complexes have been known as catalysts for the oligomerization reaction of olefins, but have been considered unsuitable for polymer production. Techniques relating to catalyst systems using nickel or palladium complexes include, for example, the polymerization of ethylene using a catalyst in which an adduct of quinone and tertiary phosphine is coordinated with (1) a Ni (0) complex. Method (Japanese Patent Publication No. 5-1796), (2) N
a catalyst system comprising an i (0) complex, an adduct of maleic anhydride and tertiary phosphine, phosphorus ylide, and an organoaluminum compound (JP-A-61-203106); (3) Ni
(0) or a catalyst system comprising a Ni (II) complex and an iminophosphorane compound (JP-A-3-115311); (4) Nos. 8 to 1 having a cis-type chelating ligand
Group 0 metal (Fe, Co, Ni, Ru, Rh, Pd, O
(5) Ni polymerization method using a borate complex of (s, Ir, Pt) (JP-A-4-227608);
(0) A catalyst system comprising a complex, an adduct of imide and tertiary phosphine, and a phosphine oxide (JP-A-6-122721)
JP), (6) BF ₄ of Pd (II) ^- a catalyst system combining methylaluminoxane in complex (JP-A-7-82
314), (7) a catalyst system comprising a Ni (II) complex, an iminophosphorane compound and an organoaluminum compound (JP-A-3-277610);
Catalyst system comprising (0) or Ni (II) complex and iminophosphorane compound having a bulky substituent
25932), and (9) a catalyst system in which a linear or cyclic aluminum compound is combined with a phosphorus-oxygen chelate complex of Ni (II) (Japanese Patent Application Laid-Open No. 64-21717).

However, the ethylene polymerization method (1) has an extremely high reaction pressure (for example, 100 kg / c).
m ² ) and extremely low activity of producing polyethylene (about 6 k / g-Ni · hr). The catalyst system of (2) is also a reaction under high-pressure ethylene, and has many catalysts. It is complex over its components and has drawbacks such as very low activity (about 1 kg / g-Ni · hr or less). In the catalyst system (3), the reaction pressure is low, but the activity is extremely low (about 1 kg / g-Ni · hr).
Also, in the ethylene polymerization method of (4) and (4), the activity is extremely low (about 0.1 kg / g-Ni · hr or less). Furthermore, the catalyst system of (5) has low activity (about 5 kg / g-N
The catalyst system of (i · hr) and (6) requires expensive methylaluminoxane for expression of activity and has low activity (about 3 kg / g-Ni
Hr), (7) and (8) also have extremely low activity (about 5 kg / g-Ni · hr or less), and the catalyst system of (9) requires expensive methylaluminoxane as a co-catalyst. Despite the high pressure correlated with the activity, the activity is low (eg about 20 k / g for 30 kg / cm ² G).
g / g-Ni · hr).

Further, recently, a combination or a combination of a nitrogen-containing ligand complex such as diimine of a Group 8-10 metal such as nickel and palladium with an organoaluminum compound such as methylaluminoxane (MAO). Nitrogen ligand complex and BF ₄ ⁻ , PF ₆ ⁻ , S as anion species
Catalyst system using bF ₆ ⁻ , BAF ⁻ [tetrakis (3,5-bistrifluoromethylphenyl) borate], for example, the following [1] and [2]

[0006]

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[0007] A catalyst system as disclosed in (WO 96/23010) has been disclosed. This catalyst system
In the polymerization of ethylene, the activity is extremely high as compared with the above-mentioned catalyst system, and the obtained polymer has a feature that it has a multi-branched structure, but it can be used only at a low temperature, and the molecular weight of the obtained polymer is low. Low and not yet practical.

Further, in order to obtain sufficient polymerization activity using a metallocene / aluminoxane-based catalyst or a Group 8-10 metal-containing nitrogen-containing ligand complex / aluminoxane-based catalyst such as [1], a large amount of aluminoxane is required. In particular, it is expensive, inconvenient to handle, has poor storage stability, and requires highly dangerous methylaluminoxane, which is not only inefficient, but also requires removing catalyst residues from the polymer produced. there were.

