JPH09302020A - Production of olefin polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce an olefin polymer in a high catalytic activity at a good efficiency by polymerizing an olefin in the presence of a catalyst comprising a transition metal compound and a specified compound and an organometallic compound. SOLUTION: An olefin is polymerized in the presence of an organometallic compound and a catalyst comprising a transition metal compound represented by formula I [wherein M is a group 8, 9 or 10 transition metal; X<1> and X<2> are each M or P; R<1> and R<2> are each H or a hydrocarbon group; R<3> is a group represented by formula II, III, IV or V (wherein R<6> to R<16> are each H or a hydrocarbon group); (m) and (n) are each 1 or 2; R<4> and R<5> are each H, a halogen, a hydrocarbon group, OR<17> , SR<18> , N(R<19> )2 , P(R<20> )2 (wherein R<17> to R<20> are each a hydrocarbon group, an organosilyl, R<19> s or R<20> s may be combined with each other to form a ring; and R<1> , R<2> and R<6> to R<16> may be suitably combined with each other to form a ring) and a compound selected among Lewis acids or ionized ionizable compounds, organoaluminumoxy compounds and alkylboric acid derivatives.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing an olefin polymer, and more specifically, to efficiently produce a polymer by polymerizing an olefin using an ionic complex having a high catalytic activity composed of a transition metal compound. The present invention relates to a method for producing an olefin polymer that can be manufactured.

[0002]

The object of the present invention is to provide a process for producing an olefin copolymer, which can efficiently produce an olefin copolymer by using an ionic complex having a high catalytic activity and comprising a transition metal compound. Is to propose. Another object of the present invention is to propose a method for producing an olefin polymer capable of efficiently producing an olefin polymer in which fine particles are uniformly dispersed, by using an ionic complex having a high catalytic activity, which comprises a transition metal compound. That is.

[0003]

The present invention is the following method for producing an olefin polymer. (1) (I) A transition metal compound (A) represented by the following general formula (1), a Lewis acid or an ionizable ionic compound (B-1), and an organoaluminum oxy compound (B-2).
And an alkylboronic acid derivative (B-3), a catalyst comprising at least one compound (B) selected from the group consisting of, and (C) an organometallic compound to polymerize an olefin. Method for producing polymer.

Embedded image [In the formula, M represents a late transition metal, that is, a transition metal selected from Group 8, Group 9, and Group 10. X ¹ and X ² are the same or different and each represents a nitrogen atom or a phosphorus atom. R ¹ and R ² are the same or different,
Indicates a hydrogen atom or a hydrocarbon group.

Embedded image (However, R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R
¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are the same or different and each represents a hydrogen atom or a hydrocarbon group. ). m and n are 1 or 2 respectively, and are numbers satisfying the valences of X ¹ and X ² . R ⁴ and R ⁵ are the same or different and each represents a hydrogen atom, a halogen atom, a hydrocarbon group, or -O.
^{R 17, -SR 18, -N (} R 19) 2 or -P (R ²⁰⁾ ₂ (provided that shows each R ¹⁷ to R ²⁰ hydrocarbon group or an organic silyl group. In addition R ¹⁹ s or R ²⁰ together May be linked to each other to form a ring). R ⁴ and R ⁵ may be linked to form a ring. R ¹ ,
^{R 2, R 6, R 7} , R 8, R 9, R 10, R 11, R 12, R 13,
Two or more of R ¹⁴ , R ¹⁵ and R ¹⁶ may be linked to each other to form a ring. (2) Transition metal compound (A), Lewis acid or ionizable ionic compound (B-1), organoaluminum oxy compound (B-2) and alkylboronic acid derivative (B
-3) The at least one compound (B) selected from the group consisting of -3) and the organometallic compound (C) are respectively supplied to the reaction system, and the production method according to (1) above. (3) Transition metal compound (A), Lewis acid or ionized ionic compound (B-1), organoaluminum oxy compound (B-2) and alkylboronic acid derivative (B
-3) The at least one compound (B) selected from the group consisting of -3) and the organometallic compound (C) are contacted in advance and then supplied to the reaction system. Method. (4) Transition metal compound (A) represented by general formula (1)
Is a transition metal compound represented by the following general formula (1-1), and the production method according to any one of (1) to (3) above.

[Chemical 6] [In the formula, M represents a late transition metal, that is, a transition metal selected from Group 8, Group 9, and Group 10. X ¹ and X ² are the same or different and each represents a nitrogen atom or a phosphorus atom. R ¹ and R ² are the same or different,
Indicates a hydrogen atom or a hydrocarbon group. R ⁴ and R ⁵ are the same or different, and represent a hydrogen atom, a halogen atom, a hydrocarbon group, —OR ¹⁷ , —SR ¹⁸ , —N (R ¹⁹ ) ₂ or —P
(R ²⁰ ) ₂ (wherein R ^{17 to} R ²⁰ each represent a hydrocarbon group or an organic silyl group; R ^{19 and} R ²⁰ may be connected to each other to form a ring). .
R ⁴ and R ⁵ may be linked to form a ring.
R ⁶ and R ⁷ are the same or different and each represent a hydrogen atom or a hydrocarbon group. R ¹ , R ² , R ⁶ and R ⁷
And two or more of these may be mutually connected to form a ring. (5) The production method according to any one of (1) to (4) above, which further comprises using fine particles (II).

In the method for producing an olefin polymer of the present invention, a homopolymer of olefin or a copolymer of olefin can be produced. Examples of the olefin polymerized by the method of the present invention include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, and 1-hexene.
Heptene, 1-octene, 1-nonene, 1-decene, 1
-Dodecene, 1-tetradecene, 1-hexadecene, 1
-Having 2 to 20 carbon atoms such as octadecene, 1-eicosene, 3-methyl-1-butene and 4-methyl-1-pentene;
Α-olefins. These olefins can be polymerized by one kind alone, or two or more kinds can be copolymerized. The molar ratio of the monomers for copolymerization can be determined arbitrarily.

In the present invention, in addition to the olefin, other copolymerizable monomers such as butadiene, 1,4-hexadiene, 7-methyl-1,6-octadiene,
Conjugated or non-conjugated dienes such as 8-nonadiene and 1,9-decadiene; and cyclic olefins such as cyclopropene, cyclobutene, cyclopentene, norbornadiene and dicyclopentadiene can also be copolymerized. These other monomers can be used alone, or
Two or more can be used in combination. The proportion of other monomers in the total monomers is not more than 80 mol%, preferably 7%.
It is 0 mol% or less.

The transition metal compound (A) used as a catalyst component in the present invention is a transition metal compound (coordination compound) represented by the general formula (1), ie, a late transition metal.
A transition metal compound of Group 5, Group 9, or Group 10. Specific examples include nickel, palladium and platinum compounds.

In the general formula (1), M is a late transition metal, that is, a transition metal of Group 8, 9, or 10, and is preferably nickel, palladium or platinum. In the general formula (1), X ¹ and X ² are a nitrogen atom or a phosphorus atom. X ¹ and X ² may be the same or different.

In the general formula (1), R¹Or R^TwoIndicated by
Specific examples of the atom or group to be obtained include a hydrogen atom;
Methyl group, ethyl group, n-propyl group, isopropyl
Group, n-butyl group, isobutyl group, sec-butyl group,
Carbon such as tert-butyl group, pentyl group, hexyl group
Linear or branched saturated or unsaturated compound of the formulas 1 to 20
Alkyl group; phenyl group, naphthyl group and the like having 6 to 2 carbon atoms
0 aryl groups; these aryl groups may be methyl groups,
Group, n-propyl group, isopropyl group, n-butyl
Group, isobutyl group, sec-butyl group, tert-butyl
1 to 5 substituents such as phenyl, pentyl, hexyl, etc.
And substituted aryl groups. R ¹And R^TwoWhat is
They may be the same or different.

In the general formula (1), R ³ is a group represented by the above formula, and specific examples of the atoms or groups represented by R ^{6 to} R ¹⁶ are those exemplified above as R ¹ and R ² . The same thing as an atom or a group is mentioned. R ^{6 to} R ¹⁶ may be the same or different.

