JP3436273B2 - Olefin polymerization catalyst and method for producing olefin polymer - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel and useful catalyst for olefin polymerization and a method for efficiently producing an olefin polymer using the catalyst.

[0002]

Conventionally, a combination of a transition metal compound and an aluminoxane is known as a highly active soluble olefin polymerization catalyst (JP-A-58-19309, JP-A-60-217209). In addition, it has been proposed that the active species of the soluble olefin polymerization catalyst is a chaotic species [J. Am. Chem. Soc. 81, 81 (1959), J. Am. Chem. Soc. 82, 195].
3 (1960), J. Am. Chem. Soc. 107, 7219 (1985)]. Also, as an example of isolating this active species and applying it to olefin polymerization,
J. Am. Chem. Soc. 108, 7410 (1986), Tokuhyo H01-5026
36, JP-A 03-139504, and European Patent Publication 468651. Examples of the combined use of an organic aluminum compound include JP-A 03-20.
7704, International Patent Publication No. 92-1723 and the like. International Patent Publication No. 87-2370 and Japanese Patent Laid-Open No. 4-185614 are known as a method for polymerizing olefins using a catalyst composed of a specific transition metal and aluminoxane.

[0003]

However, a catalyst system comprising a combination of a transition metal compound and an aluminoxane is dangerous and expensive for trialkylaluminum, which is a raw material for synthesizing an aluminoxane.
It has a drawback that it must be used in a large amount and is not necessarily industrially suitable in terms of productivity.

In addition, in the polymerization examples described in the above-mentioned documents and publications in which active species are isolated and applied to olefin polymerization, or examples in which an organoaluminum compound is used in combination, a large amount of aluminoxane must be used. Had. Furthermore, the polymer formed by the complex having a cyclopentadienyl-based ligand used in these examples has a reaction temperature of 70 to 1 which is efficient in an industrial process.
When the polymerization was carried out at 00 ° C or higher, there was a problem that the molecular weight of the obtained polymer was small.

The present invention has been made in view of the above problems, and it has high activity when used as a catalyst for olefin polymerization, and the obtained polymer or copolymer has a large molecular weight and a uniform composition. In addition to providing a catalyst for olefin polymerization in which the amount of organoaluminum remaining is small and which can control the molecular weight distribution to be narrow, an olefin polymer having excellent properties using the catalyst is used in a large amount of an organometallic compound. It is an object of the present invention to provide a method that can be efficiently manufactured without the need.

[0006]

According to the present invention , the following
There is provided a catalyst for olefin polymerization characterized by containing compounds (A), (B) and (C) . (A) Ionic compound (C) triisobutylaluminum that reacts with a transition metal compound (B) represented by the following formula (I) to form an ionic complex.

[0007]

[Chemical 1]

[In the formula, M ¹ represents tetravalent titanium, zirconium or hafnium, R ⁵ and R ⁶ are single bonds or hydrocarbon groups having 1 to 20 carbon atoms, and R ⁵ and R ⁶ are Y. To form a crosslinked structure. R ⁷ and R ⁸ are σ
A binding ligand, a chelating ligand, or a Lewis base is shown, and these may be the same as or different from each other. e and f each represent an integer of 0 to 2 (e + f is 2). Y is a single bond, divalent carbon
Charcoal which may contain hydrocarbon groups of the numbers 1 to 6, nitrogen or sulfur
Indicates an aromatic ring having a prime number of 4 to 10 , oxygen or sulfur. However,
When R ⁵ and R ⁶ are single bonds, Y is not a single bond. ]

[0009]

Further provided is a method for producing an olefin polymer using the above-mentioned polymerization catalyst. In addition to the above, the olefin polymerization catalyst according to the present invention includes those containing the Lewis acid (D) and those supported on the carrier (E).

The present invention will be specifically described below. 1. Transition Metal Compound (A) As the transition metal compound (A) as the catalyst component (A) of the polymerization catalyst of the present invention, for example, the compound of the above formula (I) can be mentioned. Preferred examples thereof include the following, and those in which titanium is replaced with zirconium or hafnium. Further, it may be a similar transition metal compound containing a metal of Group 3 to 10 of the periodic table or a lanthanoid series.