Further, there has been proposed a method of polymerizing an olefin with a metallocene-based catalyst using a clay, a clay mineral or an ion-exchange layered compound (JP-A-5-301917). However, the structure of the formed polymer is different from the metallocene-based catalyst in eighth to tenth.
It has not been known that a catalyst can be used in combination with a group III metal-containing ligand complex.
Pretreatment of clay minerals with organoaluminum, especially trimethylaluminum, which is expensive and dangerous, is essential, and has the disadvantage that the activity per aluminum is not sufficient and the amount of catalyst residues in the product is large. Was.

[0010]

SUMMARY OF THE INVENTION In this situation, the present invention is intended to convert a practical high-molecular-weight polyolefin, particularly polyethylene, from methylaluminoxane, which is inconvenient to handle, has poor storage stability, and has a high risk. Not used in large amounts, and reduce the amount of organoaluminum used in the entire polymerization system,
Good quality olefin polymer with little residual metal
It is an object of the present invention to provide a novel catalyst which is highly active, efficiently and industrially advantageously produced, and a method for producing an olefin polymer using the catalyst.

[0011]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to achieve the above object, and as a result, have found that the periodic table 8
Polymerization of olefins, especially ethylene, in the presence of a catalyst containing a transition metal compound of group XV, a clay, a clay mineral or an ion-exchangeable layered compound, a silane compound and an organoaluminum compound and / or an alkylating agent, and in the presence of the catalyst It has been found that the object can be achieved by doing so. The present invention has been completed based on such findings.

That is, the present invention provides an olefin polymer production catalyst and a method for producing an olefin polymer described below. (1) A catalyst for producing an olefin polymer, comprising (a) a transition metal compound of Groups 8 to 10 of the periodic table, (b) a clay, a clay mineral or an ion-exchangeable layered compound, and (c) a silane compound. . (2) A method for producing an olefin polymer, comprising homopolymerizing or copolymerizing olefins in the presence of the olefin polymerization catalyst according to (1). (3) The method for producing an olefin polymer according to (2), wherein the olefin is ethylene.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION The catalyst for producing an olefin polymer of the present invention comprises (a) a transition metal compound of Groups 8 to 10 of the periodic table, (b) a clay, a clay mineral or an ion-exchangeable layered compound, and (c) Contains a silane compound. The transition metal compound of Groups 8 to 10 of the periodic table of the component (a) is preferably a compound having a diimine compound as a ligand.

[0014]

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(Wherein R ¹ and R ⁴ are each independently an aliphatic hydrocarbon group having 1 to 20 carbon atoms or a total of 7 to 7 carbon atoms)
An aromatic group having a hydrocarbon group on the 20 ring, R ² and R ³ each independently represents a hydrogen atom or a hydrocarbon group having a carbon number of 1 to 20, R ² and R ³ are bonded to each other to form a ring X and Y each independently represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and M represents a transition metal belonging to Groups 8 to 10 of the periodic table. )).

In the above general formula (I), R ¹ and R
Examples of the aliphatic hydrocarbon group having 1 to 20 carbon atoms in ⁴ include a linear or branched alkyl group having 1 to 20 carbon atoms or a cycloalkyl group having 3 to 20 carbon atoms, such as methyl. Group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, octyl group, decyl group, tetradecyl group, hexadecyl group, octadecyl Group, cyclopentyl group, cyclohexyl group, cyclooctyl group and the like. An appropriate substitution difference such as a lower alkyl group may be introduced on the ring of the cycloalkyl group. In addition, the total carbon number is 7 to 20.
Examples of the aromatic group having a hydrocarbon group on the ring include those having 1 carbon atom on an aromatic ring such as a phenyl group or a naphthyl group.
And a group into which one or more linear, branched or cyclic alkyl groups of 10 to 10 have been introduced. This R ¹ and R
^{As 4} , an aromatic group having a hydrocarbon group on the ring is preferable, and a 2,6-diisopropylphenyl group is particularly preferable. R ¹ and R ⁴ may be the same or different.

Further, R ² and R ^{3 have} 1 to 1 carbon atoms.
Examples of the hydrocarbon group having 20 carbon atoms include a linear or branched alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and a carbon atom having 7 carbon atoms.
To 20 aralkyl groups. Here, the linear or branched alkyl group having 1 to 20 carbon atoms and the cycloalkyl group having 3 to 20 carbon atoms include the aliphatic hydrocarbon groups having 1 to 20 carbon atoms among the above R ¹ and R ^4. The same ones as exemplified in the description can be given. Examples of the aryl group having 6 to 20 carbon atoms include a phenyl group, a tolyl group, a xylyl group, a naphthyl group, and a methylnaphthyl group. Examples of the aralkyl group having 7 to 20 carbon atoms include a benzyl group and a phenethyl group. And the like. R ² and R ³ may be the same or different. Further, they may combine with each other to form a ring.