Further, R ¹ , R ² , R ⁶ in the general formula (1)
Two to two or more, preferably, adjacent groups of R ¹⁶ may be mutually connected to form a ring.

Specific examples of the atoms or groups represented by R ⁴ and R ⁵ in the general formula (1) include a hydrogen atom;
Halogen atoms such as chlorine, bromine, fluorine and iodine; methyl, ethyl, n-propyl, isopropyl and n-
Butyl group, isobutyl group, sec-butyl group, tert
-Having 1 to 2 carbon atoms such as butyl group, pentyl group, hexyl group, etc.
0 straight-chain or branched saturated or unsaturated alkyl groups; aryl groups having 6 to 20 carbon atoms such as phenyl group and naphthyl group; aralkyl groups having 7 to 20 carbon atoms such as benzyl group. Substituents 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, etc. May be substituted one or more times.

Examples of the groups represented by R ⁴ and R ⁵ in the general formula (1) include groups such as —OR ¹⁷ , —SR ¹⁸ , —N (R ¹⁹ ) _{2 and} —P (R ²⁰ ) ₂ . Where R ^{17 to} R ²⁰
Specific examples of the group are: methyl group, ethyl group, n
-C1-C20 linear or branched, saturated or unsaturated alkyl groups such as propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group A cycloalkyl group having 6 to 20 carbon atoms such as cyclohexyl group; an aryl group having 6 to 20 carbon atoms such as phenyl group and naphthyl group; an aralkyl group having 7 to 20 carbon atoms such as benzyl group; methylsilyl group, dimethylsilyl group And organic silyl groups such as trimethylsilyl group, ethylsilyl group, diethylsilyl group and triethylsilyl group. The aryl group and the aralkyl group include a methyl group, an ethyl group, an n-propyl group,
Isopropyl group, n-butyl group, isobutyl group, sec
One or more substituents such as -butyl group, tert-butyl group, pentyl group and hexyl group may be substituted. R ⁴
And R ⁵ may be the same or different.

The coordination compound represented by the general formula (1) is preferably the coordination compound represented by the general formula (1-1). Specific examples of the coordination compound represented by the general formula (1-1) include the following compounds. In the following formula, iPr represents an isopropyl group.

[0014]

[Chemical 7]

[0015]

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[0016]

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[0017]

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[0018]

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[0019]

[Chemical 12]

[0020]

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[0021]

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[0022]

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[0023]

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In addition to the above, specific examples of the coordination compound represented by the general formula (1-1) include coordination compounds in which palladium or nickel in the above compounds is replaced by platinum. .

Specific examples of the coordination compound represented by the general formula (1) include the following compounds.
In the following formula, iPr represents an isopropyl group.

[0026]

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[0027]

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Besides the above, specific examples of the coordination compound represented by the general formula (1) include a coordination compound in which palladium or nickel in the above compound is replaced by platinum.

Examples of the Lewis acid used as the component (B-1) in the present invention include BR ₃ (where R is a phenyl group or fluorine which may have a substituent such as fluorine, a methyl group and a trifluoromethyl group). And the like, such as trifluoroboron, triphenylboron, tris (4-fluorophenyl) boron, tris (3,5-difluorophenyl) boron,
Examples thereof include tris (4-fluoromethylphenyl) boron, tris (pentafluorophenyl) boron, tris (p-tolyl) boron, tris (o-tolyl) boron, and tris (3,5-dimethylphenyl) boron.

The ionized ionic compound (B-1) used in the present invention includes ionic compounds, borane compounds,
And carborane compounds and the like.

Examples of the ionic compound used as the component (B-1) include compounds represented by the general formula (2)

Embedded image And the compound represented by

Where R^{twenty one}Is H⁺, Carbonium cation
Ion, oxonium cation, ammonium cation,
Sulfonium cation, cycloheptyl trienyl cation
And ferrocenium cations with transition metals
Can be shown. R^{twenty two}~ R ^{twenty five}Are the same or
Different organic groups, preferably aryl groups or substituted ants.
A group.

Specific examples of the above-mentioned carbonium cations include triphenylcarbonium cations, tri (methylphenyl) carbonium cations, tri (dimethylphenyl) carbonium cations and like trisubstituted carbonium cations. Specific examples of the above-mentioned ammonium cations include trialkylammonium cations such as trimethylammonium cation, triethylammonium cation, tripropylammonium cation, tributylammonium cation, and tri (n-butyl) ammonium cation; N, N-diethylanilinium. Examples thereof include cations, N, N-dialkylanilinium cations such as N, N-2,4,6-pentamethylanilinium cation, and dialkylammonium cations such as di (isopropyl) ammonium cation and dicyclohexylammonium cation.

Specific examples of the above phosphonium cations include triarylphosphonium cations such as triphenylphosphonium cation, tri (methylphenyl) phosphonium cation and tri (dimethylphenyl) phosphonium cation. R ²¹ is preferably a carbonium cation, an ammonium cation or the like, particularly a triphenyl carbonium cation,
The N, N-diethylanilinium cation is preferred.

The ionic compound used as the component (B-1) is represented by the formula (3)

Embedded image A boron compound represented by the formula (Et represents an ethyl group) is preferable.

In addition, as the ionic compound, a trialkyl-substituted ammonium salt, N, N-dialkylanilinium salt, dialkylammonium salt, triarylphosphonium salt or the like can be used.

Specific examples of the above-mentioned trialkyl-substituted ammonium salt used as the component (B-1) include, for example, triethylammonium tetra (phenyl) boron, tripropylammonium tetra (phenyl) boron and tri (n-butyl). Ammonium tetra (phenyl) boron, trimethylammonium tetra (p-tolyl) boron, trimethylammonium tetra (o-tolyl) boron, tributylammonium tetra (pentafluorophenyl) boron, tripropylammonium tetra (o, p-dimethylphenyl) boron , Tributylammonium tetra (m, m-dimethylphenyl) boron, tributylammonium tetra (p-trifluoromethylphenyl) boron, tributylammonium tetra (3,5-ditrif) Oro-methylphenyl) boron,
Tri (n-butyl) ammonium tetra (o-tolyl)
Examples include boron.

The N, N used as the component (B-1)
-Specific examples of the dialkylanilinium salt include:
For example, N, N-dimethylanilinium tetra (phenyl) boron, N, N-diethylanilinium tetra (phenyl) boron, N, N-2,4,6-pentamethylanilinium tetra (phenyl) boron and the like can be mentioned. .

Specific examples of the dialkylammonium salt used as the component (B-1) include di (1-propyl) ammonium tetra (pentafluorophenyl) boron and dicyclohexylammonium tetra (phenyl) boron. To be

Further, as the ionic compound used as the component (B-1), triphenylcarbenium tetrakis (pentafluorophenyl) borate, N, N
-Dimethylanilinium tetrakis (pentafluorophenyl) borate, ferrocenium tetra (pentafluorophenyl) borate, triphenylcarbenium pentaphenylcyclopentadienyl complex, N, N-diethylanilinium pentaphenylcyclopentadienyl complex, Examples thereof include boron compounds represented by the following formula (4).

[Chemical 21]

Examples of the borane compound used as the component (B-1) include decaborane (14); bis [tri (n-butyl) ammonium] nonaborate, bis [tri (n-butyl) ammonium] decaborate and bis [tribo]. Tri (n-butyl) ammonium] undecaborate, bis [tri (n-butyl) ammonium] dodecaborate, bis [tri (n-butyl) ammonium] decachlorodecaborate, bis [tri (n-butyl) ammonium] Anion salts such as dodecachlorododecaborate; tri (n-butyl) ammonium bis (dodecahydride dodecaborate) cobaltate (III), bis [tri (n-butyl) ammonium] bis (dodecahydride dodecaborate) nickelate Salts of metal borane anions such as salt (III) It is below.