2,2'-thiobis (6-t-butyl-4)
-Methylphenoxy) titanium dichloride, 2,2'-thiobis (6-t-butyl-4-methylphenoxy) titanium dimethoxide, 2,2'-thiobis (6-t-butyl-4-methylphenoxy) titanium diiso Propoxide,
2,2'-thiobis (6-t-butyl-4-methylphenoxy) titanium dimethyl, 2,2'-thiobis (6-t
-Butyl-4-methylphenoxy) titanium dibenzyl,
2,2'-thiobis (6-t-butyl-4-methylphenoxy) titanium chloride hydride, 2,2'-oxybis (6-t-butyl-4-methylphenoxy) titanium dichloride, 2,2'-ethylenebis (6-t-butyl-
4-methylphenoxy) titanium dichloride, 1,1'-
Bi-2,2'-naphthoxytitanium dichloride, 1,1 '
-Bi-2,2'-naphthoxytitanium diisopropoxide, 1,1'-bi-2,2'-naphthoxytitanium dimethyl, 1,1'-bi-2,2'-phenoxytitanium dichloride, 2 , 5-thiophene dimethoxytitanium dichloride, 2,6-pyridinedimethoxytitanium dichloride, catecoxytitanium dichloride, 1,8-naphthalenedioxytitanium dichloride, 1,2-ethanedioxytitanium dichloride, 1,2-propanedioxytitanium Dichloride, meso-2,3-butanedioxytitanium dichloride,
Racemic-2,3-butanedioxytitanium dichloride, meso-2,4-pentanedioxytitanium dichloride, racemic-2,4-pentanedioxytitanium dichloride,

2. Ionic Compound (B) Reacting with Transition Metal Compound (A) to Form Ionic Complex (B) As a catalyst component (B) of the catalyst for polymerization of the present invention, ionic compound reacting with transition metal compound (A) The compound (B) forming the complex of (1) is not particularly limited, but compounds of the following general formulas (II) and (III) can be preferably used. _{^{([L 1 -R 11] k}} +) p ([Z] -) q ... (II) ([L 2] k +) p ([Z] -) q ... (III) ( provided that, ^{L 2} is ^M 2, R ¹² R ¹³ M ³ , R ¹⁴ ₃ C
Or R ¹⁵ M ³ . ) [In the formulas (II) and (III),
[Z] ^- is a non-coordinating anion ^[Z 1] ^- or ^[Z 2] ^-
[Z ¹ ] ⁻ is an anion in which a plurality of groups are bound to an element, that is, [M ¹ A ¹ A ² ... ^An ] ⁻ , (where M 1
¹ represents a group 5 to 15 element, preferably a group 13 to 15 element, and A ^{1 to An} are hydrogen atoms, dialkylamino groups, oxygen-containing groups having 1 to 20 carbon atoms, and carbonization having 1 to 20 carbon atoms. It represents a hydrogen group, an organic metalloid group, a halogen atom or a halogen-substituted hydrocarbon group, and two or more may form a ring. n is an integer of [(valence of the central metal M ¹ ) +1]. ), At least one of which is
~ Shows a non-coordinating anion which is an anion in which a plurality of groups are bound to an element selected from Group 15 Also [Z ² ]
^- represents acid dissociation constant (pKa) of -10 conjugate base of the following Bronsted acid, a combination of conjugate base of a Bronsted acid and a Lewis acid or a generally conjugate base of what is defined as super acid. A Lewis base may be coordinated. ] Here, an anion in which a plurality of groups are bound to an element [Z
¹ ] ^- , that is, as a specific example of [M ¹ A ¹ A ² ... ^An ], M ¹ is B, Al, Si, P, As, Sb, preferably B, Al, A ^{1 to An.} , Dialkylamino group:
Dimethylamino group, diethylamino group, carbon number 1-20
Oxygen-containing group: methoxy group, ethoxy group, n-butoxy group, phenoxy group, 2,6-di-t-butyl-4-methylphenoxy group, hydrocarbon group having 1 to 20 carbon atoms: methyl group, ethyl group , N-propyl group, isopropyl group, n-
Butyl group, isobutyl group, n-octyl group, n-eicosyl group, phenyl group, p-tolyl group, benzyl group, 4-
t-butylphenyl group, 3,5-dimethylphenyl group,
Halogen atom: Fluorine, chlorine, bromine, iodine, carbon number 1
To 20 halogen-substituted hydrocarbon groups: p-fluorophenyl group, 3,5-difluorophenyl group, pentachlorophenyl group, 3,4,5-trifluorophenyl group, pentafluorophenyl group, 3,5-bis (tri Fluoromethyl) phenyl group, organic metalloid group: pentamethylantimony group, trimethylsilyl group, trimethylgermyl group, diphenylarsine group, dicyclohexylantimony group, diphenylboron group. Non-coordinating anion, that is, acid dissociation constant (pKa) is -10
Specific examples of the following conjugate base of Bronsted acid, a conjugate base of a combination of Bronsted acid and Lewis acid, or a conjugate base [Z ² ] ⁻ of what is generally defined as a super strong acid include trifluoromethanesulfonate anion. (CF
₃ SO ₃ ) ^- , bis (trifluoromethanesulfonyl) methyl anion, bis (trifluoromethanesulfonyl)
Benzyl anion, bis (trifluoromethanesulfonyl) amide, perchlorate anion (ClO ₄ ) ^- , trifluoroacetate anion (CF ₃ CO ₂ ) ^- , hexafluoroantimony anion (SbF ₆ ) ^- , fluorosulfonate anion (FSO _3). ) ^- , Chlorosulfonate anion (Cl
SO ₃₎ ^-, fluorosulfonic acid anion / antimony pentafluoride (FSO ₃ -SbF ₅₎ ^-, fluorosulfonic acid anion / 5- fluoride arsenic (FSO ₃ -AsF ₅₎ ^-, trifluoromethyl meth acid / 5 -Antimony fluoride (C
_{F 3 -SO 3 / SbF 5)} - can be mentioned. L ¹ is a Lewis base, R ¹¹ is a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, and R ¹² and R ¹³ are each a cyclopentadienyl group or a substituted cyclopentadienyl group (each Cp is , May be the same as or different from each other, and two or more Cp may have a crosslinked structure. R ¹⁴ represents a hydrocarbon group having 1 to 20 carbon atoms or an oxygen-containing group having 1 to 20 carbon atoms.
k is an ionic valence of [L ¹ -R ¹ ] and [L ² ] and is 1 to
3, p is an integer of 1 or more, q = p × k. M ² is
1 to 11, 11 to 13, containing a group 17 element, M
³ represents a 7 to 12 group element. R ¹⁵ represents porphines, phthalocyanines, allyl group derivatives and the like. ]

