JPH09302021A - Production of olefin polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce an olefin polymer containing uniformly dispersed fine particles at a good efficiency by polymerizing an olefin in the presence of a transition metal compound, a specified catalyst and fine particles. SOLUTION: This polymer is obtained by using fine particles and a catalyst comprising a transition metal compound represented by formula I [wherein M is a transition metal (group 8 to 10) in the latter period; X<1> and X<2> are each N or P; R<1> and R<2> are each H or a hydrocarbon group; R<3> is formula II (wherein R<6> to R<16> are each H or a hydrocarbon group; (m) and (n) are each 1 or 2 and is a number satisfying the valence of X<1> or X<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, R<20> s, R<4> and R<5> , or R<1> R<2> and R<6> to R<1> may be suitably combined with each other to form a ring) and at least one compound selected among Lewis acids or ionized ionizable compounds, organoaluminumoxy compounds and alkylboric acid derivatives.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for producing an olefin polymer, and more specifically to a copolymer in which fine particles are uniformly dispersed by polymerizing an olefin in combination with fine particles and an ionic complex composed of a transition metal compound. The present invention relates to a method for producing an olefin polymer capable of efficiently producing a polymer.

[0002]

An object of the present invention is to propose a method for producing an olefin polymer which can efficiently produce an olefin polymer in which fine particles are uniformly dispersed.

[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) at least one compound (B) selected from the group consisting of, and (II) fine particles are used to polymerize an olefin. Manufacturing method.

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) At least one compound (B) selected from the group consisting of -3) is 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 -3) is contacted in advance and then supplied to the reaction system. (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. ]

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.

In the present invention, as the catalyst (I), a transition metal compound (A), a Lewis acid or an ionizable ionic compound (B-1), an organoaluminum oxy compound (B-) are used.
2) and at least one compound (B) selected from the group consisting of alkylboronic acid derivatives (B-3) are used, and the components (A) and (B) are used in the reaction system. It can be supplied and polymerized,
It is also possible to bring the component (A) and the component (B) into contact with each other in advance and then supply them to the reaction system for polymerization. In the latter case, (B)
It is preferable to use a Lewis acid or an ionized ionic compound (B-1) as a component.

Specific examples of the preferred component (B) to be brought into contact with the transition metal compound (A) 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.

It is speculated that the ionic coordination compound represented by the following general formula (14) is formed in the reaction system by supplying the component (A) and the component (B) to the reaction system, respectively. . Further, it is speculated that the ionic coordination compound represented by the following general formula (14) is also formed when the component (A) and the component (B) are brought into contact with each other in advance.

[0067]

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 an alkylating agent (C) described later. It is a base.

In the general formula (14), Y is a molecule formed from the component (B) upon contact between the transition metal compound (A) and the component (B). Is an anion forming an ionized ionic compound,
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).

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.

The ionic coordination compound represented by the general formula (14) includes an ether compound (ether molecule) formed from the component (B) upon contact between the transition metal compound (A) and the component (B). ) May coordinate to the transition metal represented by M. Such an ionic coordination compound is represented by the following general formula (16).

[0072]

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 between the transition metal compound (A) and the component (B). ]

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) and (B) in advance, the compound represented by the general formula (1) is used. When R ⁴ and / or R ⁵ of the coordination compound to be formed are alkyl groups, the coordination compound (A) and the component (B) are mixed in the reaction medium at −120 to + 20 ° C., preferably −80 to -20 ° C
The reaction can be performed for 5 minutes to 100 hours, preferably 30 minutes to 5 hours.

When both R ⁴ and R ⁵ of the coordination compound (A) represented by the general formula (1) are other than an alkyl group,
For example, in the case of a hydrogen atom, a halogen atom, an alkoxyl group, etc., methyllithium, ethyllithium, propyllithium, butyllithium, methylmagnesium bromide,
Methyl magnesium chloride, ethyl magnesium bromide, ethyl magnesium chloride, propyl magnesium bromide, propyl magnesium chloride, butyl magnesium bromide, butyl magnesium chloride,
In the presence of an alkylating agent (C) such as dimethylmagnesium, diethylmagnesium, dibutylmagnesium, butylethylmagnesium, trimethylaluminum, triethylaluminum, tributylaluminum, trioctylaluminum, etc., a coordination compound (A) and a component (B) Can be obtained by reacting under the same conditions as described above. In this case, the alkyl group of the alkylating agent (C) serves as the R ³³ group of the general formula (14) or (16). When one of R ⁴ and R ⁵ of the coordination compound (A) represented by the general formula (1) is an alkyl group and the other is other than an alkyl group, the alkylating agent (C) does not necessarily mean It is not necessary, but can be used.

