JP2003048911A - Method for producing olefinic polymer and catalyst for polymerizing olefin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To efficiently produce an olefinic polymer having a molecular weight distribution with a slight distribution of low-molecular weight regions and high- molecular weight regions and having an optional molecular weight by an inexpensive and highly active catalyst readily modifying the molecular weight without lowering the activity. SOLUTION: This catalyst for polymerizing an olefin comprises (A) a transition metal complex compound represented by the general formula (I), (B) an ionic compound reactive with the transition metal complex compound or its derivative and forming an ionic complex and/or a Lewis acid and (C) an organoaluminum compound. A method for producing the olefin polymer comprises using the catalyst.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing an olefin polymer and an olefin polymerization catalyst. More specifically, the present invention uses a transition metal complex compound having a unique constrained geometrical shape as one of the catalyst components, and uses an olefin homopolymer or two or more olefin homopolymers having previously unknown properties. The present invention relates to a method for efficiently producing a copolymer of olefin, and a catalyst for olefin polymerization.

[0002]

2. Description of the Related Art Conventionally, as a method for producing an olefin polymer, it has been known to use a transition metal complex compound having a unique and constrained geometrical shape as a catalyst component. For example, JP-A-3-163088 discloses a method for producing an olefin-based polymer by using a catalyst system in which a titanium-based transition metal compound as a main catalyst is combined with a methylaluminoxane as a co-catalyst. However, in this method, unless expensive methylaluminoxane is used in a large amount so that the aluminum / titanium atomic ratio becomes 20 to 1000, sufficient catalytic activity cannot be obtained, and the catalyst cost is unavoidably high. There was a flaw. Further, in JP-A-3-139504, for example, (t-butylamido) dimethyl (tetramethyl-η
⁵ -cyclopentadienyl) silane titanium dimethyl "M
There is disclosed a method for producing an olefin-based polymer by using a catalyst system which is a combination of "-[alkyl] complex" and an ionic complex. However, the "M- [alkyl] complex" is generally prepared from a halo-substituted compound such as (t-butylamido) dimethyl (tetramethyl- [eta] ⁵ -cyclopentadienyl) silane titanium dichloride, although the manufacturing process is Since it is complicated and the reaction yield is low, the production cost is high, and it is not practical, and there are drawbacks such as insufficient activity. Further, International Publication WO94 / 07927 (published on April 14, 1994)
Describes using a catalyst system containing a cyclopentadienyl-containing metal compound of Group 4 of the periodic table, an anion of Bronsted acid, and an organic compound of Group 13 element to increase productivity in olefin polymerization. ing.

[0003]

Under the circumstances described above, the present invention provides an inexpensive and highly active compound containing a transition metal complex compound having a unique constrained geometrical shape as one of the catalyst components. For the purpose of providing a method for efficiently producing a homopolymer of an olefin or a copolymer of two or more kinds of olefins having a conventionally unknown property using a catalyst system, and a catalyst for the olefin polymerization. It was made.

[0004]

Means for Solving the Problems As a result of intensive studies for achieving the above-mentioned object, the present inventors have found that a transition metal complex compound having a specific structure and a transition metal complex compound or Using at least one selected from an ionic compound and a Lewis acid that react with a derivative thereof to form an ionic complex, and an organoaluminum compound,
By polymerizing one or more olefinic monomers, it is possible to control the molecular weight of the polymer while controlling the decrease in activity and increase in the molecular weight distribution of the polymer, which were not possible with the conventional technology. In addition, it was found that an olefin polymer having a low molecular weight distribution and a low molecular weight distribution with a small distribution and having an arbitrary molecular weight can be efficiently obtained. The present invention has been completed based on such findings.

That is, the present invention uses, as a catalyst component,
(A) General formula (I)

[Chemical 3] (In the formula, M is a metal element of Groups 3 to 10 of the periodic table or a lanthanoid series metal element, L is a π-bonding ligand, and A is a thirteenth, fourteenth, or fifteenth periodic table. A divalent group containing an element selected from the elements of group 16 and B represents a bonding group containing an element selected from the elements of groups 14, 15 and 16 of the periodic table, A and B may optionally combine to form a ring, X represents a σ-bonding ligand, chelating ligand or Lewis base, and n is M
Is an integer of 0 to 6 that varies depending on the valence, and when n is 2 or more, a plurality of X may be the same or different. ) A transition metal complex compound represented by the formula (B) and the compound (A)
At least one olefin-based monomer using at least one selected from an ionic compound and a Lewis acid that react with a transition metal complex compound or a derivative thereof to form an ionic complex, and (C) an organoaluminum compound The present invention provides a method for producing an olefin polymer, characterized by polymerizing the above, and an olefin polymerization catalyst comprising the catalyst component (A), the catalyst component (B) and the catalyst component (C).

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION In the method of the present invention, (A)
As the catalyst component, the general formula (I)

[Chemical 4] The transition metal complex compound represented by is used. In the above general formula (I), M represents a metal element of Groups 3 to 10 or a lanthanoid series metal element of the periodic table. L represents a π-bonding ligand, and specific examples thereof include an allyl group, a cyclopentadienyl group, a substituted cyclopentadienyl group, a cyclopentadienyl group, a cyclopentadienyl group containing a hetero atom in the ring, and Examples thereof include the substituted cyclopentadienyl group. A is the 13th and 1st of the periodic table
B represents a divalent group containing an element selected from elements of Groups 4, 15 and 16, and B is the 14th, 15th and 16th of the periodic table.
A bondable group containing an element selected from Group elements is shown.
Further, the A and B may optionally be combined with each other to form a ring.

Further, X represents a σ-bonding ligand, a chelating ligand or a Lewis base, and specific examples thereof include a hydrogen atom, a halogen atom, an organic metalloid group, an alkoxy group,
Examples thereof include an amino group, a hydrocarbon group, a hetero atom-containing hydrocarbon group, an amide group and a carboxyl group. In the present invention, a pKa value when HX is used as X is 23 or less, and particularly, a value in the range of 12 to -10 is preferably used. If the pKa value exceeds 23, the manufacturing process becomes complicated and the manufacturing cost increases. Preferable X is specifically a halogen atom such as chlorine atom, bromine atom, carboxyl group, sulfonyl group, thioalkoxy group, thioaryloxy group, acetylacetonate group, acetylacetate group, malonate group, etc. In particular, a halogen atom is preferably used because the manufacturing cost is low (for the pKa value, "ADVANCED
ORGANIC CHEMISTRY: REACTIONS, MECHANISMS, AND STR
UCTURE ・ SECOND EDITION, Jerry March, INTERNATIO
NAL STUDENT EDITION ") n is an integer of 0 to 6 that varies depending on the valence of M, and is preferably 0 to 4 for reasons such as low manufacturing cost. When n is 2 or more, plural Xs may be the same or different.