The carborane compound used as the component (B-1) is, for example, 4-carbanonaborane (1
4), 1,3-dicarbanonaborane (13), 6,9-
Dicarba decaborane (14), Dodeca hydride-1
-Phenyl-1,3-dicarbanonaborane, dodecahydride-1 -methyl-1,3-dicarbanonaborane,
Undeca hydride-1,3-dimethyl-1,3-dicarbano naborane, 7,8-dicarbaundecaborane (13), 2,7-dicarbaundecaborane (13),
Undeca hydride-7,8-dimethyl-7,8-dicarbaundecaborane, dodecahydride-11-methyl-2,7-dicarbaundecaborane, tri (n-butyl) ammonium 1-carbadecaborate, tri ( n
-Butyl) ammonium 1-carbaundecaborate,
Tri (n-butyl) ammonium 1-carbadodecaborate, tri (n-butyl) ammonium 1-trimethylsilyl-1-carbadecaborate, tri (n-butyl)
Ammonium bromo-1-carbadodecaborate, tri (n-butyl) ammonium 6-carbadecaborate (14), tri (n-butyl) ammonium 6-carbadecaborate (12), tri (n-butyl) ammonium 7- Carbaundecaborate (13), tri (n-butyl) ammonium 7,8-dicarbaundecaborate (12), tri (n-butyl) ammonium 2,9-dicarbaundecaborate (12), tri (n-) Butyl)
Ammonium dodecahydride-8-methyl-7,9
-Dicarbaundecaborate, tri (n-butyl) ammonium undecahydride-8-ethyl-7,9-
Dicarbaundecaborate, tri (n-butyl) ammonium undecahydride-8-butyl-7,9-dicarbaundecaborate, tri (n-butyl) ammonium undecahydride-8-allyl-7,9-dicarbaun Decaborate, tri (n-butyl) ammonium undecahydride-9-trimethylsilyl-7,
8-dicarbaundecaborate, tri (n-butyl) ammonium undecahydride-4,6-dibromo-
Salts of anions such as 7-carbaundecaborate;

Tri (n-butyl) ammonium bis (nonahydride-1,3-dicarbanonaborate) cobaltate (III), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarbaun) Decaborate) ferrate (III), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarbaundecaborate) cobaltate (III), tri (n-butyl) ammonium bis (undeca) Hydride-7,8
-Dicarbaundecaborate) nickelate (III), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarbaundecaborate) cuprate (II
I), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarbaundecaborate) aurate (III), tri (n-butyl) ammonium bis (nonahydride-7,8-dimethyl-) 7,8-Dicarbaundecaborate) ferrate (III), tri (n-butyl) ammonium bis (nonahydride-7,8-dimethyl-7,8-dicarbaundecaborate) chromate (II
I), tri (n-butyl) ammonium bis (tribromooctahydride-7,8-dicarbaundecaborate) cobaltate (III), tris [tri (n-butyl)]
Ammonium] bis (undecahydride-7-carbaundecaborate) chromate (III), bis [tri (n-butyl) ammonium] bis (undecahydride-7-carbaundecaborate) manganate (I
V), bis [tri (n-butyl) ammonium] bis (undecahydride-7-carbaundecaborate) cobaltate (III), bis [tri (n-butyl) ammonium] bis (undecahydride-7) Examples thereof include salts of metal carborane anions such as (carbaundecaborate) nickelate (IV).

The above-mentioned component (B-1) may be used alone or in combination of two or more.

The organoaluminum oxy compound (B-2) used in the present invention may be a conventionally known aluminoxane or a benzene-insoluble organoaluminum oxy compound.

Such conventionally known aluminoxane is specifically represented by the following general formula (5) or (6).

Embedded image (In the formula, R ^{26 s} are the same or different and each is a hydrocarbon group such as a methyl group, an ethyl group, a propyl group or a butyl group, preferably a methyl group or an ethyl group, particularly preferably a methyl group, and m is It is zero or a positive integer, preferably an integer of 5-40.)

Here, this aluminoxane is represented by the formula (OA
l (R ²⁷ )) and an alkyloxyaluminum unit represented by the formula (OA1 (R ²⁸ )) (wherein R ²⁷ and R ²⁸ are the same hydrocarbon groups as R ²⁶ above). Can, R ²⁷
And R ²⁸ represents different groups) may be formed from a mixed alkyloxyaluminum unit.

The conventionally known aluminoxane is produced, for example, by the following method and is usually recovered as a solution of an aromatic hydrocarbon solvent. (1) Compounds containing water of adsorption or salts containing water of crystallization such as hydrated magnesium chloride, hydrated copper sulfate, hydrated aluminum sulfate, hydrated nickel sulfate, hydrated cerous chloride A method of adding an organoaluminum compound such as trialkylaluminum to an aromatic hydrocarbon solvent in which is suspended and reacting the resulting mixture to recover a solution of the aromatic hydrocarbon solvent. (2) A method in which water (water, ice or steam) is allowed to directly act on an organic aluminum compound such as a trialkylaluminum in a medium such as benzene, toluene, ethyl ether or tetrahydrofuran to recover the compound as an aromatic hydrocarbon solvent solution.

Specific examples of the organoaluminum compound used in producing the aluminoxane solution include trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, triisobutylaluminum, sec-Butyl aluminum, tri tert-
Butyl aluminum, tripentyl aluminum, tri-hexyl aluminum, tri-octyl aluminum, tridecyl aluminum, tricyclohexyl aluminum, trialkyl aluminum such as tri-cyclooctyl aluminum; formula _{(i-C 4 H 9)} xAly (C 5 H 10) z [where x, y, and z are positive numbers, and z ≧ 2x. ] Alkenyl aluminum such as isoprenyl aluminum isoprenyl aluminum; dialkyl aluminum halides such as dimethyl aluminum chloride, diethyl aluminum chloride, diethyl aluminum bromide, diisobutyl aluminum chloride; dialkyl aluminum hydrides such as diethyl aluminum hydride and diisobutyl aluminum hydride; dimethyl Examples thereof include dialkyl aluminum alkoxides such as aluminum methoxide and diethyl aluminum ethoxide; and dialkyl aluminum aryloxides such as diethyl aluminum phenoxide. Among these, trialkylaluminum is particularly preferable. The organoaluminum compound as described above is
Used alone or in combination.

The benzene-insoluble organoaluminum oxy compound used as the component (B-2) is, for example, a method of bringing a solution of aluminoxane into contact with water or an active hydrogen-containing compound, or the organoaluminum compound as described above. It can be obtained by a method of contacting water with water.

The benzene-insoluble organoaluminum oxy compound used as the component (B-2) is analyzed by infrared spectroscopy (IR) to obtain 1220c.
Ratio (D ₁₂₆₀ / D ₁₂₂₀ ) of the absorbance (D ₁₂₂₀ ) near m ^{-1 to} the absorbance (D ₁₂₆₀ ) near ₁₂₆₀ cm ^-1.
Is 0.09 or less, preferably 0.08 or less, and particularly preferably 0.04 to 0.07.

The above-mentioned benzene-insoluble organoaluminum oxy compound (B-2) is presumed to have an alkyloxy aluminum unit represented by the following general formula (7).

Embedded image

In the formula, R ²⁹ is a hydrocarbon group having 1 to 12 carbon atoms. Specific examples of such a hydrocarbon group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and an n group.
-Butyl group, isobutyl group, pentyl group, hexyl group,
Examples thereof include an octyl group, a decyl group, a cyclohexyl group and a cyclooctyl group. Of these, a methyl group and an ethyl group are preferable, and a methyl group is particularly preferable.

The benzene-insoluble organoaluminum oxy compound (B-2) contains an oxyaluminum unit represented by the following general formula (8) in addition to the alkyloxyaluminum unit represented by the above general formula (7). You can stay.

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In the formula, R ³⁰ is a hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, a hydroxyl group, a halogen or a hydrogen atom. R ³⁰ and R ²⁹ in the general formula (7) represent groups different from each other.

When containing an oxyaluminum unit, an organoaluminum oxy having an alkyloxyaluminum unit containing an alkyloxyaluminum unit in a proportion of 30 mol% or more, preferably 50 mol% or more, particularly preferably 70 mol% or more. Compounds are desirable.

The organoaluminum oxy compound (B-2) used in the present invention may contain a small amount of an organic compound component of a metal other than aluminum. As the component (B-2) as described above, one type may be used alone, or two or more types may be used in combination.