The amount of the alkylating agent (C) used is the molar ratio of the alkylating agent (C) and the component (A) [(C) / (A)].
Is usually 1 to 50, preferably 1 to 20.

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 transition metal compound (A)
And a Lewis acid or an ionizable ionic compound (B-
1), in contacting with at least one compound (B) selected from the group consisting of the organoaluminum oxy compound (B-2) and the alkylboronic acid derivative (B-3) in advance, (meth) acrylic acid alkyl ester (D)
Can coexist. In this case, as the component (B), a Lewis acid or an ionized ionic compound (B-
Preference is given to using 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 previously contacting the component (A) and the component (B) in the presence of the (meth) acrylic acid alkyl ester (D), an ionic coordination compound represented by the following general formula (18) is obtained. It is presumed that it will be formed. (Meta)
The acrylic acid alkyl ester (D) can be made to coexist when the component (A) and the component (B) are respectively supplied to the reaction system, and in this case also, the ionic property represented by the following general formula (18) is used. It is speculated that a coordination compound is formed.

[0082]

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 alkylating agent (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.)

The transition metal compound (A) and the component (B) are brought into contact with each other in the presence of the (meth) acrylic acid alkyl ester (D) to form an ionic coordination compound represented by the general formula (18). When R ⁴ and / or R ⁵ of the coordination compound represented by the general formula (1) is an alkyl group, the coordination compound (A) and the component (B) and the alkyl (meth) acrylate can be used. The ester (D) and -120 to + 40 ° C, preferably -80 to 0 ° C in the same reaction medium as described above.
The reaction can be performed 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.

When both R ⁴ and R ⁵ of the coordination compound (A) represented by the general formula (1) are other than an alkyl group,
For example, in the case of a hydrogen atom, a halogen atom, an alkoxyl group, etc., the coordination compound (A) and (B) component and the (meth) acrylic acid alkyl ester (D ) Can be obtained by reacting with) under the same conditions as above. In this case, the residue of the alkyl group of the alkylating agent (C) is R ^{35 of the} general formula (18).
It becomes the basis of. When one of R ⁴ and R ⁵ of the coordination compound (A) represented by the general formula (1) is an alkyl group and the other is other than an alkyl group, the alkylating agent (C) does not necessarily mean It is not necessary, but can be used.

The fine particles (II) used in the present invention include inorganic fine particles such as metals, metal oxides, metal carbonates, metal chlorides, metal hydroxides, metal sulfates, carbonaceous materials and mixtures thereof, and organic particles. Examples include 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 organometallic compound (E) may be used in combination, if necessary. Examples of the organometallic compound (E) include organometallic compounds of groups 1, 2, and 13 of the periodic table of the following elements. (E-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).

(E-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;

(E-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 (E-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).

More specifically, the organoaluminum compound belonging to (E-1) is 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 (E-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 (E-2) include LiAl (C ₂ H ₅ ) ₄ LiAl (C ₇ H ₁₅ ) _{4 and the} like.

[0102] Besides, as the organic metal compound (E), 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 (E)
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 (E) used in the present invention, a metal compound having a branched chain 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 (E) is a molar ratio of the organometallic compound (E) and the transition metal compound (A) [(E) /
(A)] is used in an amount of 2 to 10,000, preferably 5 to 5,000.

When the alkylating agent (C) for the transition metal compound (A) is used in the present invention, the alkylating agent (C)
Is used as part or all of the organometallic compound (E). Usually, since the amount used as the organometallic compound (E) is larger than the amount used as the alkylating agent (C), the amount used as the alkylating agent (C) is supplemented to use the organometallic compound (E). It becomes the amount.

The organometallic compound (E) also acts as a scavenger and removes water and other impurities from the system to keep the reaction system in dispute, so that the high activity of the catalyst can be stably expressed. .

In the present invention, the catalyst (I) comprising the transition metal compound (A) and the component (B), and the fine particles (II).
Although various methods can be adopted to polymerize olefins using, for example, 1) component (A), component (B) and fine particles (II) are separately supplied to the reaction system to polymerize olefins. 2) The components (A) and (B) are brought into contact with each other in advance, and then the catalyst (I) and the fine particles (II) which have been brought into contact with each other are separately supplied to the reaction system to polymerize the olefin. Method 3) Part or all of the component (A) and part or all of the component (B) are contacted with each other in advance, and then the catalyst (I), component (A) and / or ( A method in which the remaining portion of the component B) that has not been used for contact and fine particles (II) are separately supplied to the reaction system to polymerize the olefin, 4) A part of the component (A) and / or the component (B) Or all and a part of fine particles (II) or After the pre-contact with the parts, the pre-contacted components and, if not all of the pre-contacted components, are fed separately to the reaction system to polymerize the olefin, 5) (A ), The component (B) and a part or all of the fine particles (II) and the olefin are contacted with each other in advance,
This pre-contacted component, and a method in which when the whole is not used for the contact, the rest is separately fed to the reaction system to polymerize the olefin, 6) The fine particles (II) and the component (A) and / or Alternatively, a method of carrying the component (B) and then supplying it to the reaction system to polymerize the olefin, 7) of the alkylating agent (C), the organometallic compound (E) and the (meth) acrylic acid alkyl ester (D) The method of any one of the above 1) to 6) in which any one or all of them coexist can be adopted.