In the present invention, it is used as the component (A).
Of the transition metal complex compound represented by the above general formula (I)
A good example is (t-butylamido) dimethyl (the
Tramethyl-η^Five-Cyclopentadienyl) silanetita
Dichloride, (t-butylamido) dimethyl (tetra
Methyl-η^Five-Cyclopentadienyl) silane titanium di
Bromide, (t-butylamido) dimethyl (tetramethyi
Le-η^Five-Cyclopentadienyl) silane titanium diflu
Olido, (t-butylamido) dimethyl (tetramethyl
−η^Five-Cyclopentadienyl) silane zircon dichloro
Lido, (t-butylamido) dimethyl (tetramethyl-
η^Five-Cyclopentadienyl) silane zircon dibromine
De, (t-butylamido) dimethyl (tetramethyl-η
^Five-Cyclopentadienyl) silane zircon difluoride
De, (t-butylamido) dimethyl (tetramethyl-η
^Five-Cyclopentadienyl) silane titanium dihydrate
De, (t-butylamido) dimethyl (tetramethyl-η
^Five-Cyclopentadienyl) silane titanium chlorohydrate
Ride, (t-butylamido) dimethyl (tetramethyl
−η^Five-Cyclopentadienyl) silane titanium dimethyl
, (T-butylamido) dimethyl (tetramethyl-η
^Five-Cyclopentadienyl) silane titanium methyl chloride
De, (t-butylamido) dimethyl (tetramethyl-η
^Five-Cyclopentadienyl) silane titaniumdiethyl,
(T-Butylamido) dimethyl (tetramethyl-η^Five−
Cyclopentadienyl) silane titanium diisopropoxa
Id, (t-butylamido) dimethyl (tetramethyl-
η^Five-Cyclopentadienyl) silane titanium di (ortho
Dimethylamino) benzyl, (t-butylamido) dime
Chill (tetramethyl-η^Five-Cyclopentadienyl) si
Lanthanum (III) (orthodimethylamino) benzyl,
(T-Butylamido) dimethyl (tetramethyl-η^Five−
Cyclopentadienyl) silane titanium di (N-methyl-)
N-phenylamine), (t-butylamido) dimethyl
(Tetramethyl-η^Five-Cyclopentadienyl) silane
Titanium (orthodimethylamino) benzyl chloride,
(T-Butylamido) dimethyl (tetramethyl-η^Five−
Cyclopentadienyl) silane titanium (III) chloride,
(T-Butylamido) dimethyl (tetramethyl-η^Five−
Cyclopentadienyl) silane tantalum dichloride,
(T-Butylamido) dimethyl (tetramethyl-η^Five−
Cyclopentadienyl) silane tantalum trichloride,
(T-Butylamido) dimethyl (tetramethyl-η^Five−
Cyclopentadienyl) silane vanadium chloride,
(T-Butylamido) dimethyl (tetramethyl-η^Five−
Cyclopentadienyl) silane lanthanum chloride, (t
-Butylamido) dimethyl (tetramethyl-η^Five-Siku
Lopentadienyl) silane yttrium chloride, (t
-Butylamido) dimethyl (tetramethyl-η^Five-Siku
Lopentadienyl) silane neodymium chloride, (t-
Butyramide) (tetramethyl-η^Five-Cyclopentadi
(Enyl) -1,2-ethanediyl titanium dichloride,
(Methylamide) (Tetramethyl-η^Five-Cyclopenta
Dienyl) -1,2-ethanediyl titanium dichloride,
(Ethylamide) (Tetramethyl-η^Five-Cyclopenta
Dienyl) -1,2-ethanediyl titanium dichloride,
(T-butylamide) (tetramethyl-η^Five-Cyclope
Methylene titanium dichloride, (ethyl adiene)
Mid) (tetramethyl-η^Five-Cyclopentadienyl)
Methylene titanium dichloride, (benzylamide) dimethyl
(Tetramethyl-η^Five-Cyclopentadienyl) sila
Titanium dichloride, (phenylphosphide) dimethyl
(Tetramethyl-η ^Five-Cyclopentadienyl) sila
Nylcondichloride, (t-butylamido) dimethyl
(Indenyl) silane titanium dichloride, (t-butyl
Amido) dimethyl (1-phospha-2,3,4,5-thene
(Tramethylcyclopentadienyl) silane titanium dichloride
Lido, (t-butylamido) dimethyl (1-phospha-
3,4-diphenylcyclopentadienyl) silanetita
Dichloride, (t-butylamido) dimethyl (3-pho
Sfinenyl) silane titanium dichloride, (t-bu
(Cylamido) dimethyl (1-bora-2,3,4,5-te
(Tramethylcyclopentadienyl) silane titanium dichloride
Lido and the like. Among these compounds,
In addition, (t-butylamido) dimethyl (tetramethyl-η
^Five-Cyclopentadienyl) silane titanium dichloride,
(T-Butylamido) dimethyl (tetramethyl-η^Five−
Cyclopentadienyl) silane titanium dibromide, (t
-Butylamido) dimethyl (tetramethyl-η^Five-Siku
Such as lopentadienyl) silane titanium (III) chloride
Halo-substituted compounds are preferred.

In the present invention, when a halo-substituted compound as described above is used, as will be described later, it is alkylated by an organoaluminum compound in the catalyst system to exhibit catalytic activity. Therefore, the halo-substituted compound can be directly used in the polymerization reaction, and the catalyst preparation step can be simplified,
It is also possible to improve the production efficiency of the polymer. Of the halo-substituted compounds, chlorine-substituted compounds are preferred because they are particularly easily alkylated by organoaluminum compounds. In the present invention, the transition metal complex compound as the catalyst component (A) may be used alone or in combination of two or more.

In the present invention, as (B) catalyst component
(B-1) The transition metal complex compound or its component (A)
Which reacts with a derivative of to form an ionic complex
A compound and / or a (B-2) Lewis acid is used. The
As the compound of the component (B-1), the transition of the component (A)
Ionic by reacting with metal transfer complex compound or its derivative
Any ionic compound that forms a complex
However, from the viewpoint of productivity and stability, the following
General formula (II), (III) ([L¹-R¹]^{k +})_p([Z]^-)_q   ... (II) ([L²]^{k +})_p([Z]^-)_q       ... (III) (However, L²Is M², R²R³M³, R^Four ₃C or R^FiveM³And
It ) [In the formulas (II) and (III), [Z]^-Is a non-coordinating anion
[Z¹]^-And [Z²]^-, Here [Z¹]^-Is based on multiple groups
The anion bound to the element, ie [M¹Y¹Y²... Yⁿ]
(Where M¹Is an element of Groups 5 to 15 of the Periodic Table, preferably
The elements of Groups 13 to 15 of the periodic table are shown. Y¹~ YⁿIs hydrogen
Child, halogen atom, organic metalloid group, amino group, al
Coxy group, hydrocarbon group or hydrocarbon group containing hetero atom
Show. Y¹~ YⁿTwo or more of them may form a ring
Yes. n is [(central metal M¹Valence of +1)
You ) [Z²]^-Has an acidity constant (pKa) of -10 or less
Bronsted acid alone or Bronsted acid and Lewis
Conjugate base of acid combination, or generally defined as super strong acid
Is a conjugated base. In addition, the Lewis base is coordinated
May be. Furthermore, L¹Is Lewis base, R¹Is a hydrogen atom
Represents a hydrocarbon group, R ²And R³Each is a cyclopen
A tadienyl group or a substituted cyclopentadienyl group is shown.
Each cyclopentadienyl group may be the same or different
Two or more cyclopentadienyl groups have a crosslinked structure.
You may. R^FourIs hydrocarbon group, hydrocarbon water containing hetero atom
R represents an elementary group or an alkoxy group, and R^FiveIs a porphyrin,
Examples include phthalocyanines and allyl group derivatives. k is
[L¹-R¹], [L²] With an ionic valence of 1 to 3 is an integer,
p is an integer of 1 or more, and q = (p × k). M²Is the cycle
It contains elements of Groups 1 to 11, 11 to 13 and 17 of the Periodic Table.
R, M³Indicates an element belonging to Groups 7 to 12 of the periodic table. ]]
What is mentioned can be used conveniently.