Examples of the alkylboronic acid derivative (B-3) used in the present invention include compounds represented by the following general formula (9).

Embedded image (In the formula, R ³¹ represents a hydrocarbon group having 1 to 10 carbon atoms. R
³² are the same or different and each represents a hydrogen atom, a halogen atom, a siloxy group, a lower alkyl group-substituted siloxy group or a hydrocarbon residue having 1 to 10 carbon atoms. )

The alkylboronic acid derivative (B-3) represented by the general formula (9) has the general formula (10).

[Chemical formula 26] (In the formula, R ³¹ is the same as above.) The alkylboronic acid and the organoaluminum compound are mixed in an inert gas atmosphere in an inert solvent at a temperature of −80 ° C. to room temperature to give 1 It can be produced by reacting for from minutes to 24 hours.

Specific examples of the alkylboronic acid represented by the general formula (10) include methylboronic acid, ethylboronic acid, isopropylboronic acid, n-propylboronic acid, n-butylboronic acid, isobutylboronic acid and n-. Hexylboronic acid, cyclohexylboronic acid, phenylboronic acid, 3,5-difluoroboronic acid, pentafluorophenylboronic acid, 3,5-bis (trifluoromethyl) phenylboronic acid and the like can be mentioned. Of these, methylboronic acid, isobutylboronic acid, 3,5-difluorophenylboronic acid, and pentafluorophenylboro are preferable, and methylboronic acid is particularly preferable. These may be used alone or in combination of two or more.

The organoaluminum compound to be reacted with the alkylboronic acid is represented by the following general formula (1
Examples thereof include organoaluminum compounds represented by 1) to (13).

Embedded image (In the formula, X is a hydrogen atom or a halogen atom, R ³³ is the same or different, and each is a hydrogen atom, a halogen atom or a hydrocarbon residue having 1 to 10 carbon atoms, and p is 0 ≦ p <3. R ³² Are the same or different and represent the same as above.)

Specific examples of the organoaluminum compounds represented by the general formulas (11) to (13) include trimethylaluminum, triethylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum and tridecylaluminum. n
-Trialkylaluminum such as butylaluminum, tri-n-propylaluminum and triisoprenylaluminum; alkyl such as dimethylaluminum chloride, diethylaluminum monochloride, diisobutylaluminum monochloride, methylaluminum sesquichloride, ethylaluminum sesquichloride, ethylaluminum dichloride Aluminum halides; alkyl aluminum hydrides such as dimethyl aluminum hydride, diethyl aluminum hydride, and diisobutyl aluminum hydride; alkyl aluminum siloxides such as dimethyl aluminum (trimethylsiloxide) and diethyl aluminum (trimethylsiloxide); tetraisobutylalumoxane, tetraethylalumoxane etc Such as tetra-alkyl alumoxane and the like. Among these, trimethyl aluminum, triisobutyl aluminum, dimethyl aluminum chloride, diisobutyl aluminum chloride, diisobutyl aluminum hydride and the like are preferable, and trimethyl aluminum and triisobutyl aluminum are particularly preferable. These may be used alone or in combination of two or more.

The above-mentioned component (B-3) may be used alone or in combination of two or more kinds.

Examples of the organometallic compound (C) used in the present invention include organometallic compounds of groups 1, 2 and 13 of the periodic table of the following elements. (C-1) the general formula _{^{R a m Al (OR b)}} n H p X q ( wherein, R
^a and R ^b are hydrocarbon groups having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, and these may be the same or different from each other. X represents a halogen atom, m is 0 <m ≦ 3,
n is a number 0 ≦ n <3, p is a number 0 ≦ p <3, q is a number 0 ≦ q <3, and m + n + p + q = 3. The organoaluminum compound represented by).

(C-2) General formula M ¹ AlR ^a ₄ (wherein
M ¹ is Li, Na or K. R ^a has 1 to 1 carbon atoms
5, preferably 1-4 hydrocarbon groups. A) a complex alkylated product of a Group 1 metal and aluminum;

(C-3) General formula R ^a R ^b M ² (wherein R ^a
And R ^b are hydrocarbon groups having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, which may be the same or different from each other. M ² is Mg, Zn or Cd. ) A dialkyl compound of a Group 2 or Group 13 metal represented by

Examples of the organoaluminum compound belonging to the above (C-1) include the following compounds. In the general formula _{^{R a m Al (OR b)}} 3-m ( wherein, R ^a and R ^b are 1 to 15 carbon atoms, preferably 1 to 4 hydrocarbon groups, which are be the same or different from each other Good m
Is preferably a number of 1.5 ≦ m ≦ 3. The organoaluminum compound represented by). In the general formula R ^a _m AlX _3-m (wherein, R ^a is 1 to carbon atoms
15, preferably 1 to 4 hydrocarbon groups, X is a halogen atom, and m is preferably 0 <m <3. The organoaluminum compound represented by). In the general formula R ^a _m AlH _3-m (wherein, R ^a is 1 to carbon atoms
15, preferably 1 to 4 hydrocarbon groups, m is preferably 2 ≦ m <3. The organoaluminum compound represented by). General formula R ^a _m Al (OR ^b ) _n X _q (wherein R ^a and R ^b
Is a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, which may be the same or different from each other.
X represents a halogen atom, m is 0 <m ≦ 3, and n is 0 ≦ n
<3, q is a number 0 ≦ q <3, and m + n + q = 3
It is. The organoaluminum compound represented by).

As the organoaluminum compound belonging to (C-1), more specifically, trimethylaluminum,
Tri-n-alkylaluminum such as triethylaluminum and tri-n-butylaluminum; triisopropylaluminum, triisobutylaluminum, tris
ec-butyl aluminum, tri-tert-butyl aluminum, tri-2-methylbutyl aluminum, tri 3
-Methylbutylaluminum, tri-2-methylpentylaluminum, tri-3-methylpentylaluminum,
Tri-branched alkylaluminum such as tri-4-methylpentylaluminum, tri2-methylhexylaluminum, tri3-methylhexylaluminum, tri2-ethylhexylaluminum; tricycloalkylaluminum such as tricyclohexylaluminum; triphenylaluminum, tritolyl Triaryl aluminums such as aluminum; Dialkyl aluminum hydrides such as diisobutyl aluminum hydride; Trialkenyl aluminums such as triisoprenyl aluminum; Alkyl aluminum alkoxides such as isobutyl aluminum methoxide, isobutyl aluminum ethoxide, isobutyl aluminum isopropoxide; Diethyl aluminum ethoxy Debutyl aluminum Dialkylaluminum alkoxides such as Tokishido; ethylaluminum sesquichloride ethoxide, alkyl sesquichloride such as butyl sesquichloride butoxide alkoxide; R ^a _2.5 Al (O
R ^b ) Partially alkoxylated alkylaluminum having an average composition represented by _0.5 or the like; Dialkylaluminum halides such as diethylaluminum chloride, dibutylaluminum chloride, diethylaluminum bromide; ethylaluminum sesquichloride, butylaluminum sesquichloride, Alkyl aluminum sesquihalides such as ethylaluminum sesquibromide; Partially halogenated alkylaluminums such as ethylaluminum dichloride, propylaluminum dichloride, butylaluminium dibromide and other alkylaluminum dihalides; such as diethylaluminium hydride and dibutylaluminum hydride. Dialkyl aluminum hydride; ethyl aluminum dihydride, propyl Other partially hydrogenated alkylaluminum such as alkylaluminum dihydride such as Rumi um dihydride; ethylaluminum ethoxy chloride, butyl aluminum butoxide cycloalkyl chloride,
Partially alkoxylated and halogenated alkyl aluminums such as ethyl aluminum ethoxy bromide can be mentioned.

A compound similar to (C-1) can also be used, and examples thereof include an organoaluminum compound in which two or more aluminum compounds are bonded via a nitrogen atom. Specific examples of such a compound include (C ₂ H ₅ ) ₂ AlN (C ₂ H ₅ ) Al (C ₂ H ₅ ) _{2 and the} like.