Specific examples of the Lewis base (L ¹ ) include amines: ammonia, methylamine, aniline, dimethylamine, diethylamine, N-methylaniline, diphenylamine, N, N-dimethylaniline,
Trimethylamine, triethylamine, tri-n-butylamine, methyldiphenylamine, pyridine, p-bromo-N, N-dimethylaniline, p-nitro-N, N
-Dimethylaniline, phosphines: triethylphosphine, triphenylphosphine, diphenylphosphine, ethers: dimethyl ether, diethyl ether, dioxane, tetrahydrofuran, thioethers: tetrahydrothiophene, esters: ethyl benzoate, nitriles: acetonitrile, benzonitrile,
Chain unsaturated hydrocarbons: ethylene, butadiene, 1-pentene, isoprene and their derivatives, and cyclic unsaturated hydrocarbons: benzene, toluene, xylene, cyclooctadiene, cyclooctatetraene.
Specific examples of R ¹¹ include hydrogen, methyl group, ethyl group, benzyl group and trityl group. R ¹² , R ¹³
Examples of are cyclopentadienyl group, methylcyclopentadienyl group, ethylcyclopentadienyl group,
Mention may be made of a pentamethylcyclopentadienyl group. Specific examples of R ¹⁴ include phenyl, p-tolyl, p
-Methoxyphenyl and the like can be mentioned. Specific examples of R ¹⁵ include tetraphenylporphyrin, phthalocyanine, allyl and methallyl. M ²
Specific examples of Li, Na, K, Ag, Cu, Br,
I, I _3, etc. can be mentioned. Specific examples of M ³ include Mn, Fe, Co, Ni and Zn.

Specific examples of the ionic compound (B) which reacts with the transition metal compound (A) to form an ionic complex include triethylammonium tetraphenylborate and tri (n-butyl) ammonium tetraphenylborate. Trimethylammonium tetraphenylborate, tetraethylammonium tetraphenylborate, methyl (tri-n-butyl) ammonium tetraphenylborate, benzyl (tri-n-butyl) ammonium tetraphenylborate, dimethyldiphenylammonium tetraphenylborate, triphenyltetraborate Phenyl (methyl) ammonium, trimethylanilinium tetraphenylborate, methylpyridinium tetraphenylborate, benzylpyridinium tetraphenylborate, methyl tetraphenylborate (2-sia Pyridinium), triethylammonium tetrakis (pentafluorophenyl) borate, tri (n-butyl) ammonium tetrakis (pentafluorophenyl) borate, triphenylammonium tetrakis (pentafluorophenyl) borate, tetra-n-tetrakis (pentafluorophenyl) borate Butylammonium, tetraethylammonium tetrakis (pentafluorophenyl) borate, benzyl (tri-n-butyl) ammonium tetrakis (pentafluorophenyl) borate, methyldiphenylammonium tetrakis (pentafluorophenyl) borate, trikis (pentafluorophenyl) borate tri Phenyl (methyl) ammonium, tetrakis (pentafluorophenyl) methylanilinium borate, tetrakis (penta Ruorofeniru)
Dimethylanilinium borate, trimethylanilinium tetrakis (pentafluorophenyl) borate, methylpyridinium tetrakis (pentafluorophenyl) borate,
Benzylpyridinium tetrakis (pentafluorophenyl) borate, methyl tetrakis (pentafluorophenyl) borate (2-cyanopyridinium), benzyl tetrakis (pentafluorophenyl) borate (2-cyanopyridinium), methyl tetrakis (pentafluorophenyl) borate (4 -Cyanopyridinium), trikis (pentafluorophenyl) borate triphenylphosphonium, tetrakis [bis (3,5-ditrifluoromethyl) phenyl] dimethylanilinium borate, ferrocenium tetraphenylborate, silver tetraphenylborate, trityl tetraphenylborate, Tetraphenylborate Tetraphenylporphyrin Manganese, Tetrakis (pentafluorophenyl) ferrocenium borate, Tetrakis (pentafluorophenyl) Acid (1,1′-dimethylferrocenium), tetrakis (pentafluorophenyl) decamethylferrocenium borate, silver tetrakis (pentafluorophenyl) borate, trityl tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) Lithium borate, sodium tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) tetraphenylporphyrin manganese borate,
Examples thereof include silver tetrafluoroborate, silver hexafluorophosphate, silver hexafluoroarsenate, silver perchlorate, silver trifluoroacetate, and silver trifluoromethanesulfonate.