[0011] anion [Z ^1] attached to said plurality of groups are element ^-, i.e. in the ^{[M 1 Y 1 Y 2 ··· Y} n ], M ¹
Specific examples of B include Al, Si, P, As and Sb, and preferably B and Al. Also, Y ¹ ,
Specific examples of Y ^{2 to} Y ⁿ include a dimethylamino group and a diethylamino group as an amino group, a methoxy group, an ethoxy group, and n- as an alkoxy group or an aryloxy group.
Hydrocarbon groups such as butoxy group and phenoxy group are methyl group, ethyl group, n-propyl group, isopropyl group, n
-Butyl group, isobutyl group, n-octyl group, n-eicosyl group, phenyl group, p-tolyl group, benzyl group, 4
Fluorine, chlorine, bromine, iodine as a halogen atom such as -t-butylphenyl group, 3,5-dimethylphenyl group, p-fluorophenyl group, 3,5-difluorophenyl group, pentachlorophenyl as a hydrocarbon group containing a hetero atom. Group, 3,4,5-trifluorophenyl group, pentafluorophenyl group, 3,5-bis (trifluoromethyl) phenyl group, bis (trimethylsilyl) methyl group, etc. as organic metalloid group pentamethylantimony group, trimethylsilyl group , Trimethylgermyl group, diphenylarsine group, dicyclohexylantimony group,
Examples include diphenylboron. The non-coordinating anion i.e. the acidity constant (pKa) -10 below Bronsted acid alone or Bronsted the slashed.nsted acid and Lewis acid combination conjugate base [Z ^{2] -} trifluoromethanesulfonic Specific examples of Acid anion (CF ₃ SO ₃ ) ^- ,
Bis (trifluoromethanesulfonyl) methyl anion, bis (trifluoromethanesulfonyl) benzyl anion, bis (trifluoromethanesulfonyl) amide, perchlorate anion (ClO ₄ ) ^- , trifluoroacetic acid anion (CF ₃ CO ₂ ) ^- , hexafluoro Antimony anion (SbF ₆ ) ^- , fluorosulfonate anion (FSO ₃ ) ^- , chlorosulfonate anion (ClS
O ₃ ) ^- , fluorosulfonate anion / 5-antimony fluoride (FSO ₃ / SbF ₅ ) ^- , fluorosulfonate anion / 5-arsenic fluoride (FSO ₃ / AsF ₅ ) ^- , trifluoromethanesulfonate / 5- Antimony fluoride (C
_{F 3 SO 3 / SbF 5)} - and the like.

Further, specific examples of L ¹ include ammonia, methylamine, aniline, dimethylamine, diethylamine, N-methylaniline, diphenylamine,
N, N-dimethylaniline, trimethylamine, triethylamine, tri-n-butylamine, methyldiphenylamine, pyridine, amines such as p-bromo-N, N-dimethylaniline, p-nitro-N, N-dimethylaniline, triethylphosphine , Phosphines such as triphenylphosphine and diphenylphosphine, ethers such as dimethyl ether, diethyl ether, dioxane and tetrahydrofuran, thioethers such as tetrahydrothiophene, esters such as ethyl benzoate, nitriles such as acetonitrile and benzonitrile, ethylene, Chain unsaturated hydrocarbons such as butadiene, 1-pentene, isoprene and their derivatives, benzene, toluene, xylene, cyclooctadiene and cyclooctatetraene. , And the like of cyclic unsaturated hydrocarbons.

Specific examples of R ¹ include hydrogen, methyl group, ethyl group, benzyl group and trityl group, and specific examples of R ² and R ³ include cyclopentadienyl group and methylcyclopentadiene. Examples thereof include an enyl group, an ethylcyclopentadienyl group and a pentamethylcyclopentadienyl group. Specific examples of R ⁴ include phenyl group, p-tolyl group, p-methoxyphenyl group and the like, and specific examples of R ⁵ include tetraphenylporphyrin, phthalocyanine, allyl, methallyl and the like. . Further, specific examples of M ² include Li, Na, K, Ag, Cu, Br, I, and I3, and specific examples of M ³³ include Mn,
Fe, Co, Ni, Zn etc. can be mentioned.

Specific examples of the ionic compound which reacts with the transition metal complex compound of the component (A) or its derivative to form an ionic complex, that is, the component compound (B-1) are tetra Triethylammonium phenylborate, tri-n-butylammonium tetraphenylborate, trimethylammonium tetraphenylborate, tetraethylammonium tetraphenylborate, methyl (tri-n-butyl) ammonium tetraphenylborate,
Benzyl (tri-n-butyl) ammonium tetraphenylborate, dimethyldiphenylammonium tetraphenylborate, triphenyltetramethylborate (methyl)
Ammonium, trimethylanilinium tetraphenylborate, methylpyridinium tetraphenylborate, benzylpyridinium tetraphenylborate, methyl (2-cyanopyridinium) tetraphenylborate, triethylammonium tetrakis (pentafluorophenyl) borate,
Tetrakis (pentafluorophenyl) borate tri-n-
Butylammonium, triphenylammonium tetrakis (pentafluorophenyl) borate, tetra-n-butylammonium tetrakis (pentafluorophenyl) borate, tetraethylammonium tetrakis (pentafluorophenyl) borate, benzyl tetrakis (pentafluorophenyl) borate (tri-n -Butyl) ammonium, tetrakis (pentafluorophenyl) borate methyldiphenylammonium, tetrakis (pentafluorophenyl) borate triphenyl (methyl) ammonium, tetrakis (pentafluorophenyl) borate methylanilinium, tetrakis (pentafluorophenyl)
Dimethylanilinium borate, trimethylanilinium tetrakis (pentafluorophenyl) borate, methylpyridinium tetrakis (pentafluorophenyl) borate,
Benzylpyridinium tetrakis (pentafluorophenyl) borate, methyl tetrakis (pentafluorophenyl) borate (2-cyanopyridinium), benzyl tetrakis (pentafluorophenyl) borate (2-cyanopyridinium), methyl tetrakis (pentafluorophenyl) borate (4 -Cyanopyridinium), trikis (pentafluorophenyl) borate triphenylphosphonium, tetrakis [bis (3,5-ditrifluoromethyl) phenyl] dimethylanilinium borate, ferrocenium tetraphenylborate, silver tetraphenylborate, trityl tetraphenylborate, Tetraphenylborate Tetraphenylporphyrin Manganese, Tetrakis (pentafluorophenyl) ferrocenium borate, Tetrakis (pentafluorophenyl) Acid (1,1′-dimethylferrocenium), tetrakis (pentafluorophenyl) decamethylferrocenium borate, silver tetrakis (pentafluorophenyl) borate, trityl tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) Lithium borate, sodium tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) theoraphenylporphyrin manganese tetraborate,
Silver tetrafluoroborate, silver hexafluorophosphate, silver hexafluoroarsenate, silver perchlorate, silver trifluoroacetate,
Examples thereof include silver trifluoromethanesulfonate.

Among these compounds, preferred from the viewpoints of productivity and stability are, for example, triethylammonium tetraphenylborate, tri-n-butylammonium tetraphenylborate, trimethylammonium tetraphenylborate, tetraethylammonium tetraphenylborate. , Methyl (tri-n-butyl) ammonium tetraphenylborate, benzyl (tri-n-butyl) ammonium tetraphenylborate, dimethyldiphenylammonium tetraphenylborate, triphenyl (methyl) ammonium tetraphenylborate, trimethylanilinium tetraphenylborate , Tetraphenylborate methylpyridinium, tetraphenylborate benzylpyridinium, tetraphenylborate methyl (2-cyanopyridinium), tetrakis Pentafluorophenyl) borate triethylammonium, tetrakis (pentafluorophenyl) borate tri-n-butylammonium, tetrakis (pentafluorophenyl) borate triphenylammonium, tetrakis (pentafluorophenyl) borate tetra-n-butylammonium, tetrakis (penta Tetraethylammonium fluorophenyl) borate, benzyl tetrakis (pentafluorophenyl) borate (tri-
n-butyl) ammonium, tetrakis (pentafluorophenyl) borate methyldiphenylammonium, tetrakis (pentafluorophenyl) borate triphenyl (methyl) ammonium, tetrakis (pentafluorophenyl) borate methylanilinium, tetrakis (pentafluorophenyl) borate dimethyl Anilinium, trimethylanilinium tetrakis (pentafluorophenyl) borate, methylpyridinium tetrakis (pentafluorophenyl) borate, benzylpyridinium tetrakis (pentafluorophenyl) borate, methyl tetrakis (pentafluorophenyl) borate (2-cyanopyridinium), tetrakis Benzyl (pentafluorophenyl) borate (2-cyanopyridinium), tetrakis (pentafluorophenyl) Acid methyl (4-cyanopyridinium), tetrakis (pentafluorophenyl) borate triphenylphosphonium, tetrakis [bis (3,5-ditrifluoromethyl) phenyl] borate dimethylanilinium, tetraphenylborate trityl, tetrakis (pentafluorophenyl) Mention may be made of trityl borate. As the component (B-1), one type of ionic compound that reacts with the transition metal complex compound of the component (A) or a derivative thereof to form an ionic complex may be used, or two or more types thereof may be used. You may use it in combination. The (A) in the present invention
The molar ratio of the catalyst component to the (B-1) catalyst component is 20: 1 to 1:20, preferably 2: 1 to 1: 2. Within the above range, the catalyst cost is particularly low and the polymerization activity is high, which is preferable.