Examples of compounds belonging to the above (C-2) include LiAl (C ₂ H ₅ ) ₄ LiAl (C ₇ H ₁₅ ) ₄ .

[0071] Besides, as the organometallic compound (C), the general formula _{(i-C 4 H 9)} x Al y (C 5 H 10) z ( wherein, x, y and z are positive numbers And z ≧ 2x), it is also possible to use isoprenylaluminum.

In addition to the above, the organometallic compound (C)
As, methyllithium, ethyllithium, propyllithium, butyllithium, methylmagnesium bromide, methylmagnesium chloride, ethylmagnesium bromide, ethylmagnesium chloride, propylmagnesium bromide, propylmagnesium chloride, butylmagnesium bromide, butylmagnesium chloride, dimethylmagnesium, It is also possible to use diethyl magnesium, dibutyl magnesium, butyl ethyl magnesium and the like. It is also possible to use a compound such that the organoaluminum compound is formed in the polymerization system, for example, a combination of aluminum halide and alkyllithium, or a combination of aluminum halide and alkylmagnesium.

As the organometallic compound (C) used in the present invention, a metal compound having a branched alkyl group is preferable, and a metal compound having an isobutyl group is particularly preferable, and a triisobutyl metal compound is particularly preferable. Aluminum is preferable as the metal, and triisobutylaluminum is most preferable.

The organometallic compound (C) used in the present invention acts as an alkylating agent, and R bonded to the transition metal (M) in the transition metal compound (A) represented by the general formula (1).
⁴ and / or R ⁵ is an atom or group other than an alkyl group,
For example, when it is a halogen atom such as chlorine and bromine; and a group such as an alkoxy group such as a methoxy group, an ethoxy group and a butoxy group, these are substituted with an alkyl group. Such an alkyl group-substituted transition metal compound (A) reacts with the component (B), particularly the component (B-1), and forms an ionic complex having high catalytic activity.

The organometallic compound (C) also acts as a scavenger and removes water and other impurities from the system to keep the reaction system clean, so that it is possible to stably exhibit high activity of the catalyst. The effect is obtained. This action is also exhibited when R ⁴ and / or R ⁵ bonded to the transition metal (M) in the transition metal compound (A) is an alkyl group. Therefore, the organometallic compound (C) is replaced by the general formula (1)
The same as above when used in combination with the transition metal compound (A) in which R ⁴ and / or R ⁵ bonded to the transition metal (M) in the transition metal compound (A) represented by The effect of is obtained.

The transition metal compound (A) used in the present invention,
Lewis acid or ionized ionic compound (B-1),
At least one compound (B) selected from the group consisting of the organoaluminum oxy compound (B-2) and the alkylboronic acid derivative (B-3), and the organometallic compound (C) are respectively supplied to the reaction system. The olefin can be polymerized, or the olefin can be polymerized by previously contacting these components and then supplying them to the reaction system.

When the components (A) to (C) are brought into contact with each other in advance, as the transition metal compound (A) represented by the general formula (1), R ⁴ bonded to the transition metal (M) and / or A transition metal compound in which R ⁵ is an atom or group other than an alkyl group is preferable, and a Lewis acid or an ionized ionic compound (B-1) is preferably used as the component (B).

Specific examples of the component (B) that can be preferably used in the case of contacting in advance include the boron compounds represented by the above general formulas (2) to (4). Among these, the boron compound represented by the general formula (3) is preferable.

By supplying the components (A) to (C) to the reaction system, the following general formula (1)
It is presumed that the ionic coordination compound represented by 4) is formed. Further, it is speculated that the ionic coordination compound represented by the following general formula (14) is also formed when the components (A) to (C) are brought into contact with each other in advance.

[0080]

Embedded image [In the formula, M, X ¹ , X ² , R ¹ , R ² , R ³ , m and n are the same as those in the general formula (1). R ³³ represents a hydrocarbon group. Y is the aforementioned Lewis acid or ionized ionic compound (B-1), organoaluminum oxy compound (B-2)
And a molecule formed from at least one compound (B) selected from the group consisting of and an alkylboronic acid derivative (B-3). ]

In the general formula (14), R ³³ is a hydrocarbon group of R ⁴ or R ^{5 in} the general formula (1), for example, an alkyl group, or an alkyl group introduced by the organometallic compound (C). Is.

In the general formula (14), Y is from (A) to
A molecule formed from the component (B) upon contact with the component (C), which is, for example, an anion forming the ionized ionic compound of the above (B-1). (15)

[Chemical 29] A boron compound represented by This formula (15)
The boron compound represented by is a molecule formed from the boron compound represented by the formula (3).

Specific examples of Y other than the above are:
Examples of the anion that forms the ionized ionic compound exemplified in (B-1) include tetrakis (pentafluorophenyl) borate and tetra (phenyl) boron.

In the ionic coordination compound represented by the general formula (14), an ether compound (ether molecule) formed from the component (B) upon contact with the components (A) to (C) is M. May be coordinated to the transition metal represented by. Such an ionic coordination compound is represented by the following general formula (16).

[0085]

Embedded image [In the formula, M, X ¹ , X ² , R ¹ , R ² , R ³ , m and n are the same as those in the general formula (1). R ³³ and Y are the same as in the general formula (14). R ³⁴ represents an ether compound (ether molecule) formed from the component (B) upon contact with the components (A) to (C). ]

Specific examples of the ether compound (ether molecule) represented by R ³⁴ in the general formula (16) include dimethyl ether, diethyl ether, dipropyl ether and dibutyl ether.

Specific examples of the ionic coordination compound represented by the general formula (16) include ionic coordination compounds represented by the following formula (17).

[Chemical 31] (In the formula, iPr represents an isopropyl group and Et represents an ethyl group.)

In order to form the ionic coordination compound represented by the general formula (14) or (16) by contacting the components (A) to (C) in advance, the components (A) to (C) are added. -120 to + 20 ° C, preferably -80 to -20 ° C in the reaction medium
The reaction can be performed for 5 minutes to 100 hours, preferably 30 minutes to 5 hours.

As the reaction medium, hexane, heptane,
Inert hydrocarbons such as octane, cyclohexane, mineral oil, benzene, toluene and xylene; halogenated hydrocarbons such as chloroform, methylene chloride, dichloroethane and chlorobenzene can be used.

In the present invention, the (meth) acrylic acid alkyl ester (D) may be allowed to coexist when the components (A) to (C) are brought into contact with each other in advance. in this case,
As the component (B), it is preferable to use a Lewis acid or an ionized ionic compound (B-1).

Examples of the (meth) acrylic acid alkyl ester (D) include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate. , 2-ethylhexyl acrylate,
Methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate and the like can be mentioned.

By pre-contacting the components (A) to (C) in the presence of the (meth) acrylic acid alkyl ester (D), an ionic coordination compound represented by the following general formula (18) is formed. Presumed to be. The (meth) acrylic acid alkyl ester (D) can coexist when the components (A) to (C) are supplied to the reaction system, and in this case also, it is represented by the following general formula (18). It is speculated that an ionic coordination compound is formed.

[0093]

Embedded image [In the formula, M, X ¹ , X ² , R ¹ , R ² , R ³ , m and n are the same as those in the general formula (1). Y is the general formula (1
Same as 4). R ³⁵ represents a residue of a hydrocarbon group. R
³⁶ and R ³⁷ represent a part of the residues of the (meth) acrylic acid alkyl ester (D). ]

In the general formula (18), R ³⁵ is a residue of a hydrocarbon group of R ⁴ or R ^{5 in} the general formula (1), for example, an alkyl group, or is introduced by the organometallic compound (C). Is the residue of an alkyl group. Specific examples of the group represented by R ³⁵ include

[Chemical 33] And so on.

In the general formula (18), R ³⁶ and R ³⁷
Is a part of the residue formed from the (meth) acrylic acid alkyl ester (D) along with the contact between the transition metal compound (A) and the (meth) acrylic acid alkyl ester (D). Specific examples of the group represented by R ³⁶ include

Embedded image And so on.