3. Organoaluminum Compound (C) The polymerization catalyst of the present invention may contain an organoaluminum compound (C) as a catalyst component (C). As the organoaluminum compound (C) used in the present invention,
Examples thereof include those represented by the following general formula (IV), (V) or (VI). R ¹⁶ _r AlQ _3-r (IV) (R ¹⁶ is an alkyl group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms, Q is a hydrogen atom, a halogen atom, an alkoxy group having 1 to 20 carbon atoms or 6 carbon atoms. To 20 aryl groups Q
May be the same or different. r is an integer of 0-3. ) As the compound of formula (IV), specifically, trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, dimethylaluminum chloride, diethylaluminum chloride, methylaluminum dichloride, ethylaluminum dichloride, dimethylaluminum fluoride,
Diisobutyl aluminum hydride, diethyl aluminum hydride, ethyl aluminum sesquichloride and the like can be mentioned.

[0017]

[Chemical 2] (R ¹⁷ represents a hydrocarbon group such as an alkyl group, an alkenyl group, an aryl group and an arylalkyl group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms and a halogen atom, which may be the same or different. Further, s represents the degree of polymerization, and the number of repeating units is preferably 3 to 50, and more preferably 7 to 40.) A chain aluminoxane.

[0018]

[Chemical 3] (R ¹⁷ is the same as that of formula (V), s is the degree of polymerization, and the number of repeating units is preferably 3 to 50, more preferably 7 to 40.) Aluminoxane.

Among the compounds of the formulas (IV) to (VI), preferred are alkyl groups having 3 or more carbon atoms, among them, alkyl group-containing aluminum compounds or aluminoxanes having at least one branched alkyl group. Particularly preferred is triisobutylaluminum or aluminoxane having a degree of polymerization of 7 or more. When this triisobutylaluminum, an aluminoxane having a degree of polymerization of 7 or more, or a mixture thereof is used, high activity can be obtained.

As a method for producing the aluminoxane, there may be mentioned a method in which an alkylaluminum and a condensing agent such as water are brought into contact with each other, but the means therefor is not particularly limited and the reaction may be carried out according to a known method. For example, a method in which an organoaluminum compound is dissolved in an organic solvent and then brought into contact with water, a method in which an organoaluminum compound is initially added at the time of polymerization, and water is added later, water of crystallization contained in a metal salt, etc. , A method of reacting water adsorbed on an inorganic substance or an organic substance with an organoaluminum compound, a method of reacting a tetraalkyldialuminoxane with a trialkylaluminum, and further reacting with water. The aluminoxane may be insoluble in toluene.

When the component (C) is used, the amount used is usually 1 to 2,000 mol per 1 mol of the component (A),
Preferably 5 to 1,000 moles, particularly preferably 10 to
It is 500 mol. When the component (C) is used, the polymerization activity can be improved, but if it is too much, the organoaluminum compound is wasted and a large amount remains in the polymer, which is not preferable. The component (C) may be used in contact with the catalyst of the present invention. The contact may be made in advance or in the polymerization system.

4. Lewis Acid (D) The polymerization catalyst of the present invention may contain a Lewis acid (D) as a catalyst component (D). The Lewis acid (D) used in the present invention is not particularly limited, and may be an organic substance or a solid inorganic substance. A boron compound and an aluminum compound are preferably used as the organic substance, and a magnesium compound and the like are suitably used as the inorganic substance. Aluminum compounds include bis (2,6-di-t-butyl-4-methyl) aluminum methyl, [1,1′-bis (2-naphthoxy)] aluminum methyl, and magnesium compounds include magnesium chloride and diethoxy. Examples of magnesium and boron compounds include triphenylboron, tris (pentafluorophenyl) boron, tris [3,5-bis (trifluoromethyl) phenyl] boron, tris [(4-fluoromethyl)
Phenyl] boron, trimethylboron, triethylboron, tri (n-butyl) boron, tris (fluoromethyl) boron, tris (pentafluoroethyl) boron, tris (nonafluorobutyl) boron, tris (2,4,6-tri) Fluorophenyl) boron, tris (3,5, -difluorophenyl) boron, bis (pentafluorophenyl) fluoroboron, diphenylfluoroboron, bis (pentafluorophenyl) chloroboron, dimethylfluoroboron, diethylfluoroboron, di (n -Butyl) fluoroboron,
(Pentafluorophenyl) difluoroboron, phenyldifluoroboron, (pentafluorophenyl) difluoroboron, phenyldifluoroboron, (pentafluorophenyl) dichloroboron, methyldifluoroboron, ethyldifluoroboron, (n-butyl) difluoroboron. .