On the other hand, X and Y have 1 to 20 carbon atoms.
The hydrocarbon group of has the same meaning as described above for the hydrocarbon group having 1 to 20 carbon atoms in R ² and R ³ . X and Y are particularly preferably a methyl group. X and Y may be the same or different. Examples of transition metals of Groups 8 to 10 of the periodic table of M include nickel, palladium, platinum,
Iron, cobalt, rhodium, ruthenium and the like,
Nickel and palladium are preferred.

Examples of the complex compound represented by the general formula (I) include the following formulas [3], [4], [5],
[6], [7], [8],

[9], [10] and [1
And the like.

[0020]

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In the present invention, as the component (a), one of the above complex compounds may be used, or two or more of them may be used in combination. On the other hand, as the component (b), clay, clay mineral or ion-exchange layered compound is used. Clay is an aggregate of fine hydrated silicate minerals, and refers to a substance that produces plasticity when mixed with an appropriate amount of water, exhibits rigidity when dried, and sinters when baked at high temperatures. The clay mineral refers to a hydrated silicate that is a main component of clay. The ion-exchangeable layered compound is a compound having a crystal structure in which surfaces formed by ionic bonds and the like are stacked in parallel with a weak bonding force, and means a compound whose contained ions are exchangeable. Most clay minerals are ion-exchangeable layered compounds. These are not limited to natural products, and may be artificially synthesized. As an ion-exchange layered compound, for example, hexagonal close-packing type,
Examples thereof include an ionic crystalline compound having a layered crystal structure such as an antimony type, a cadmium chloride type, and a cadmium iodide type.

Specific examples of the component (b) include kaolin,
Bentonite, kibushi clay, gairome clay, allophane,
Hisingelite, pyrophyllite, talc, plum group,
Montmorillonite group, vermiculite, ryokudeite group, palygorskite, kaolinite, nacrite, dickite, halloysite and the like. As the component (b), a pore volume having a radius of 20 ° or more measured by a mercury intrusion method is 0.1 ml / g or more, and particularly 0.3 ml / g.
Those having a concentration of ５5 ml / g or more are preferred. It is also preferable to perform a chemical treatment from the viewpoint of removing impurities from the clay or changing the structure and function.

Here, the chemical treatment means either a surface treatment for removing impurities adhering to the surface or a treatment for affecting the crystal structure of the clay. Specifically, acid treatment, alkali treatment, salt treatment, organic matter treatment and the like can be mentioned. The acid treatment removes impurities on the surface and increases the surface area by eluting cations such as aluminum, iron and magnesium in the crystal structure. Alkali treatment destroys the crystal structure of the clay, resulting in a change in the structure of the clay. In the salt treatment and the organic substance treatment, an ion complex, a molecular complex, an organic complex, and the like are formed, and the surface area, the interlayer distance, and the like can be changed. By replacing the exchangeable ions between layers with another bulky ion by utilizing ion exchangeability, an interlayer material having an enlarged interlayer can be obtained. It is also possible to secure a polymerization reaction field where the main catalyst is present between the layers.