On the other hand, the Lewis acid as the component (B-2) is not particularly limited and may be an organic compound or a solid inorganic compound. A boron compound or an aluminum compound is preferably used as the organic compound, and a magnesium compound or the like is preferably used as the inorganic compound. Examples of the aluminum compound include bis (2,6-di-t-butyl-4-
Methylphenoxy) aluminum methyl, (1,1-bi-2-naphthoxy) aluminum methyl and the like, magnesium compounds such as magnesium chloride and diethoxymagnesium, and boron compounds such as triphenylboron and tris (penta). Fluorophenyl) boron, tris [3,5-bis (trifluoromethyl) phenyl] boron, tris [(4-fluoromethyl)
Phenyl] boron, trimethylboron, triethylboron, tri-n-butylboron, tris (fluoromethyl) boron,
Tris (pentafluoroethyl) boron, Tris (nonafluorobutyl) boron, Tris (2,4,6-trifluorophenyl) boron, Tris (3,5-difluoro) boron, Tris [3,5-bis (trifluoro) Methyl) phenyl) boron, bis (pentafluorophenyl) fluoroboron, diphenylfluoroboron, bis (pentafluorophenyl) chloroboron, dimethylfluoroboron, diethylfluoroboron, di-n-butylfluoroboron, pentafluorophenyldifluoroboron, Examples thereof include phenyldifluoroboron, pentafluorophenyldichloroboron, methyldifluoroboron, ethyldifluoroboron and n-butyldifluoroboron. These Lewis acids may be used alone or in combination of two or more. The use ratio of the catalyst component (A) and the catalyst component (B-2) is
The molar ratio is 1: 0.1 to 1: 2000, preferably 1 :.
0.2 to 1: 1000, more preferably 1: 0.5 to
The range of 1: 200 is desirable, and it may be appropriately selected depending on the kind of the specific Lewis acid used. Within the above range, the catalyst cost is particularly low and the activity is high, which is preferable. This (B) catalyst component (B-1) component and (B-2)
The components may be used alone or in combination with each other.

In the present invention, an organoaluminum compound is used as the catalyst component (C). As the organoaluminum compound, during normal general formula ^{_{(IV) R 6 r AlQ r}} -3 ··· (IV) ( wherein, R ⁶ is an alkyl group having 1 to 12 carbon atoms, Q is a hydrogen atom, C 1 -C To 20 alkoxy groups or halogen atoms, and r is a number of 1 to 3). Specific examples of the compound represented by the general formula (IV) include trimethylaluminum, triethylaluminum, tri-n-propylaluminum, triisopropylaluminum, triisobutylaluminum,
Tri-n-hexylaluminum, tri (2-methylpentyl) aluminum, tri-n-octylaluminum, tri-n-decylaluminum, triphenylaluminum, methyldiisobutylaluminum, dimethylaluminium chloride, diethylaluminum chloride, ethylisobutylaluminum chloride. , Diisobutyl aluminum chloride, methyl aluminum dichloride, ethyl aluminum dichloride, isobutyl aluminum dichloride, dimethyl aluminum fluoride, diisobutyl aluminum hydride, diethyl aluminum hydride, ethyl aluminum sesquichloride.

As will be described later, the organoaluminum compound in the present invention exerts various actions, but in any case, it has 3 or more carbon atoms, particularly 3 to 10 carbon atoms, from the viewpoint of efficiently performing the alkylation described below. It is preferable to use a hydrocarbon group-containing aluminum compound having at least one hydrocarbon group of, and triisobutylaluminum is particularly preferable from the viewpoint of catalytic activity and control of molecular weight distribution.

The use ratio of the organoaluminum of the catalyst component (C) to the catalyst component (A) is preferably 30 or more, more preferably 200 or more, and particularly 200 to 2500 in terms of the element ratio of aluminum / transition metal element. desirable. Within the above range, the polymerization activity per transition metal can be remarkably improved, but when it is outside the above range, the organoaluminum compound is wasted and a large amount remains in the polymer, which is not preferable. Also,
When the amount is small, the effect of improving the polymerization activity is low. In the polymerization reaction of the present invention, the organoaluminum compound exhibits the following effects. First, by using the organoaluminum compound as the component (C), it is possible to obtain a polymerization catalyst having a much higher catalytic efficiency than the polymerization catalyst comprising the catalyst component (A) and the catalyst component (B). . Further, by using two or more kinds of hydrocarbon group-containing aluminum compounds having at least one hydrocarbon group having 1 or more carbon atoms as the organoaluminum compound as the catalyst component (C), it becomes possible to control the molecular weight. The two or more kinds of organoaluminum compounds may be used at the same time or may be used stepwise. By charging two or more of the organoaluminum compounds at the same time, the molecular weight can be adjusted while suppressing a decrease in catalytic activity and an increase in molecular weight distribution. on the other hand,
A polymer having a molecular weight distribution in which the distributions in the low molecular weight region and the high molecular weight region are suppressed can be obtained by charging two or more of the organoaluminum compounds in a stepwise manner.
As such two or more kinds of organoaluminum compounds, a combination of triisobutylaluminum and trimethylaluminum or triethylaluminum is preferably used. There is no particular limitation on the use ratio of the two or more kinds of organoaluminum compounds, and polymers having various molecular weights and molecular weight distributions can be obtained by variously changing the mixing ratio or the use ratio.

In addition, by using two or more kinds of hydrocarbon group-containing aluminum compounds having at least one hydrocarbon group having 1 or more carbon atoms as described above, it is possible to prepare a lower olefin monomer (for example, ethylene, propylene, etc.) In the case of polymerizing with a higher olefin monomer (for example, 1-butene, 1-hexene, 1-octene, etc.) as one or more comonomers, conventional Ziegler
A copolymer having an extremely high comonomer content, which cannot be obtained by the Natta catalyst, is obtained. Also in this case, the comonomer content of the higher α-olefin can be adjusted by variously changing the mixing ratio or the use ratio of two or more organoaluminum compounds. As a specific usage mode,
It is desirable to use triisobutylaluminum and another organoaluminum compound in a molar ratio of 1000: 1 to 1: 1000, preferably 100: 1 to 1: 100. At a use ratio within this range, a particularly excellent molecular weight adjusting action is obtained.

In the present invention, the organoaluminum compound, when a halo-substituted compound is used as the component (A),
It also acts as an alkylating agent. By this action,
The halo-substituted compound as the component (A) can be directly used in the polymerization reaction, and the catalyst preparation process can be simplified. Conventionally, even if a halo-substituted compound was directly used as a catalyst component, no or almost no catalytic activity was obtained. Therefore, the halo-substituted compound has been added to the catalyst system after the step of replacing the halogen in the compound with another substituent. For example, a dichloro-substituted compound was alkylated to give a dimethyl compound and then used as a catalyst component. Further, in such a case, the yield of dimethylation is 5
It is about 6%, and the effect of the present invention which does not require the alkylation step is great from the viewpoint of simplifying the catalyst preparation step. That is, in the present invention, since the organoaluminum compound also acts as an alkylating agent for the halo-substituted compound, the halo-substituted compound is alkylated in the catalyst system and the catalytic activity is exhibited. From this point of view, as described above, an alkyl group-containing aluminum compound having at least one alkyl group having 3 or more carbon atoms, preferably 3 to 10 carbon atoms is preferable, and triisobutylaluminum is particularly preferable.