The mixing ratio (molar ratio) of the compound (A) and the Lewis acid (D) is 1: 0.1 to 1: 2000, preferably 1: 0.2 to 1: 1000, and particularly preferably 1: 1. ~
It is 1: 500. By using the Lewis acid (D), the polymerization activity per transition metal can be improved.

5. Carrier (E) In the polymerization catalyst of the present invention, the catalyst component (A) to
At least one component of (D) may be supported on the carrier (E). In this case, the type of carrier (E) is not particularly limited, and any of an inorganic carrier, an inorganic oxide carrier or an organic carrier can be used, but an inorganic carrier or an inorganic oxide carrier is particularly preferable. Specifically, as an inorganic carrier,
Magnesium compounds such as MgCl ₂ , MgCl (OEt), Mg (OEt) ₂ and complex salts thereof, or MgR ¹⁸ _X X ¹ _Y
The organomagnesium compound represented by
Here, R ¹⁸ is an alkyl group having 1 to 20 carbon atoms and 1 carbon atom.
˜20 alkoxy group or aryl group having 6 to 20 carbon atoms, X ¹ represents a halogen atom or alkyl group having 1 to 20 carbon atoms, x is 0 to 2 and y is 0 to 2.

As the inorganic oxide carrier, SiO ₂ , Al
₂ O ₃ , MgO, ZrO ₂ , TiO ₂ , Fe ₂ O ₃ , B
Examples include ₂ O ₃ , CaO, ZnO, BaO, ThO _2, and mixtures thereof such as silica alumina, zeolite, ferrite, and glass fiber. Among these, SiO ₂ and Al ₂ O ₃ are particularly preferable. The inorganic oxide carrier may contain a small amount of carbonate, nitrate, sulfate or the like. Examples of the organic carrier include polymers such as polystyrene, polyethylene, linear low-density polyethylene, polypropylene, substituted polystyrene and polyarylate, starch, carbon and the like.

The carrier (E) used in the present invention has the following properties.
The average particle size is usually 1
The thickness is 300 μm, preferably 10 to 200 μm, and more preferably 20 to 100 μm. When the particle size is small, fine powder in the polymer increases, and when the particle size is large, coarse particles in the polymer increase, which causes a decrease in bulk density and clogging of the hopper. The specific surface area of the carrier (E) is usually 1 to 1,000.
0 m ² / g, preferably 50 to 500 m ² / g, pore volume is usually 0.1 to 5 cm ³ / g, preferably 0.3 to 3
It is cm ³ / g. If either the specific surface area or the pore volume deviates from the above range, the catalytic activity may decrease. The specific surface area and the pore volume can be obtained, for example, from the volume of nitrogen gas adsorbed according to the BET method [“Journal of American Chemical Society (J. Am. Chem. Soc.)” 60, p. 309 (1983)]. Furthermore, it is desirable that the carrier (E) is usually used after firing at 150 to 1000 ° C, preferably 200 to 800 ° C.

The polymerization catalyst of the present invention contains the above-mentioned compounds (A) and (B) as main components, and contains at least one of the compounds (A) and (B), preferably the compounds (A) and (B). Both can be supported on the carrier (E). The method for supporting at least one of the compounds (A) and (B) on the carrier (E) is not particularly limited, but the following methods (1) to (4) can be exemplified. A method of mixing at least one of the compounds (A) and (B) with the carrier (E). A method in which the carrier (E) is treated with the organoaluminum compound (C) or the halogen-containing silicon compound and then mixed with at least one of the compounds (A) and (B) in an inert solvent. A method of reacting the carrier (E) with the compound (A) and / or (B) and the organoaluminum compound (C) or the halogen-containing silicon compound. A method in which the compound (A) or (B) is supported on the carrier (E) and then mixed with the compound (B) or (A). A method of mixing a contact reaction product of a compound (A) and a compound (B) with a carrier (E). A method in which the carrier (E) is allowed to coexist during the contact reaction between the compound (A) and the compound (B). The organoaluminum compound (C) may be added in the above reactions. The catalyst thus obtained may be used for the polymerization after the solvent is once distilled off and taken out as a solid, or may be used for the polymerization as it is.

In the present invention, the catalyst can also be produced by carrying out the loading operation of at least one of the compounds (A) and (B) on the carrier (E) in the polymerization system. At least one of the compounds (A) and (B), the carrier (E) and, if necessary, the organoaluminum compound (C) are added, and an olefin such as ethylene is added at atmospheric pressure to 20.
There is a method of adding Kg / cm ² and performing prepolymerization at −20 to 100 ° C. for 1 minute to 2 hours to generate catalyst particles.