The above-mentioned component (b) may be used as it is, may be used by newly adding and adsorbing water, or may be used after being heated and dehydrated. Preferred as component (b) are clays or clay minerals,
Most preferred is montmorillonite. Examples of the silane compound used as the component (c) in the present invention include trimethylsilyl chloride, triethylsilyl chloride, triisopropylsilyl chloride, and t
trialkylsilyl chlorides such as tert-butyldimethylsilyl chloride, tert-butyldiphenylsilyl chloride, phenethyldimethylsilyl chloride, dimethylsilyl dichloride, diethylsilyl dichloride, diisopropylsilyl dichloride, bisdiphenethylsilyl dichloride, methylphenethylsilyl dichloride, diphenyl Dialkylsilyl dichlorides such as silyl dichloride, dimesityl silyl dichloride, ditolyl silyl dichloride, methyl silyl trichloride, ethyl silyl trichloride, isopropyl silyl trichloride, phenyl silyl trichloride, mesityl silyl trichloride, tolyl silyl trichloride , Alkylsilyl trichlorides such as phenethylsilyl trichloride, and a portion of the above chloride. Halides, bis (trimethylsilyl) amine, bis (triethylsilyl) amine, bis (triisopropylsilyl) amine, bis (dimethylethylsilyl) amine, bis (diethylmethylsilyl) amine, bis (dimethylphenyl) Silyl) amine, bis (dimethyltolylsilyl)
Amine, bis (dimethylmesitylsilyl) amine, N,
Silylamines such as N-dimethylaminotrimethylsilane, (diethylamino) trimethylsilane, N- (trimethylsilyl) imidazole, polysilanols which are referred to by common names of peralkyl polysiloxy polyols;
Silanols such as tris (trimethylsiloxy) silanol and the like, silylamides such as N, O-bis (trimethylsilyl) acetamide, bis (trimethylsilyl) trifluoroacetamide, N- (trimethylsilyl) acetamide, bis (trimethylsilyl) urea and trimethylsilyldiphenylurea; Linear siloxanes such as 1,3-dichlorotetramethyldisiloxane, cyclic siloxanes such as pentamethylcyclopentanesiloxane, tetraalkylsilanes such as dimethyldiphenylsilane, diethyldiphenylsilane, diisopropyldiphenylsilane, trimethylsilane, triethyl Silane, triisopropylsilane, tri-t-butylsilane, triphenylsilane, tolylsilane, trimesitylsilane, methyldiphenylsilane Dinaphthyl methylsilane, bis (diphenyl) trialkylsilane such as methylsilane, also silicon tetrachloride, silicon tetrabromide, inorganic silicon compounds and the like. Of these, preferred are silylamines, and more preferred are trialkylsilane chlorides. As the component (c), one type may be used from among these, but in some cases, two or more types may be used in any combination.

There are no particular restrictions on the proportion of each catalyst component used in the present invention.
(B) The proportion of the hydroxyl group in the component is usually 0.1 to 100000 mol, preferably 0.5 to 10000 mol,
(C) The silicon atom in the component is usually 0.1 to 100,000.
Mol, preferably 0.5 to 10000 mol. When the component (b) is other than clay or clay mineral, the ratio of the transition metal in the component (a) to 0.00001 to 1 g with respect to 1 g of the component (b) is satisfied. It is preferable to use the atom in a ratio of 0.001 to 100 g. If the ratio is outside the above range, the polymerization activity may decrease.

The method for preparing the polymerization catalyst is not particularly limited, and various methods can be applied. For example, (1) a method in which the component (a) is brought into contact with the component (b), and the component (c) is added thereto;
A method of contacting the component with the component and adding the component (b) to the component,
(3) A method in which the component (b) is brought into contact with the component (c) and the component (a) is added thereto, and a method (4) in which the component (a) is brought into contact with the component (b) and the component (c) simultaneously. Etc. can be used. Among these methods, the method (3) is preferable. Upon or after the contact of each component, a polymer such as polyethylene or polypropylene, or an inorganic oxide such as silica or alumina may coexist or be brought into contact.

The contact may be carried out in an inert gas such as nitrogen or in a hydrocarbon such as pentane, hexane, heptane, toluene and xylene. The addition or contact of each component can be performed at the polymerization temperature, or
It is preferably carried out at a temperature of from 30 ° C. to the boiling point of the solvent used, particularly from room temperature to the boiling point of the solvent used. According to the method for producing a polyolefin of the present invention, homopolymerization of olefins or copolymerization of olefins with other olefins and / or other monomers (that is, heterogeneous olefins) using the polymerization catalyst described above Copolymerization with olefins, copolymerization of olefins with other monomers, or copolymerization of different olefins with other monomers).