In the present invention, at least one of the catalyst components can be used by supporting it on a suitable carrier. There is no particular limitation on the type of the carrier, an inorganic oxide carrier,
Although any other inorganic carrier or organic carrier can be used, an inorganic oxide carrier or another inorganic carrier is particularly preferable from the viewpoint of morphology control and easy handling. As the inorganic oxide carrier, specifically, S
iO ₂ , Al ₂ O ₃ , MgO, ZrO ₂ , TiO ₂ , Fe ₂ O
₃ , B ₂ O ₃ , CaO, ZnO, BaO, ThO ₂ and mixtures thereof, such as silica-alumina, zeolite, ferrite, glass fiber, and smectite. Of these, SiO ₂ and Al ₂ O ₃ are particularly preferable. The inorganic oxide carrier may contain a small amount of carbonate, nitrate, sulfate and the like. On the other hand, examples of carriers other than the above include magnesium compounds represented by the general formula MgR ⁷ _x X ¹ _y represented by magnesium compounds such as MgCl ₂ and Mg (OC ₂ H ₅ ) ₂ and complex salts thereof. it can. Here, R ⁷ is an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or 6 to 20 carbon atoms.
Aryl group, X ¹ is a halogen atom or has 1 to 20 carbon atoms.
Is an alkyl group, x is 0 to 2, y is 0 to 2, and x + y = 2. Each R ⁷ and each X ¹ may be the same or different. Examples of the organic carrier include polystyrene, polyethylene, polypropylene, substituted polystyrene, polymers such as polyarylate, starch, and carbon.

The carrier used in the present invention includes
From the viewpoint of morphology control and ease of handling, MgCl
_{2, Mg (OC 2 H 5} ) 2, MgCl (OC 2 H 5) 2, Mg
(OC ₂ H ₅ ) ₂ , SiO ₂ , Al ₂ O _{3 and the} like are preferable. The property of the carrier varies depending on its type and production method, but the average particle size is usually 1 to 300 μm, preferably 10 to 200.
μm, more preferably 20 to 100 μm. When the particle size is small, fine powder in the polymer increases, and when the particle size is large, coarse particles in the polymer increase, which causes decrease in bulk density and clogging of the hopper. The specific surface area of the carrier is usually 1 to 1.
000 m ² / g, preferably 50 to 500 m ² / g, the pore volume is usually 0.1 to ⁵ cm ³ / g, preferably 0.3 to
It is 3 cm ³ / g. If either the specific surface area or the pore volume deviates from the above range, the catalytic activity may decrease. The specific surface area and the pore volume can be obtained from the volume of nitrogen gas adsorbed according to, for example, the BET method (Journal of the American Chemical Society, Volume 60, page 309 (1983)).
reference). Further, the carrier is usually 150 to 1000.
It is desirable to use it after firing at ℃, preferably 200 to 800 ℃.

When at least one catalyst component is supported on the carrier, at least one of (A) catalyst component and (B) catalyst component, preferably (A) catalyst component and (B).
It is desirable to support both catalyst components. In the carrier,
The method of supporting at least one of the component (A) and the component (B) is not particularly limited. For example, a method of mixing at least one of the component (A) and the component (B) with a carrier, an organoaluminum compound as a carrier. Alternatively, a method of treating with a halogen-containing silicon compound and then mixing with at least one of the components (A) and (B) in an inert solvent, a carrier, a component (A) and / or a component (B) and an organoaluminum compound, or Method of reacting with halogen-containing silicon compound, method of loading component (A) or component (B) on carrier and then mixing with component (B) or component (A), component (A) and component (B) It is possible to use a method of mixing a reaction product of contact with the carrier with a carrier, a method of allowing a carrier to coexist in the contact reaction between the component (A) and the component (B), and the like.

The catalyst thus obtained may be used for the polymerization after the solvent is once distilled off and taken out as a solid, or may be used for the polymerization as it is. Further, in the present invention, the catalyst can be produced by carrying out the loading operation of at least one of the component (A) and the component (B) on the carrier in the polymerization system. For example, at least one of the component (A) and the component (B), a carrier and, if necessary, the organoaluminum compound of the component (C) are added, and an olefin such as ethylene is added at atmospheric pressure to 20 Kg / cm ² to obtain a temperature of −20 to 200. It is possible to use a method in which catalyst particles are produced by carrying out prepolymerization at a temperature of 1 minute to 2 hours. In the present invention, the weight ratio of the component (B) to the carrier is 1: 5 to 1: 10000, preferably 1:10 to 1: 500. Also (A)
The weight ratio of the components to the carrier is 1: 5 to 1:10.
000, preferably 1:10 to 1: 500. Use ratio of the component (B) and carrier, or (A)
If the use ratio of the component and the carrier deviates from the above range, the activity may decrease. The average particle size of the polymerization catalyst of the present invention thus prepared is usually 2 to 200 μm, preferably 10 to 150 μm, particularly preferably 20 to 10 μm.
0 μm, and the specific surface area is usually 20 to 1000 m ² /
g, preferably 50 to 500 m ² / g. If the average particle diameter is less than 2 μm, fine powder in the polymer may increase, and if it exceeds 200 μm, coarse particles in the polymer may increase. If the specific surface area is less than 20 m ² / g, the activity may decrease, and if it exceeds 1000 m ² / g, the bulk density of the polymer may decrease. In the catalyst of the present invention, the amount of transition metal in 100 g of the carrier is usually 0.05 to 10 g, preferably 0.1 to 2 g. If the amount of transition metal is out of the above range, the activity may decrease. By thus supporting on a carrier, a polymer having a high bulk density industrially advantageous and an excellent particle size distribution can be obtained.

According to the method for producing a polymer of the present invention, homopolymerization of olefins or copolymerization of olefins with other olefins and / or other monomers using the above-mentioned polymerization catalyst ( That is, copolymerization with different olefins, copolymerization with olefins and other monomers, or copolymerization with different olefins and other monomers) can be suitably performed. The olefins are not particularly limited, but α-olefins having 2 to 20 carbon atoms are preferable. Examples of the α-olefin include ethylene, propylene, 1-butene, 3-methyl-1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1 -Dodecene, 1
-Tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene and the like can be mentioned. Also,
The other olefins described above may be appropriately selected from the above olefins.

In the present invention, the olefins may be used alone or in combination of two or more. When copolymerizing two or more olefins, the above olefins can be combined arbitrarily. The use ratio in that case is, for example, in the case of copolymerizing propylene and ethylene, or ethylene and α-olefin having 3 to 10 carbon atoms, propylene and ethylene, or ethylene and α-olefin having 3 to 10 carbon atoms. Copolymerization ratio (molar ratio)
Is usually selected in the range of 99.9: 0.1 to 0.1: 99.9, preferably 99.5: 0.5 to 75.0: 25.0. Further, in the present invention, the above-mentioned olefins may be copolymerized with other monomers, and examples of the other monomer used at this time include styrene, p-methylstyrene, isopropylstyrene and t- Vinyl aromatic compounds such as butyl styrene, butadiene, isoprene, 1,
Chain diolefins such as 5-hexadiene, norbornene, 1,4,5,8-dimethano-1,2,3,4,4
Cyclic olefins such as a, 5,8,8a-octahydronaphthalene, cyclic diolefins such as norbornadiene, 5-ethylidene norbornene, 5-vinyl norbornene and dicyclopentadiene, unsaturated such as ethyl acrylate and methyl methacrylate Esters, lactones such as β-propiolactone, β-butyrolactone and γ-butyrolactone, lactams such as ε-caprolactam and δ-valerolactam, epoxypropane, 1,2-
Examples thereof include epoxides such as epoxybutane. The catalyst for polymerization of the present invention can be used not only for polymerization of the above-mentioned olefins but also for polymerization of other than olefins.