Specific examples of the group represented by R ³⁷ include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, 2
Examples thereof include an alkyl group having 1 to 20 carbon atoms such as an ethylhexyl group.

Specific examples of the ionic coordination compound represented by the general formula (18) include ionic coordination compounds represented by the following formula (19).

Embedded image (In the formula, iPr represents an isopropyl group.)

In order to form the ionic coordination compound represented by the general formula (18) by previously contacting the components (A) to (C) in the coexistence of the (meth) acrylic acid alkyl ester (D). (Meth) acrylic acid alkyl ester (D)
Components (A) to (C) in the same reaction medium as above at -120 to + 40 ° C, preferably at -80 to 0 ° C in the presence of
It can be obtained by reacting for 5 minutes to 100 hours, preferably 30 minutes to 5 hours.

The amount of the (meth) acrylic acid alkyl ester (D) used is usually such that the molar ratio [(D) / (A)] of the (meth) acrylic acid alkyl ester (D) and the component (A) is 0. It is desirable to set it to 3 to 3, preferably 0.8 to 1.1.

In the present invention, the fine particles (II) can also be used. Examples of the fine particles (II) include inorganic fine particles such as metals, metal oxides, metal carbonates, metal chlorides, metal hydroxides, metal sulfates, carbonaceous materials, and mixtures thereof, and organic fine particles. Examples of the metal include copper, aluminum, nickel, iron, tin and the like.

Examples of the above metal oxides include alumina, titania, zirconia, silica, iron oxide, silica-alumina, mica, ferrite, magnesia and calcia. Examples of the metal carbonates include calcium carbonate and barium carbonate. Examples of the carbonaceous material include carbon black such as furnace black and ketjen black, graphite, graphite and activated carbon.

Examples of the organic fine particles include polyethylene,
Polypropylene, poly 3-methyl-1-butene, poly 4
-Methyl-1-pentene, polystyrene, styrene / divinylbenzene copolymer and the like.

The fine particles (II) as described above may be used alone or in combination of two or more.

The shape of the fine particles (II) is not particularly limited, and any shape can be used. The fine particles (II) have an average particle diameter of usually 3 to 300 μm, preferably 5 to 15 μm.
Porous microparticles having a specific surface area of 0 μm and a specific surface area of ² to 800 m ² / g are preferred.

In the present invention, the transition metal compound (A),
Lewis acid or ionized ionic compound (B-1),
A compound (B) selected from the group consisting of an organoaluminum oxy compound (B-2) and an alkylboronic acid derivative (B-3), an organometallic compound (C), or fine particles (II) in addition to these components. Various methods can be adopted to polymerize an olefin by using, for example, 1) component (A), component (B) and component (C) are separately supplied to a reaction system to polymerize an olefin. 2) a method of contacting the components (A) to (C) in advance and then supplying the mixture to the reaction system to polymerize an olefin, 3) contacting the components (A) and (B), A method in which the catalysts (I) and (C) are separately supplied to the reaction system to polymerize an olefin, 4) Part or all of the components (A), (B) and (C) are contacted in advance. After this, A method of polymerizing an olefin by supplying the contacted components and the rest of the components (A) to (C) separately to the reaction system when not all are used for contact, 5) (A) -(C) After contacting part or all of the components with the olefin in advance, the components contacted in advance and the rest if not used for the contacting are separately charged into the reaction system. Method of supplying and polymerizing olefin, 6) At least one of components (A) to (C) in fine particles (II)
A method of supporting an ingredient and then supplying it to a reaction system to polymerize an olefin, 7) Any one of the above 1) to 5) in which a (meth) acrylic acid alkyl ester (D) and / or fine particles (II) are allowed to coexist. Can be adopted.

The components (A) to (C) can be brought into contact with each other as described above. Other contact is normally -10
It is preferably carried out at 0 to + 100 ° C. for 10 minutes to 3 hours.
Upon contact, components (A), (B) and (C), optionally used (meth) acrylic acid alkyl ester (D) and / or fine particles (II), and olefin can be used in the form of a solution or a slurry. . As the medium used at this time, inert hydrocarbons such as hexane, heptane, octane, cyclohexane, mineral oil, benzene, toluene, xylene; chloroform,
Examples thereof include halogenated hydrocarbons such as methylene chloride, dichloroethane and chlorobenzene.

To carry the components (A) to (C) on the fine particles (II), for example, the fine particles (II) and (A) to (C) are mixed and contacted in an inert medium. It can be performed by the method.

During the polymerization, the transition metal compound (A) is
The concentration of the transition metal atom in the transition metal compound (A) in the polymerization system is 10 ^-8 to 1 gram atom, preferably 10 ^{-7 to} 0.1 gram atom per 1 liter of the polymerization volume. To be

The Lewis acid or ionizable ionic compound (B-1) is a molar ratio of the Lewis acid or ionizable ionic compound (B-1) to the transition metal compound (A) [(B
-1) / (A)] is 0.01 to 10, preferably 0.5.
It is used in an amount such that it ranges from -5.

Organoaluminum oxy compound (B-2)
Is the molar ratio of the aluminum atom in the organoaluminum oxy compound (B-2) to the transition metal compound (A) [(B
-2) / (A)] is 10 to 10,000, preferably 20.
It is used in an amount so as to be in the range of up to 5000.

The alkylboronic acid derivative (B-3) has a molar ratio [(B-3) / (A)] of the alkylboronic acid derivative (B-3) to the transition metal compound (A) of 5 to 100.
It is used in an amount such that it is in the range of 00, preferably 10 to 5000.

The organometallic compound (C) is a molar ratio of the organometallic compound (C) and the transition metal compound (A) [(C) /
(A)] is used in an amount of 2 to 10,000, preferably 5 to 5,000.

The amount of the fine particles (II) used is 10 ^-6 to 10% by weight, preferably 10 ^{-5 to} 5% by weight of the polymer produced.

Polymerization of olefins is usually carried out by using a supported catalyst, such as a flow method, a stirring gas phase method, a slurry method in an inert hydrocarbon solvent, a solution method in an inert hydrocarbon solvent at a high temperature, a high temperature and high pressure. Any method such as a method can be adopted.

Regarding the reaction conditions for the polymerization, in the gas phase method or the slurry method, the temperature is −100 to + 100 ° C., the time is 10 minutes to 6 hours, and the pressure is atmospheric pressure to 100 kg / cm ² (gauge pressure). preferable. In the solution method, the temperature is -50 to
+ 250 ° C, time from 1 minute to 1 hour, pressure from normal pressure to 30
It is preferably 0 kg / cm ² (gauge pressure). In the high-temperature high-pressure method, the temperature is preferably +120 to + 300 ° C., the time is 5 seconds to 10 minutes, and the pressure is preferably 400 kg / cm ² (gauge pressure) or more.

As the reaction medium used for the polymerization, inert hydrocarbons such as hexane, heptane, octane, cyclohexane, mineral oil, benzene, toluene, xylene; halogenated hydrocarbons such as chloroform, methylene chloride, dichloroethane, chlorobenzene, etc. Can be given.

Further, in the present invention, improvement of polymerization activity,
For the purpose of maintaining the shape of the solid catalyst of the produced polymer, facilitating the introduction of the catalyst into the reactor, preventing the catalyst from adhering to the reactor, and improving the fluidity in the gas phase reactor, the olefin was previously prepared. A prepolymerized product can also be used.

The transition metal compound (A) used in the method of the present invention, a Lewis acid or an ionizable ionic compound (B-1), and an organoaluminum oxy compound (B-2).
When a catalyst (I) consisting of a compound (B) selected from the group consisting of and an alkylboronic acid derivative (B-3) is used in combination with an organometallic compound (C), the catalytic activity is high, so that the olefin copolymerization The coalescence can be efficiently manufactured.

In addition to the above components, fine particles (I
By polymerizing an olefin using (I), an olefin polymer in which fine particles (II) are uniformly dispersed can be obtained.