The olefin is not particularly limited, but is preferably an α-olefin having 2 to 20 carbon atoms. Examples of the α-olefin include ethylene, propylene, 1-butene, 3-methyl-1-butene, 4-methyl-1-butene, 4-phenyl-1-butene, 1-pentene, and 3-methyl-1- Pentene, 4-methyl-1-pentene, 3,3-dimethyl-1-pentene, 3,4-dimethyl-1-pentene, 4,4-dimethyl-1-pentene, 1-hexene, 4-methyl-1- Hexene, 5-methyl-1-hexene, 6-phenyl-1-hexene, 1
Α-olefins such as -octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, vinylcyclohexane,
Hexafluoropropene, tetrafluoroethylene, 2
Halogen-substituted α-olefins such as -fluoropropene, fluoroethylene, 1,1-difluoroethylene, 3-fluoropropene, trifluoroethylene, 3,4-dichloro-1-butene, cyclopentene, cyclohexene, norbornene, and 5-methylnorbornene , 5-ethylnorbornene, 5-propylnorbornene, 5,6-
Cyclic olefins such as dimethylnorbornene and 5-benzylnorbornene;
-Methylstyrene, p-ethylstyrene, p-propylstyrene, p-isopropylstyrene, p-butylstyrene, p-tert-butylstyrene, p-phenylstyrene, o-methylstyrene, o-ethylstyrene, o
-Propylstyrene, o-isopropylstyrene, m-
Methyl styrene, m-ethyl styrene, m-isopropyl styrene, m-butyl styrene, mesityl styrene,
Alkylstyrenes such as 2,4-dimethylstyrene, 2,5-dimethylstyrene and 3,5-dimethylstyrene, p-methoxystyrene, o-methoxystyrene, m
Alkoxystyrenes such as -methoxystyrene, p-chlorostyrene, m-chlorostyrene, o-chlorostyrene, p-bromostyrene, m-bromostyrene, o-bromostyrene, p-fluorostyrene, m-fluorostyrene, o Halogenated styrenes such as -fluorostyrene and o-methyl-p-fluorostyrene; and further, trimethylsilylstyrene, vinyl benzoate, divinylbenzene and the like. Further, the other olefins described above may be appropriately selected from the olefins.

In the present invention, the above olefins may be used alone or in combination of two or more. When copolymerizing two or more olefins, the above olefins can be arbitrarily combined. Also,
In the present invention, the above-mentioned olefins and other monomers may be copolymerized. Examples of the other monomers used in this case include butadiene, isoprene, 1,4-pentadiene, and 1,5-pentadiene. Chain diolefins such as hexadiene, norbornene, 1,4,5,8-dimethano-1,
Polycyclic olefins such as 2,3,4,4a, 5,8,8a-octahydronaphthalene and 2-norbornene, cyclic diolefins such as norbornadiene, 5-ethylidene norbornene, 5-vinylnorbornene and dicyclopentadiene; Examples include unsaturated esters such as ethyl acrylate and methyl methacrylate.

In the present invention, ethylene is particularly preferred as the olefin. The method for polymerizing olefins is not particularly limited, and any polymerization method such as a slurry polymerization method, a solution polymerization method, a gas phase polymerization method, a bulk polymerization method, and a suspension polymerization method can be employed. When a polymerization solvent is used, examples of the solvent include hydrocarbons such as benzene, toluene, xylene, n-hexane, n-heptane, cyclohexane, methylene chloride, chloroform, 1,2-dichloroethane, and chlorobenzene, and halogenated hydrocarbons. Hydrogens and the like. These may be used alone or in combination of two or more. Also,
The monomers used for the polymerization can also be used depending on the type.

The amount of the catalyst used in the polymerization reaction is as follows:
The component (a) is usually 2 to 100 per liter of the solvent.
It is advantageous from the viewpoints of polymerization activity and reactor efficiency to select the amount to be in the range of micromol, preferably 7 to 25 micromol. As for the polymerization conditions, the pressure is usually selected from the range of normal pressure to 2000 kg / cm ² G. The reaction temperature is usually in the range of -50 to 250C. Examples of the method for adjusting the molecular weight of the polymer include the type and amount of each catalyst component, the selection of the polymerization temperature, and the introduction of hydrogen.

[0032]

Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. Example 1 Production of Polyethylene (1) Chemical Treatment of Clay Mineral 40 g of commercially available montmorillonite (Kunimine F, manufactured by Kunimine Industries) was pulverized by a pulverizer for 4 hours. 20 g of crushed montmorillonite is placed in a 500 ml four-necked flask, dispersed in 100 ml of deionized water in which 20 g of magnesium chloride hexahydrate is dissolved, and stirred for 90 hours.
Treated at 0 ° C for 0.5 hour. After the treatment, the solid component was washed with water. This treatment operation was repeated once to obtain montmorillonite treated with magnesium chloride. After drying this,
The mixture was dispersed in 160 ml of a 6% aqueous hydrochloric acid solution and treated under reflux with stirring for 2 hours. After the treatment, washing with water and filtration are repeated until the filtrate becomes neutral, and drying is performed.
A chemically treated montmorillonite was obtained. (2) Chemical treatment with silane compound A chemically treated montmorillonite obtained in (1) (water content: 15% by weight: 150) was placed in a 300 ml Schlenk tube.
It was determined from the weight loss during heat dehydration treatment at 1 ° C. for 1 hour. 1.0 g was added thereto, and 25 ml of toluene was added thereto and dispersed to obtain a slurry. To this, 1.13 g (5.2 mmol) of methylphenethylsilyl dichloride was added, and the mixture was stirred at room temperature for 60 hours.
The mixture was heated and stirred at 0 ° C. for 1 hour. After cooling to room temperature and extracting the supernatant, the solid component was washed with 200 ml of toluene. Toluene was newly added to the obtained slurry to make the total amount 50 ml. (3) Polymerization of ethylene An autoclave having an internal volume of 1.6 liters was sufficiently dried,
After the replacement with nitrogen, 400 ml of toluene dehydrated at room temperature, 5 ml of the clay mineral solution prepared in (2) (equivalent to 0.1 g clay mineral), and 6.8 micromol of nickel complex [3] were sequentially added. At 25 ° C.
Polymerization was carried out for one hour while continuously supplying ethylene so as to maintain a pressure of 8 kg / cm ² G. Thereafter, the polymerization was stopped by adding methanol. The polymer was separated by filtration and dried at 90 ° C. under reduced pressure for 12 hours. As a result, 2
3.1 g of polymer were obtained. The polymerization activity per catalyst was 57.8 kg / g-Ni · h.

This polymer had an intrinsic viscosity [η] of 3.12 deciliters / g measured in decalin at 135 ° C., and a melting point of 132.4 determined by a differential scanning calorimeter (DSC).
° C and the density were 0.9309 g / cm ³ . [Example 2] Production of polyethylene The same procedure as in Example 1 was carried out except that the nickel complex [4] was used instead of the nickel complex [3], to obtain 29.8 g of a polymer. The polymerization activity per catalyst is 74.6 kg /
g-Ni · h.

This polymer has an intrinsic viscosity [η] of 22.5 deciliters / g measured in decalin at 135 ° C. and a melting point of 113.7 determined by a differential scanning calorimeter (DSC).
° C and the density were 0.9047 g / cm ³ . Example 3 Production of Polyethylene The procedure of Example 1 was repeated except that the nickel complex [5] was used instead of the nickel complex [3], to obtain 16.4 g of a polymer. The polymerization activity per catalyst is 41.0 kg /
g-Ni · h.

This polymer has an intrinsic viscosity [η] of 9.54 deciliter / g measured in decalin at 135 ° C. and a melting point of 123.6 determined by a differential scanning calorimeter (DSC).
° C and density were 0.9178 g / cm ³ . Comparative Example 1 A polymer 9.3 was prepared in the same manner as in Example 1 except that the treatment with the silane compound in (2) was not performed.
g (activity 23.3 kg / g-Ni · hr) was obtained.

This polymer has an intrinsic viscosity [η] of 3.12 deciliter / g measured in decalin at 135 ° C., a melting point of 132 ° C. determined by a differential scanning calorimeter (DSC), and a density of 0.9373 g / cm ^3. Met. The structures of the nickel complexes [3], [4] and [5] used in the above Examples and Comparative Examples are shown below.

[0037]

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[0038]

According to the present invention, the handling is inconvenient, the storage stability is poor, the amount of highly dangerous methylaluminoxane is not used in large amounts, and the amount of organoaluminum used in the entire polymerization system can be reduced. Since a large amount of metal does not remain in the produced polymer, there is no need for post-treatment of the polymer, and an olefin polymer can be obtained with high activity, efficiently and at low cost.

Claims (3)

[Claims] 1. An olefin polymer comprising (a) a transition metal compound of Groups 8 to 10 of the periodic table, (b) a clay, a clay mineral or an ion-exchangeable layered compound, and (c) a silane compound. Production catalyst. 2. A method for producing an olefin polymer, comprising homopolymerizing or copolymerizing an olefin in the presence of the olefin polymerization catalyst according to claim 1. 3. The method according to claim 2, wherein the olefin is ethylene.
The method for producing the olefin polymer according to the above.