In the present invention, the polymerization method is not particularly limited.
No, slurry polymerization method, gas phase polymerization method, bulk polymerization method, solution weight
Any method such as a legal method or a suspension polymerization method may be used.
However, the slurry polymerization method and the gas phase polymerization method are particularly preferable. polymerization
Regarding the conditions, the polymerization temperature is usually −100 to 250 ° C.,
It is preferably -50 to 250 ° C, more preferably 0 to 22.
It is 0 ° C. Also, the ratio of catalyst used to the reaction raw materials
Is preferably the raw material monomer / the above-mentioned component (A) (molar ratio)
Kuha 1-10 ⁸, Especially from 10 to 10^FiveIs preferred
Yes. Furthermore, the polymerization time is usually 5 minutes to 10 hours, and the reaction pressure is
Is preferably normal pressure to 200 kg / cm²G, especially preferred
Kubo normal pressure to 100 kg / cm²G. Polymer molecule
To adjust the amount, the type of catalyst component, amount used, and weight
Selection of synthesis temperature, and further polymerization in the presence of hydrogen
It When a polymerization solvent is used, for example, benzene or toluene
Aromatic hydrocarbons such as benzene, xylene, ethylbenzene,
Cyclopentane, cyclohexane, methylcyclohexa
Alicyclic hydrocarbons such as benzene, pentane, hexane, hepta
And aliphatic hydrocarbons such as octane, octane, chloroform,
Do not use halogenated hydrocarbons such as chloromethane.
You can These solvents may be used alone.
Alternatively, two or more kinds may be combined. Also, α-
Monomers such as olefins may be used as a solvent.
Depending on the polymerization method, it can be carried out without a solvent.
The molecular weight of the polymer thus obtained is not particularly limited.
Intrinsic viscosity [η] (135 ° C decalin
(Measured in) is 0.1 deciliter / g or more, preferably
Is 0.2 to 20 deciliters / g, more preferably
0.3 to 15 deciliter / g is desirable.

In the present invention, prepolymerization can be carried out using the above-mentioned polymerization catalyst. The prepolymerization can be carried out by contacting the solid catalyst component with, for example, a small amount of olefin, but the method is not particularly limited,
A known method can be used. The olefin used in the prepolymerization is not particularly limited and may be the same as those exemplified above, for example, ethylene, α-olefin having 3 to 20 carbon atoms, or a mixture thereof. It is advantageous to use the same olefin as used in. The prepolymerization temperature is usually -20 to 200 ° C, preferably -10 to 10.
130 degreeC, More preferably, it is 0-80 degreeC. In the prepolymerization, an inert hydrocarbon, an aliphatic hydrocarbon, an aromatic hydrocarbon, a monomer or the like can be used as a solvent. Of these, aliphatic hydrocarbons are particularly preferable. Further, the prepolymerization may be carried out without a solvent. In the prepolymerization, the intrinsic viscosity [η] (13) of the prepolymerized product is
0.2 deciliter / g or more, particularly 0.5 deciliter / g or more, measured in 5 ° C. decalin, and the amount of the prepolymerized product per 1 mmol of the transition metal component in the catalyst is 1 to 10000 g, particularly 10 to 1000 g. It is desirable to adjust the conditions so that

[0030]

EXAMPLES The present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. In the examples and comparative examples, the physical properties of polymers were measured as follows. (1) Intrinsic viscosity [η] Measured in decalin at 135 ° C. (2) Weight average molecular weight (Mw), number average molecular weight (Mn) Using 1,2,4-trichlorobenzene as a solvent, 1
Gel permeation chromatography (GPC) at 35 ° C (apparatus: Waters ALC / GPC
150C, column: Tosoh TSK HM + GMH
6 × 2, flow rate: 1.0 ml / min) was calculated in terms of polyethylene. (3) Melting point DSC (differential scanning calorimeter) analysis was performed. Measurement conditions: Fast heating: Room temperature to 190 ° C, 10 ° C /
Hold for min, 3min Fast cooling: 190 ℃ to room temperature, 10 ℃ / m
In, 3min holding second heating: room temperature to 190 ℃, 10 ℃ / m
in (4) Octene unit content (mol%) Measured by ¹ H-NMR.

Example 1 (1) Synthesis of dimethylanilinium tetrakis (pentafluorophenyl) borate Pentafluorolithium prepared from 152 mmol of bromopentafluorobenzene and 152 mmol of butyllithium was added to 45 mmol of boron trichloride in hexane. The reaction was performed to obtain tris (pentafluorophenyl) boron as a white solid. 41 mmol of the obtained tris (pentafluorophenyl) boron was reacted with 41 mmol of pentafluorophenyllithium to isolate lithium tetrakis (pentafluorophenyl) boron as a white solid. Next, 16 mmol of lithium tetrakis (pentafluorophenyl) boron and 16 mmol of dimethylaniline hydrochloride.
Dimethylanilinium tetrakis (pentafluorophenyl) borate ([PhMe ₂ MH] [B (C ₆ F ₅ ) ₄ ]) was obtained as a white solid in an amount of 11.4 mmol by reacting with millimole in water. It was confirmed by ¹ H-NMR and ¹³ C-NMR that the product was the target product. (2) Polymerization of ethylene In a 1.4 liter autoclave substituted with dry nitrogen, 400 ml of toluene, 2.0 mmol of triisobutylaluminum (TIBA) [(C ₄ H ₉ ) ₃ Al], (tertiary butylamide) ) dimethyl (tetramethyl-eta ⁵ - cyclopentadienyl) silane titanium dichloride _{[{C 5 (Me) 4} } SiMe 2 N (t-Bu) T
1 micromol of iCl ₂ ], and 1 micromol of dimethylanilinium tetrakis (pentafluorophenyl) borate obtained in (1) above were added. Next, ethylene was continuously supplied to the autoclave at 80 ° C. so that the pressure in the system was 4 kg / cm ² G, and polymerization was carried out for 1 hour to obtain 9.47 g of polyethylene. The obtained polymer Mw was 118,000 and Mw / Mn was 1.9. The polymerization results are shown in Table 1.

Comparative Example 1 In a 1.4 liter autoclave purged with dry nitrogen, 400 ml of toluene, (tertiary butylamido) dimethyl (tetramethyl-η ⁵ -cyclopentadienyl) silanetitanium dichloride [{C ₅ (Me) ₄ }
SiMe ₂ N (t-Bu) TiCl ₂ ] 1 micromol,
1 micromol of dimethylanilinium tetrakis (pentafluorophenyl) borate obtained in Example 1- (1) was added. Next, at 80 ° C., the pressure in the system was 4 kg / cm ² G
Ethylene was continuously supplied to the autoclave so as to obtain the desired polymerization, and polymerization was carried out for 1 hour, but the intended polyethylene could not be obtained. The polymerization conditions and the polymerization results are shown in Table 1.

Example 2 In Example 1, triisobutylaluminum (TI
BA) to triethyl aluminum (TEA) [(C
_[2 H ₅ ) ₃ Al] was used, but the polymerization was carried out in the same manner as in Example 1 to obtain 0.5 g of polyethylene. Mw of the obtained polymer was 22,000, Mw / Mn
Was 2.9. The polymerization conditions and the polymerization results are shown in Table 1.

Example 3 In Example 1, triisobutylaluminum (TI
BA) to trimethylaluminum (TMA) [(C
Was replaced by H _{3) 3} Al] is was subjected Polymerization was in the same manner as in Example 1, polyethylene 1.15g was obtained. Mw of the obtained polymer was 277,000, Mw / M
n was 1.7. The polymerization conditions and the polymerization results are shown in Table 1.