[0120]

INDUSTRIAL APPLICABILITY The process for producing an olefin polymer according to the present invention comprises a transition metal compound (A), a Lewis acid or an ionizable ionic compound (B-1), an organoaluminum oxy compound (B-2) and an alkylboronic acid derivative. (B-
Since the olefin is polymerized by using the catalyst (I) composed of the compound (B) selected from the group consisting of 3) and the organometallic compound (C), an olefin polymer can be efficiently produced. . Further, when the olefin is further polymerized using the fine particles (II), an olefin polymer in which the fine particles (II) are uniformly dispersed in the polymer can be efficiently produced.

[0121]

BEST MODE FOR CARRYING OUT THE INVENTION Next, embodiments of the present invention will be described. Example 1 250 ml of toluene was charged into a glass autoclave having an internal volume of 500 ml that had been sufficiently replaced with nitrogen, and ethylene was added to 2 ml.
It was distributed at 00 liter / h and left at 25 ° C. for 10 minutes. Then, add triisobutylaluminum to 0.25 m.
Mol was added, then 0.1 mmol of methylaluminoxane in terms of Al atom was added, and then 0.001 mmol of the transition metal compound represented by the following formula (20) was added to start polymerization. Continuously supply ethylene gas under normal pressure for 2
Polymerization was carried out at 5 ° C for 30 minutes. After the completion of the polymerization, a small amount of methanol was added to stop the polymerization. The polymer solution was added to a large excess of methanol to precipitate the polymer,
It was dried under reduced pressure for 2 hours. As a result, the polymer 2.4
g was obtained.

[0122]

Embedded image (In the formula, iPr represents an isopropyl group.)

Example 2 250 ml of toluene was charged into a glass autoclave having an internal volume of 500 ml which had been sufficiently replaced with nitrogen, and a mixed gas of ethylene and propylene was passed through the autoclave (120 li each).
ter / h, 80 liter / h) and left at 25 ° C. for 10 minutes. Then, add triisobutylaluminum to 0.25 m.
Then, 0.1 mol of methylaluminoxane in terms of Al atom and 0.001 mmol of the transition metal compound represented by the above formula (20) were added to initiate polymerization. A mixed gas of ethylene and propylene was continuously supplied, and polymerization was carried out at 25 ° C. for 30 minutes under normal pressure. After the completion of the polymerization, a small amount of methanol was added to stop the polymerization. The polymer solution was added to a large excess of methanol to precipitate the polymer, which was dried under reduced pressure at 130 ° C. for 12 hours. As a result, 1.5 g of a polymer was obtained.

Example 3 250 ml of toluene was charged into a glass autoclave having an internal volume of 500 ml that had been sufficiently replaced with nitrogen, and ethylene was added to 2 ml.
It was distributed at 00 liter / h and left at 25 ° C. for 10 minutes. Then, add triisobutylaluminum to 0.25 m.
Then, 0.001 mmol of the transition metal compound represented by the above formula (20) was added, and then 0.002 mmol of triphenylcarbenium tetrakis (pentafluorophenyl) borate was added to initiate polymerization. Ethylene gas was continuously supplied, and polymerization was carried out at 25 ° C. for 30 minutes under normal pressure. After the completion of the polymerization, a small amount of methanol was added to stop the polymerization. The polymer solution was added to a large excess of methanol to precipitate a polymer, and the polymer was dried at 80 ° C. for 12 hours under reduced pressure. As a result, 1.1 g of a polymer was obtained.

Example 4 250 ml of toluene was charged into a glass autoclave having an internal volume of 500 ml which had been sufficiently replaced with nitrogen, and a mixed gas of ethylene and propylene was passed through the autoclave (120 li each).
ter / h, 80 liter / h) and left at 25 ° C. for 10 minutes. Then, add triisobutylaluminum to 0.25 m.
Then, 0.001 mmol of the transition metal compound represented by the above formula (20) was added, and then 0.002 mmol of triphenylcarbenium tetrakis (pentafluorophenyl) borate was added to initiate polymerization. A mixed gas of ethylene and propylene was continuously supplied, and polymerization was carried out at 25 ° C. for 30 minutes under normal pressure. After the completion of the polymerization, a small amount of methanol was added to stop the polymerization. The polymer solution was added to a large excess of methanol to precipitate the polymer,
It was dried under reduced pressure at 30 ° C. for 12 hours. As a result, 0.7 g of a polymer was obtained.

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[Procedure amendment]

[Submission date] April 8, 1996

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] Claim 3

[Correction method] Change

[Correction contents]

[Procedure amendment 2]

[Document name to be amended] Statement

[Name of item to be corrected] 0003

[Correction method] Change

[Correction contents]

[0003]

The present invention is the following method for producing an olefin polymer. (1) (I) A transition metal compound (A) represented by the following general formula (1), a Lewis acid or an ionizable ionic compound (B-1), and an organoaluminum oxy compound (B-2).
And an alkylboronic acid derivative (B-3), a catalyst comprising at least one compound (B) selected from the group consisting of, and (C) an organometallic compound to polymerize an olefin. Method for producing polymer.

Embedded image [In the formula, M represents a late transition metal, that is, a transition metal selected from Group 8, Group 9, and Group 10. X ¹ and X ² are the same or different and each represents a nitrogen atom or a phosphorus atom. R ¹ and R ² are the same or different,
Indicates a hydrogen atom or a hydrocarbon group.

Embedded image (However, R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R
¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are the same or different and each represents a hydrogen atom or a hydrocarbon group. ). m and n are 1 or 2 respectively, and are numbers satisfying the valences of X ¹ and X ² . R ⁴ and R ⁵ are the same or different and each represents a hydrogen atom, a halogen atom, a hydrocarbon group, or -O.
^{R 17, -SR 18, -N (} R 19) 2 or -P (R ²⁰⁾ ₂ (provided that shows each R ¹⁷ to R ²⁰ hydrocarbon group or an organic silyl group. In addition R ¹⁹ s or R ²⁰ together May be linked to each other to form a ring). R ⁴ and R ⁵ may be linked to form a ring. R ¹ ,
^{R 2, R 6, R 7} , R 8, R 9, R 10, R 11, R 12, R 13,
Two or more of R ¹⁴ , R ¹⁵ and R ¹⁶ may be linked to each other to form a ring. (2) Transition metal compound (A), Lewis acid or ionizable ionic compound (B-1), organoaluminum oxy compound (B-2) and alkylboronic acid derivative (B
-3) The at least one compound (B) selected from the group consisting of -3) and the organometallic compound (C) are respectively supplied to the reaction system, and the production method according to (1) above. (3) Transition metal compound (A), Lewis acid or ionized ionic compound (B-1), organoaluminum oxy compound (B-2) and alkylboronic acid derivative (B
-3) at least one compound (B) selected from the group consisting of, or further an organometallic compound (C),
The production method according to (1) above, which comprises supplying the reaction system with the pre-contacted product. (4) Transition metal compound (A) represented by general formula (1)
Is a transition metal compound represented by the following general formula (1-1), and the production method according to any one of (1) to (3) above.

[Chemical 6] [In the formula, M represents a late transition metal, that is, a transition metal selected from Group 8, Group 9, and Group 10. X ¹ and X ² are the same or different and each represents a nitrogen atom or a phosphorus atom. R ¹ and R ² are the same or different,
Indicates a hydrogen atom or a hydrocarbon group. R ⁴ and R ⁵ are the same or different, and represent a hydrogen atom, a halogen atom, a hydrocarbon group, —OR ¹⁷ , —SR ¹⁸ , —N (R ¹⁹ ) ₂ or —P
(R ²⁰ ) ₂ (wherein R ^{17 to} R ²⁰ each represent a hydrocarbon group or an organic silyl group; R ^{19 and} R ²⁰ may be connected to each other to form a ring). .
R ⁴ and R ⁵ may be linked to form a ring.
R ⁶ and R ⁷ are the same or different and each represent a hydrogen atom or a hydrocarbon group. R ¹ , R ² , R ⁶ and R ⁷
And two or more of these may be mutually connected to form a ring. (5) The production method according to any one of (1) to (4) above, which further comprises using fine particles (II).