In the present invention, the mixing ratio (weight ratio) of the compound (B) and the carrier (E) is 1: 5 to 1: 100.
It is preferably 00, particularly 1:10 to 1: 500. The mixing ratio (weight ratio) of the compound (A) and the carrier (E) is 1: 5 to 1: 10000, and particularly 1:10.
It is preferably 1: 500. If the mixing ratio of the compound (B) and the carrier (E) or the mixing ratio of the compound (A) and the carrier (E) is out of the above range, the activity may decrease. The average particle diameter of the polymerization catalyst of the present invention prepared as described above is usually 2 to 200 μm, preferably 10 to
150 μm, particularly preferably 20 to 100 μm,
The specific surface area is usually 20 to 1000 m ² / g, preferably 50 to 500 m ² / g. If the average particle size is less than 2 μm, the fine powder in the polymer may increase.
If it exceeds m, coarse particles in the polymer may increase. If the specific surface area is less than 20 m ² / g, the activity may decrease, and if it exceeds 1000 m ² / g, the bulk density of the polymer may decrease.

Further, in the catalyst of the present invention, the carrier 100
The amount of transition metal in g is usually 0.05 to 10 g, and especially 0.
It is preferably 1 to 2 g. If the amount of the transition metal is out of the range, the activity may decrease. By thus supporting the polymer on the carrier (E), a polymer having industrially advantageous high bulk density and excellent particle size distribution can be obtained.

6. Method for producing polymer According to the method for producing a polymer according to the present invention, by using the above-mentioned catalyst for polymerization of the present invention, for example, homopolymerization of olefin or ethylene or propylene with other olefin or other unsaturated Copolymerization with a compound can be suitably performed. In this case, the kind of olefin is not particularly limited, but ethylene or α-olefin having 3 to 20 carbon atoms is preferable. Specifically, ethylene, propylene, 1
-Butene, 3-methyl-1-butene, 1-pentene, 1
-Hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1
-Hexadecene, 1-octadecene, 1-eicosene, etc., styrene, p-methylstyrene, p-chlorostyrene, pt-butylstyrene, p-phenylstyrene,
Styrenes such as p-methylsilylstyrene and p-trimethylsilylmethylstyrene can be preferably used.

In the present invention, when the copolymerization of two or more kinds of olefins is carried out, the above monomers can be arbitrarily combined. For example, when propylene and ethylene or ethylene and an α-olefin having 3 to 10 carbon atoms are copolymerized, the copolymerization ratio of propylene and ethylene or ethylene and the α-olefin having 3 to 10 carbon atoms is:
Usually, the molar ratio is 99.9: 0.1-60.0: 40.0.
It is preferably 99.5: 0.5 to 75.0: 25.0.

The method for producing a polymer of the present invention is particularly suitable for the polymerization of olefins, but copolymerization with other unsaturated compounds such as butadiene, isoprene,
Chain diolefins such as 1,5-hexadiene, norbornene, 1,4,5,8-dimethano-1,2,3,3
Cyclic olefins such as 4,4a, 5,8,8a-octahydronaphthalene, cyclic diolefins such as norbornadiene and ethylidene norbornene, unsaturated esters such as ethyl acrylate and methyl methacrylate, β-propiolactone, It can also be used for copolymerization with lactones such as β-butyrolactone and γ-butyrolactone.

In the present invention, the polymerization method is not particularly limited, and any method such as slurry polymerization method, gas phase polymerization method, bulk polymerization method, solution polymerization method and suspension polymerization method may be used. The legal method and the gas phase polymerization method are particularly preferable. Regarding the polymerization conditions, the polymerization temperature is usually -100 to 250 ° C, preferably -50 to 200 ° C, more preferably 0 to 130 ° C.
Is. Further, the ratio of the catalyst to the reaction raw material is such that the raw material monomer / the above-mentioned component (A) (molar ratio) or the raw material monomer / the above-mentioned (B) component (molar ratio) is 1 to 10 ⁸ , and particularly 1
It is preferably from 00 to 10 ⁵ . Further, the polymerization time is usually 5 minutes to 10 hours, and the reaction pressure is atmospheric pressure to 100 Kg /
cm ² G, preferably atmospheric pressure to 30 Kg / cm ² G.
The method for controlling the molecular weight of the polymer includes the selection of the type and amount of each catalyst component, the polymerization temperature, and further the polymerization in the presence of hydrogen. When a polymerization solvent is used, for example, aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene, alicyclic hydrocarbons such as cyclopentane, cyclohexane and methylcyclohexane, aliphatic hydrocarbons such as pentane, hexane, heptane and octane. , Halogenated hydrocarbons such as chloroform and dichloromethane can be used. These solvents may be used alone or in combination of two or more. Also, α
-A monomer such as an olefin may be used as a solvent.
The polymerization may be performed without a solvent.