Example 4 In Example 1, triisobutylaluminum (TI
BA) 2.0 mmol is added to TIBA 2.0
Polymerization was carried out in the same manner as in Example 1 except that mmol and TEA of 0.2 mmol were added.
0.66 g of polyethylene was obtained. M of the obtained polymer
The w was 69,000 and the Mw / Mn was 2.5. The polymerization conditions and the polymerization results are shown in Table 1.

[0036]

[Table 1]

[0037]

[Table 2] [Notes to Table 1] Polymerization condition: Polymerization temperature 80 ° C, Polymerization time 1 hour Ti complex: {C ₅ (Me) ₄ } SiMe ₂ N (t-Bu)
TiCl ₂ (pKa value of HX is -7) ionic complex: [PhMe ₂ NH] [B (C ₆ F _{5) 4]} TIBA: triisobutylaluminum TEA: triethylaluminum TMA: trimethylaluminium

Example 5 Copolymerization of ethylene and 1-octene In a 1.4 liter autoclave purged with dry nitrogen, 360 ml of toluene and 40 of 1-octene were placed.
Milliliter, triisobutylaluminum (TIB
A) [(C ₄ H ₉ ) ₃ Al] 2.0 mmol, (tertiary butylamido) dimethyl (tetramethyl-η ⁵ -cyclopentadienyl) silanetitanium dichloride [{C
_{5 (Me) 4} SiMe 2} N (t-Bu) TiCl 2] 1 micromolar, was added tetrakis (pentafluorophenyl) borate dimethylanilinium 1 micromolar obtained in the above Example 1- (1). Next, ethylene was continuously supplied to the autoclave at 80 ° C. so that the pressure in the system became 4 kg / cm ² G, and polymerization was carried out for 1 hour.
46.52 g of an ethylene-1-octene copolymer was obtained. Mw of the obtained polymer was 127,000, Mw / M
n was 2.46. The polymerization conditions and the polymerization results are shown in Table 2.

Comparative Example 2 In a 1.4 liter autoclave purged with dry nitrogen, 360 ml of toluene, 40 ml of 1-octene, (tertiary butylamido) dimethyl (tetramethyl-η ⁵ -cyclopentadienyl) silane. Titanium dichloride [{C ₅ (Me) ₄ } SiMe ₂ N (t-B
u) TiCl ₂ ] 1 micromol and 1 micromol of dimethylanilinium tetrakis (pentafluorophenyl) borate obtained in Example 1- (1) were added. Next, 80 ℃
At that time, ethylene was continuously fed to the autoclave so that the pressure in the system became 4 kg / cm ² G, and polymerization was carried out for 1 hour, but the intended ethylene-1-octene copolymer was not obtained. . The polymerization conditions and the polymerization results are shown in Table 2.

Example 6 In Example 5, triisobutylaluminum (TI
Polymerization was performed in the same manner as in Example 5 except that 2.0 mmol of BA) was added instead of 2.0 mmol of TIBA and 0.4 mmol of TEA was added. As a result, 7.04 g of an ethylene-1-octene copolymer was obtained. was gotten. The Mw of the obtained polymer was 46,000, and Mw / Mn
Was 1.80. The polymerization conditions and the polymerization results are shown in Table 2.

Example 7 In Example 5, triisobutylaluminum (TI
Polymerization was performed in the same manner as in Example 5 except that 2.0 mmol of BA) was added instead of 2.0 mmol of TIBA and 0.2 mmol of TEA was added. As a result, 23.17 g of an ethylene-1-octene copolymer was obtained. was gotten.
The polymer obtained had Mw of 87,400 and Mw / Mn of 1.94. The polymerization conditions and the polymerization results are shown in Table 2.

Example 8 In Example 5, triisobutylaluminum (TI
Polymerization was carried out in the same manner as in Example 5 except that 2.0 mmol of BA) was added instead of 2.0 mmol of TIBA and 0.2 mmol of TMA was added. As a result, 2.75 g of ethylene-1-octene copolymer was obtained. was gotten. The Mw of the obtained polymer was 40,700, and Mw / Mn
Was 1.88. The polymerization conditions and the polymerization results are shown in Table 2.

Example 9 In Example 5, triisobutylaluminum (TI
Polymerization was carried out in the same manner as in Example 5 except that 2.0 mmol of BA) was added instead of 2.0 mmol of TIBA and 0.05 mmol of TMA was added. As a result, 20.63 g of ethylene-1-octene copolymer was obtained. was gotten. Mw of the obtained polymer was 64,200, Mw / Mn
Was 1.85. The polymerization conditions and the polymerization results are shown in Table 2.

[0044]

[Table 3]

[0045]

[Table 4] [Notes to Table 2] Polymerization conditions: Polymerization temperature 80 ° C, polymerization time 1 hour Ti complex: {C ₅ (Me) ₄ } SiMe ₂ N (t-Bu)
TiCl ₂ (pKa value of HX is -7) ionic complex: [PhMe ₂ NH] [B (C ₆ F _{5) 4]} TIBA: triisobutylaluminum TEA: triethylaluminum TMA: trimethylaluminium * 1: broad peak * 2 : Not observed under the measuring device and conditions used.

Example 10 (1) [{C ₅ (Me) ₄ } SiMe ₂ N (t-Bu) T
i] Preparation of [OTf] _{2 In} 10 ml of dry toluene, (tert-butylamido) dimethyl (tetramethyl-η ⁵ -cyclopentadienyl) silanetitanium dichloride [{C ₅ (Me) ₄ }
_{SiMe 2 N (t-Bu)} TiCl 2] 0.0737g
(Solution A: 0.02 mol / liter), or silver trifluoromethanesulfonate [AgOTf] in dry toluene.
0.103 g (Solution B: 0.04 mol / liter) was prepared, and Solution B was gradually added dropwise to Solution A at room temperature. The generated silver chloride (solid) was filtered off, and (tertiary butylamido) dimethyl (tetramethyl-η ⁵ -cyclopentadienyl) silanetitanium ditriflate ([{C _{5
(Me) 4} SiMe 2 N} (t-Bu) Ti ] [OTf]
A 0.01 mol / liter solution of ₂ ) was prepared. (2) Copolymerization of ethylene and 1-octene In a 1.4 liter autoclave substituted with dry nitrogen, 360 ml of toluene, 40 ml of 1-octene and triisobutylaluminum (TIBA) were added.
[(C ₄ H ₉ ) ₃ Al] 2.0 mmol, triethylaluminum (TEA) 0.2 mmol, Example 10- above
(1) obtained in (tertiary butylamido) dimethyl (tetramethyl-eta ⁵ - cyclopentadienyl) silane titanium ditriflate _{([{C 5 (Me)} 4} SiMe 2 N
1 micromol of (t-Bu) Ti] [OTf] ₂ ) and 1 micromol of dimethylanilinium tetra (pentafluorophenyl) borate obtained in Example 1- (1) above were added. Next, ethylene was continuously supplied to the autoclave at 80 ° C. so that the pressure in the system became 4 kg / cm ² .
When polymerization was carried out for 1 hour, 31.22 g of ethylene-
A 1-octene copolymer was obtained. M of the obtained polymer
The w was 79,000 and the Mw / Mn was 2.01. The octene unit content was 26.5 mol%.

Example 11 In the ethylene polymerization of Example 1 (2), (tert-butylamido) dimethyl (tetramethyl-η ⁵ -cyclopentadienyl) silanetitanium dichloride was used instead of
(Tertiary butylamide) dimethyl (tetramethyl-η ⁵
Polymerization was carried out for 1 hour in the same manner as in Example 1 except that -cyclopentadienyl) silanetitanium dimethyl was used, and 8.2 g of polyethylene was obtained.