The contact between the component (A) and the component (B) can be carried out as described above. Other contact is preferably carried out usually at -100 to + 100 ° C for 10 minutes to 3 hours. Upon contact, the component (A), the component (B), the fine particles (II), the alkylating agent (C) and / or the (meth) acrylic acid alkyl ester (D) optionally used, and the olefin are in a solution or slurry form. Can be used. As the medium used at this time,
Inert hydrocarbons such as hexane, heptane, octane, cyclohexane, mineral oil, benzene, toluene, xylene; halogenated hydrocarbons such as chloroform, methylene chloride, dichloroethane, chlorobenzene and the like.

To carry the component (A) and / or the component (B) on the fine particles (II), for example, the fine particles (II) and the component (A) and / or the component (B) are mixed in an inert medium. It can be carried out by a method such as preparation by contacting.

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) and 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 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 a flow method using a supported catalyst, a stirred 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 / 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.

Thus, by polymerizing the olefin in the presence of the fine particles (II), an olefin polymer in which the fine particles (II) are uniformly dispersed can be obtained.

[0121]

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 fine particles (II), the fine particles (II) are uniformly dispersed in the polymer. The olefin polymer can be efficiently produced.

[0122]

BEST MODE FOR CARRYING OUT THE INVENTION Next, embodiments of the present invention will be described. Example 1 Silica 5 was prepared by charging 250 ml of toluene into a glass autoclave having an internal volume of 500 ml which had been sufficiently replaced with nitrogen, and then calcined at 700 ° C. in a glow box under a nitrogen atmosphere.
mg was charged. Next, add ethylene at 200 liter / h
And then left at 25 ° C. for 10 minutes. After that, methyl aluminoxane was converted into 1.25 mmo in terms of Al atom.
1, and subsequently 0.0025 mmol of a transition metal compound represented by the following formula (20) was added to initiate polymerization. Ethylene gas was continuously supplied, and polymerization was carried out at 25 ° C. for 15 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, 3.2 g of a polymer was obtained. Using the obtained polymer, the haze of a 0.5 mm-thick press sheet molded at 200 ° C. according to ASTM D1003 was measured, and the result was 10%.

[0123]

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

Example 2 To a glass autoclave having an internal volume of 500 ml which had been sufficiently replaced with nitrogen, 250 ml of toluene was charged, and then silica 5 calcined at 700 ° C. in a glow box under a nitrogen atmosphere was used.
mg was charged. Next, add ethylene at 200 liter / h
And then left at 25 ° C. for 10 minutes. Thereafter, 0.05 mmol of triisobutylaluminum was added, then 0.0025 mmol of the same transition metal compound as that used in Example 1 was added, and subsequently 0.005 mmol of triphenylcarbenium tetrakis (pentafluorophenyl) borate. Was added to initiate polymerization. Continuously supply ethylene gas at 25 ℃ under normal pressure
Polymerization was carried out for 15 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 a polymer, and the polymer was dried at 80 ° C. for 12 hours under reduced pressure. As a result, 1.5 g of a polymer was obtained.

─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] June 6, 1997

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0095

[Correction method] Change

[Correction contents]

In the present invention, the organometallic compound (E) may be used in combination, if necessary. Examples of the organometallic compound (E) include organometallic compounds of groups 1, 2, 12, and 13 of the periodic table of the following elements. (E-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 2]

[Document name to be amended] Statement

[Correction target item name] 0097

[Correction method] Change

[Correction contents]

(E-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).

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

Claims (4)

[Claims] (I) A transition metal compound (A) represented by the following general formula (1), a Lewis acid or an ionizable ionic compound (B-1),
Polymerization of olefins using a catalyst composed 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 (II) fine particles. A method for producing an olefin polymer, comprising: 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). At least 1 sort (s) of compound (B) which are provided are each supplied to a reaction system, The manufacturing method of Claim 1 characterized by the above-mentioned. 3. 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 for producing according to claim 1, wherein the at least one compound (B) to be prepared is contacted in advance and then supplied to the reaction system. 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. ]