In the method for producing a polymer of the present invention, prepolymerization can be carried out using the catalyst of the present invention. The prepolymerization can be carried out by bringing the solid catalyst component into contact with, for example, a small amount of olefin, but the method is not particularly limited, and a known method can be used.
The olefin used in the prepolymerization is not limited, and examples thereof include the same ones as described above, for example, ethylene, C _{3 to} C ₂₀ α-olefins, or a mixture thereof. It is preferable to use. The prepolymerization temperature is usually -20.
-100 degreeC, Preferably it is -10-70 degreeC, More preferably, it is 0-50 degreeC. In the prepolymerization, an inert hydrocarbon, an aliphatic hydrocarbon, an aromatic hydrocarbon, a monomer or the like can be used as a solvent. Of these, aliphatic hydrocarbons are particularly preferable. Further, the prepolymerization may be carried out without a solvent. In the prepolymerization, the intrinsic viscosity [η] of the prepolymerized product (measured in decalin at 135 ° C.) is 0.2 dl / g or more, particularly 0.5 dl / g or more,
The amount of the prepolymerized product is 1 to 10,000 g, particularly 10 to 1,000 per 1 mmol of the transition metal component in the catalyst.
It is preferable to adjust the conditions so that it becomes 0 g.

[0036]

EXAMPLES The present invention will be specifically described below based on examples. Example 1 (1) Catalyst component (A): 2,2′-thiobis (6-t-
Butyl-4-methylphenoxy) titanium dichloride was synthesized according to literature: Makromol. Chem., Rapid Commun. 10, 349 (1989).

(2) Preparation of catalyst Under a nitrogen atmosphere, a Schlenk that had been sufficiently replaced with nitrogen was used.
0.082 g of 2'-thiobis (6-t-butyl-4-methylphenoxy) titanium dichloride (catalyst (1))
(0.173 mmol) was taken and purified toluene 1 was added to it.
7.3 ml was added to prepare a 0.01 M toluene solution. In a nitrogen atmosphere, a Schlenk that has been sufficiently substituted with nitrogen is used as a catalyst component (B): tetrakis (pentafluorophenyl) borate N, N-dimethylanilinium [PhNMe ₂ H].
[B (C ₆ F ₅ ) ₄ ] 0.0876 g (0.109 mm
ol), 10.9 ml of purified toluene was added thereto, and [PhNMe ₂ H] [B (C ₆ F ₅ ) ₄ ] of 0.0
A 1M toluene solution was prepared.

(3) Polymerization 360 ml of purified toluene and 40 ml of 1-octene were introduced into a 1-liter autoclave with a stirring blade, which had been sufficiently replaced with nitrogen, under a nitrogen atmosphere, and 1.0 M toluene of triisobutylaluminum (TIBA) was introduced under a nitrogen atmosphere. 1.0 ml (1.0 mmol) of the solution was added and kept at 60 ° C. After 30 minutes, 0.05 ml (0.5 μmol) of the catalyst (1) prepared in (2) was added in a nitrogen atmosphere, and then prepared in (2) under a nitrogen atmosphere [PhNMe ₂ H].
[B (C ₆ F ₅ ) ₄ ] 0.05 ml (0.5 μmo
l) added. Introduce ethylene into this while stirring,
Polymerization was carried out for 1 hour while continuously introducing ethylene so that the temperature was kept constant at 80 ° C. and 8 atm. As a result, as shown in Table 1, 0.60 g of polyethylene copolymer was obtained. Also, the intrinsic viscosity [η] of this polymer was 9.25,
The melting point (Tm, second heating) obtained from
It was ℃. The DSC measurement was performed under the following conditions. Model: Seiko Denshi Co., Ltd., DSC220 Conditions: Fast heating room temperature to 190 ° C 10 ° C / min Hold at 190 ° C for 3 minutes Fast cooling 190 ° C to room temperature 10 ° C / min Hold at room temperature for 3 minutes Second heating room temperature to 190 ℃ 10 ℃ / min

Polymerization was carried out according to Example 1 except that the catalyst species, olefins and polymerization conditions used in Examples 2 to 6 and Comparative Example 1 were those shown in Table 1. The results are shown in Table 2.

[0040]

[Table 1]

[Table 2] ───────────────────────── No. Yield Tm [η] ^* g ° C dl / g ───────────────────────── Example 1 0.60 79 9.25 Example 2 4.8 129-Example 3 4.5 129 6.25 Example 4 0.66 138 6.87 Example 5 3.5 83 83.56 Example 6 0.13 132-Comparative Example 1 65 117 2. 78 ───────────────────────── * −: Not measured

Polymerization was carried out in the same manner as in Example 1 except that the catalyst species, olefins and polymerization conditions used in Examples 7 to 14 were as shown in Table 3. The results are shown in Table 4. In addition, the catalysts (4) to (7) in Table 3 represent compounds (Formula 4 to Formula 7) represented by the following formulas (VII) to (X), respectively.

[0043]

[Chemical 4]

[0044]

[Chemical 5]

[0045]

[Chemical 6]

[0046]

[Chemical 7]

The transition metal complex is a Chemistry Express Vol.
2. Synthesized according to No. 7 P445-448 (1987).