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0064

[Correction method] Change

[Correction contents]

[0064] organometallic compound used in the present invention as (C) is 1 group of the periodic table of the elements as described below, Group 2, 12
Examples thereof include organometallic compounds of Group 13 and Group 13. (C-1) the general formula _{^{R a m Al (OR b)}} n H p X q ( wherein, R
^a and R ^b are hydrocarbon groups having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, and these may be the same or different from each other. X represents a halogen atom, m is 0 <m ≦ 3,
n is a number 0 ≦ n <3, p is a number 0 ≦ p <3, q is a number 0 ≦ q <3, and m + n + p + q = 3. The organoaluminum compound represented by).

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0066

[Correction method] Change

[Correction contents]

(C-3) General formula R ^a R ^b M ² (wherein R ^a
And R ^b are hydrocarbon groups having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, which may be the same or different from each other. M ² is Mg, Zn or Cd. 2 or Group 1 Group 2 dialkyl compound of a metal represented by).

[Procedure Amendment 5]

[Document name to be amended] Statement

[Correction target item name] 0077

[Correction method] Change

[Correction contents]

(A) and (B), or further (C)
When the components are brought into contact with each other in advance, as the transition metal compound (A) represented by the general formula (1), R ⁴ and / or R ⁵ bonded to the transition metal (M) is an atom or a group other than an alkyl group. And a Lewis acid or an ionizable ionic compound (B-
Preference is given to using 1).

[Procedure correction 6]

[Document name to be amended] Statement

[Correction target item name] 0079

[Correction method] Change

[Correction contents]

By supplying the components (A) to (C) to the reaction system, the following general formula (1)
It is presumed that the ionic coordination compound represented by 4) is formed. In addition, (A) and (B), or further (C)
It is speculated that the ionic coordination compound represented by the following general formula (14) is also formed when the components are brought into contact with each other in advance.

[Procedure amendment 7]

[Document name to be amended] Statement

[Correction target item name]

[Correction method] Change

[Correction contents]

[0082] In the general formula (14), Y is (A) and
(B) or a molecule formed from the component (B) upon contact with the component (C), which is, for example, an anion forming the ionized ionic compound of the above (B-1), Specifically, equation (15)

[Chemical 29] A boron compound represented by This formula (15)
The boron compound represented by is a molecule formed from the boron compound represented by the formula (3).

[Procedure amendment 8]

[Document name to be amended] Statement

[Correction target item name]

[Correction method] Change

[Correction contents]

The ionic coordination compound represented by the general formula (14) includes an ether compound formed from the component (B) upon contact of the components (A) and (B) or the component (C). (Ether molecule) or the like may coordinate with the transition metal represented by M. Such an ionic coordination compound is represented by the following general formula (16).

[Procedure amendment 9]

[Document name to be amended] Statement

[Correction target item name] 0085

[Correction method] Change

[Correction contents]

[0085]

Embedded image [In the formula, M, X ¹ , X ² , R ¹ , R ² , R ³ , m and n are the same as those in the general formula (1). R ³³ and Y are the same as in the general formula (14). R ³⁴ is (A) and (B),
Alternatively, it further represents an ether compound (ether molecule) formed from the component (B) upon contact with the component (C). ]

[Procedure amendment 10]

[Document name to be amended] Statement

[Correction target item name] 0088

[Correction method] Change

[Correction contents]

(A) and (B), or further (C)
The components are brought into contact with each other in advance to obtain the compound represented by the general formula (14) or (16)
To form an ionic coordination compound represented by
The components (A) to (C) are added in the reaction medium from -120 to +20.
C., preferably -80 to -20.degree. C., for 5 minutes to 100 hours, preferably 30 minutes to 5 hours.

[Procedure amendment 11]

[Document name to be amended] Statement

[Correction target item name] 0090

[Correction method] Change

[Correction contents]

Further, in the present invention, there are (A) and (B)
Upon contacting further (C) a component previously Inami, or in the presence of (meth) acrylic acid alkyl ester (D). In this case, it is preferable to use a Lewis acid or an ionizable ionic compound (B-1) as the component (B).

[Procedure amendment 12]

[Document name to be amended] Statement

[Correction target item name] 0092

[Correction method] Change

[Correction contents]

(A) and (B), or further (C)
By pre-contacting the components in the presence of (meth) acrylic acid alkyl ester (D), the following general formula (18)
It is presumed that an ionic coordination compound represented by In addition, (meth) acrylic acid alkyl ester (D)
Can coexist when components (A) to (C) are respectively supplied to the reaction system, and in this case as well, it is speculated that an ionic coordination compound represented by the following general formula (18) is formed. To be done.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Tetsuo Hayashi 6-1-2 Waki, Waki-cho, Kuga-gun, Yamaguchi Mitsui Petrochemical Industry Co., Ltd.

Claims (5)

[Claims] (I) A transition metal compound (A) represented by the following general formula (1), a Lewis acid or an ionizable ionic compound (B-1),
An olefin using a catalyst consisting of an organoaluminum oxy compound (B-2) and at least one compound (B) selected from the group consisting of alkylboronic acid derivatives (B-3), and (C) an organometallic compound. A method for producing an olefin polymer, which comprises polymerizing. Embedded image [In the formula, M represents a late transition metal, that is, a transition metal selected from Group 8, Group 9, and Group 10. X ¹ and X ² are the same or different and each represents a nitrogen atom or a phosphorus atom. R ¹ and R ² are the same or different,
Indicates a hydrogen atom or a hydrocarbon group. Embedded image (However, R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R
¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are the same or different and each represents a hydrogen atom or a hydrocarbon group. ). m and n are 1 or 2 respectively, and are numbers satisfying the valences of X ¹ and X ² . R ⁴ and R ⁵ are the same or different and each represents a hydrogen atom, a halogen atom, a hydrocarbon group, or -O.
^{R 17, -SR 18, -N (} R 19) 2 or -P (R ²⁰⁾ ₂ (provided that shows each R ¹⁷ to R ²⁰ hydrocarbon group or an organic silyl group. In addition R ¹⁹ s or R ²⁰ together May be linked to each other to form a ring). R ⁴ and R ⁵ may be linked to form a ring. R ¹ ,
^{R 2, R 6, R 7} , R 8, R 9, R 10, R 11, R 12, R 13,
Two or more of R ¹⁴ , R ¹⁵ and R ¹⁶ may be linked to each other to form a ring. ] 2. A compound selected from the group consisting of a transition metal compound (A), a Lewis acid or an ionizable ionic compound (B-1), an organoaluminum oxy compound (B-2) and an alkylboronic acid derivative (B-3). The method according to claim 1, wherein the at least one compound (B) and the organometallic compound (C) are supplied to the reaction system, respectively. 3. A transition metal compound (A), a Lewis acid or an ionizable ionic compound (B-1), an organoaluminum oxy compound (B-2) and an alkylboronic acid derivative (B-3). The at least one compound (B) to be produced and the organometallic compound (C) are contacted in advance and then supplied to the reaction system.
The manufacturing method as described. 4. The method according to claim 1, wherein the transition metal compound (A) represented by the general formula (1) is a transition metal compound represented by the following general formula (1-1). The production method according to any one of the above. Embedded image [In the formula, M represents a late transition metal, that is, a transition metal selected from Group 8, Group 9, and Group 10. X ¹ and X ² are the same or different and each represents a nitrogen atom or a phosphorus atom. R ¹ and R ² are the same or different,
Indicates a hydrogen atom or a hydrocarbon group. R ⁴ and R ⁵ are the same or different, and represent a hydrogen atom, a halogen atom, a hydrocarbon group, —OR ¹⁷ , —SR ¹⁸ , —N (R ¹⁹ ) ₂ or —P
(R ²⁰ ) ₂ (wherein R ^{17 to} R ²⁰ each represent a hydrocarbon group or an organic silyl group; R ^{19 and} R ²⁰ may be connected to each other to form a ring). .
R ⁴ and R ⁵ may be linked to form a ring.
R ⁶ and R ⁷ are the same or different and each represent a hydrogen atom or a hydrocarbon group. R ¹ , R ² , R ⁶ and R ⁷
And two or more of these may be mutually connected to form a ring. ] 5. The method according to claim 1, further comprising using fine particles (II).