[0048]

[Table 3]

[Table 4] ───────────────────────── No. Yield Tm [η] ^* g ° C dl / g ───────────────────────── Example 7 0.27 139-Example 80 0. 06 121 x Example 9 1.20 140-Example 10 1.20 127 3.09 Example 11 0.71 138-Example 12 0.25 120 x Example 13 0.45 138-Example 14 0. 42 118 × ───────────────────────── *-: Not measured ×: [η] Indicates a high molecular weight polymer that does not dissolve under the measurement conditions.

Polymerization was carried out according to Example 7 except that the catalyst species, olefins and polymerization conditions used in Examples 15 to 22 were as shown in Table 5. The results are shown in Table 6. The catalysts (8) to (11) in Table 5 are represented by the following formulas (XI) to (XIV), respectively.
The compounds represented by (Chemical formulas 8 to 11) are shown below.

[0051]

[Chemical 8]

[0052]

[Chemical 9]

[0053]

[Chemical 10]

[0054]

[Chemical 11]

[0055]

[Table 5]

[Table 6] ───────────────────────── No. Yield Tm [η] ^* g ° C dl / g ───────────────────────── Example 15 0.23 139-Example 160 0. 33 122-Example 17 0.32 137-Example 18 0.65 121-Example 19 0.78 138-Example 20 0.88 120-Example 21 0.52 138-Example 22 0.44 123 − ───────────────────────── * −: Not measured

Example 23 Silica (average particle size: 70 μm, specific surface area: 260 m ² / g, pore volume: 260 c) was placed in a nitrogen-substituted 200 ml flask.
c / g) baked at 300 ° C. for 4 hours 3.0 g,
Toluene solution of 1,1′-bi-2,2′-naphthoxyzirconium dichloride (0.01 mol / l) 100 m
1, triisobutylaluminum 5 mmol, and tetrakis (pentafluorophenyl) borate dimethylanilinium 2 mmol were added, the mixture was reacted for 30 minutes at room temperature with stirring, and then toluene was removed under reduced pressure to obtain a solid catalyst. In a 1 liter autoclave that was dried under heating and reduced pressure, 360 ml of toluene, 40 ml of 1-octene, and TIBA1
mmol was added and the solution was heated to 60 ° C. 2 μmol of the above solid catalyst was added in terms of zirconium, and the temperature was raised to 80 ° C. Polymerization was carried out at 80 ° C. for 1 hour while continuously introducing ethylene at 8 atm. The amount of the polymer obtained was 5.2 g, and the melting point was 124 ° C.

Example 24 360 ml of toluene, 40 ml of 1-octene and 1 mmol of tris (pentafluorophenyl) boron were placed in a 1 liter autoclave which was dried under heating and reduced pressure, and the temperature was raised to 60 ° C. Catecoxitanium dichloride (2 μmol) was added, the temperature was raised to 80 ° C., and polymerization was performed at 80 ° C. for 1 hour while continuously introducing ethylene at 8 atm. The obtained polymer was 1.1 g, and the melting point was 121 ° C.

[0059]

INDUSTRIAL APPLICABILITY According to the present invention, when used as a catalyst for olefin polymerization, the activity of the obtained polymer or copolymer is high, the composition thereof is uniform, and the organoaluminum remains. It is possible to provide a catalyst for olefin polymerization in which the amount is small and the molecular weight distribution can be controlled narrowly. Further, an olefin polymer having excellent properties using the catalyst can be efficiently produced without using a large amount of organometallic compound.

─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Nobuo Kawasaki 1280, Kamizumi, Sodegaura-shi, Chiba Idemitsu Kosan Co., Ltd. (56) References JP-A-4-185614 (JP, A) JP-A-3-290411 ( JP, A) JP 4-69394 (JP, A) JP 4-25514 (JP, A) JP 3-207704 (JP, A) JP 63-3008 (JP, A) JP Hei 5-279418 (JP, A) International publication 91/014713 (WO, A1) (58) Fields investigated (Int.Cl. ⁷ , DB name) C08F 4/60-4/70

Claims (2)

(57) [Claims] 1. An olefin polymerization catalyst comprising the following compounds (A), (B) and (C). (A) Ionic compound (C) triisobutylaluminum which forms an ionic complex by reacting with a transition metal compound (B) represented by the following formula (I) and a transition metal compound (A): [In the formula, M ¹ represents tetravalent titanium, zirconium or hafnium, and R ⁵ and R ⁶ are single bonds or have 1 to 2 carbon atoms.
In the hydrocarbon group of 0, R ⁵ and R ⁶ form a crosslinked structure via Y. R ⁷ and R ⁸ are σ-bonding ligands,
A chelating ligand or a Lewis base is shown, and these may be the same as or different from each other. e and f each represent an integer of 0 to 2 (e + f is 2). Y is a single bond, divalent carbonized carbon number 1 to 6
C4-C10 which may contain hydrogen group, nitrogen or sulfur
Indicates an aromatic ring , oxygen or sulfur. However, R ⁵ and R ⁶ are
When a single bond, Y is not a single bond. ] 2. A method for producing an olefin polymer, which comprises using the catalyst according to claim 1.