Example 12 400 ml of styrene was placed in a 1.4 liter autoclave, which was purged with dry nitrogen, to which T was added.
0.2 mmol of IBA was added and the temperature was raised to 70 ° C. In addition thereto, dimethylanilinium tetrakis (pentafluorophenyl) borate 20 obtained in (1) of Example 1 in advance
Toluene solution (10 milliliters) mixed with micromol, TIBA 0.2 mmol, (tertiary butylamido) dimethyl (tetramethyl-η ⁵ -cyclopentadienyl) silane titanium dichloride (10 ml) was added, and the system was adjusted to 70 ° C. Ethylene was continuously supplied to the autoclave so that the internal pressure became 8 kg / cm ² G, and 2
Copolymerization was carried out for a time. As a result, 130 g of a copolymer was obtained. This copolymer has an [η] of 1.11 (135
℃, trichlorobenzene), glass transition point is 20 ℃ and 1
It was observed at 03 ° C. (measured by DSC at a temperature rising rate of 10 ° C./min). The composition of the copolymer is 50% by weight of ethylene,
It was 50% by weight of styrene.

[0049]

EFFECTS OF THE INVENTION According to the present invention, it becomes possible to control the molecular weight of a polymer while controlling a decrease in catalytic activity and an increase in the molecular weight distribution of the polymer, which are impossible in the prior art. It is possible to efficiently produce an olefin polymer having a low molecular weight distribution in the region and the high molecular weight region and having an arbitrary molecular weight. Further, by polymerizing a lower olefin monomer with a higher olefin monomer as one or more comonomers, a polymer having a very high comonomer content, which has not been obtained by a conventional Ziegler-Natta catalyst, can be obtained. Furthermore, when a halogen-substituted compound is used as the catalyst component, the catalyst preparation process can be simplified. Further, by selectively using triisobutylaluminum as the organic aluminum, it is possible to produce the polyolefin with high productivity.

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 4J128 AA01 AB01 AC10 AC13 AC18                       AC19 AD02 AD16 BA01B                       BB01B BC12B BC15B CB05                       EA01 EB02 EC01 EC02 GA01                       GA06 GB01 GB07

Claims (7)

[Claims] 1. As a catalyst component, (A) general formula (I) [Chemical 1] (In the formula, M is a metal element of Group 3 to 10 of the periodic table or
Metal element of the tantanoid series, L is a π-bonding ligand, A
Is an element of Groups 13, 14, 15 and 16 of the Periodic Table
A divalent group containing an element selected from B is the first in the periodic table
A bonding group containing an element of Group 5 is shown, and A and B are optionally
X may be a halogen atom together with each other to form a ring.
Represents a child, and n is an integer of 0 to 6 that varies depending on the valence of M.
And when n is 2 or more, even if a plurality of Xs are the same,
It may be different. ) Transition metal complex compound
A transition metal complex compound of the component (B) or the component (A) thereof
The following general formula that reacts with the derivative to form an ionic complex
(II), (III) ([L¹-R¹]^{k +})_p([Z]^-)_q   ... (II) ([L²]^{k +})_p([Z]^-)_q       ... (III) (However, L²Is M², R²R³M³, R^Four ₃C or R^FiveM³And
It ) [In the formulas (II) and (III), [Z]^-Is a non-coordinating anion
[Z¹]^-And [Z²]^-, Here [Z¹]^-Is based on multiple groups
The anion bound to the element, ie [M¹Y¹Y²... Yⁿ]
(Where M¹Is an element of Groups 5 to 15 of the Periodic Table, preferably
The elements of Groups 13 to 15 of the periodic table are shown. Y¹~ YⁿIs hydrogen
Child, halogen atom, organic metalloid group, amino group, al
Coxy group, hydrocarbon group or hydrocarbon group containing hetero atom
Show. Y¹~ YⁿTwo or more of them may form a ring
Yes. n is [(central metal M¹Valence of +1)
You ) [Z²]^-Has an acidity constant (pKa) of -10 or less
Bronsted acid alone or Bronsted acid and Lewis
Conjugate base of acid combination, or generally defined as super strong acid
Is a conjugated base. In addition, the Lewis base is coordinated
May be. Furthermore, L¹Is Lewis base, R¹Is a hydrogen atom
Represents a hydrocarbon group, R ²And R³Each is a cyclopen
A tadienyl group or a substituted cyclopentadienyl group is shown.
Each cyclopentadienyl group may be the same or different
Two or more cyclopentadienyl groups have a crosslinked structure.
You may. R^FourIs hydrocarbon group, hydrocarbon water containing hetero atom
R represents an elementary group or an alkoxy group, and R^FiveIs a porphyrin,
Examples include phthalocyanines and allyl group derivatives. k is
[L¹-R¹], [L²] With an ionic valence of 1 to 3 is an integer,
p is an integer of 1 or more, and q = (p × k). M²Is the cycle
It contains elements of Groups 1 to 11, 11 to 13 and 17 of the Periodic Table.
R, M³Indicates an element belonging to Groups 7 to 12 of the periodic table. ]]
Selected from ionic compounds and boron compounds
And one type, and (C) general formula (IV) R⁶ _rAlQ_r-3      ... (IV) (In the formula, R⁶Is an alkyl group having 1 to 12 carbon atoms, Q is hydrogen
Atom, alkoxy group having 1 to 20 carbon atoms or halogen atom
And r is a number from 1 to 3. ), Carbon number 3
Organic alumini having at least one of the above hydrocarbon groups
And at least one olefinic model
Olefin-based polymerization characterized by polymerizing a nomer
Body manufacturing method. 2. The method for producing an olefin polymer according to claim 1, wherein X in the general formula (I) is a chlorine atom. 3. The method for producing an olefin polymer according to claim 1, wherein M in the general formula (I) is a titanium atom, and n is 2. 4. The method for producing an olefin polymer according to claim 1, wherein the organoaluminum compound is triisobutylaluminum. 5. A hydrocarbon group-containing aluminum compound represented by the general formula (IV) and having at least one hydrocarbon group having 1 or more carbon atoms is used together with the organoaluminum compound as the component (C). Item 2. A method for producing an olefin polymer according to Item 1. 6. The production of an olefin polymer according to claim 5, wherein the organoaluminum compound as the component (C) is triisobutylaluminum, and the other hydrocarbon group-containing aluminum compound is trimethylaluminum or triethylaluminum. Method. 7. (A) General formula (I) [Chemical 2] (In the formula, M is a metal element of Group 3 to 10 of the periodic table or
Metal element of the tantanoid series, L is a π-bonding ligand, A
Is an element of Groups 13, 14, 15 and 16 of the Periodic Table
A divalent group containing an element selected from B is the first in the periodic table
A binding group containing an element of Group 6 is shown, and A and B are optionally
They may together form a ring, and X is a sigma bond.
A ligand, a chelating ligand or a Lewis base, n
Is an integer of 0 to 6 that varies depending on the valence of M, and n is
In case of 2 or more, multiple Xs may be the same or different.
Good. ) A transition metal complex compound represented by the formula (B),
Reaction with the transition metal complex compound of component (A) or its derivative
To form an ionic complex by the following general formulas (II) and (II
I) ([L¹-R¹]^{k +})_p([Z]^-)_q   ... (II) ([L²]^{k +})_p([Z]^-)_q       ... (III) (However, L²Is M², R²R³M³, R^Four ₃C or R^FiveM³And
It ) [In the formulas (II) and (III), [Z]^-Is a non-coordinating anion
[Z¹]^-And [Z²]^-, Here [Z¹]^-Is based on multiple groups
The anion bound to the element, ie [M¹Y¹Y²... Yⁿ]
(Where M¹Is an element of Groups 5 to 15 of the Periodic Table, preferably
The elements of Groups 13 to 15 of the periodic table are shown. Y¹~ YⁿIs hydrogen
Child, halogen atom, organic metalloid group, amino group, al
Coxy group, hydrocarbon group or hydrocarbon group containing hetero atom
Show. Y¹~ YⁿTwo or more of them may form a ring
Yes. n is [(central metal M¹Valence of +1)
You ) [Z²]^-Has an acidity constant (pKa) of -10 or less
Bronsted acid alone or Bronsted acid and Lewis
Conjugate base of acid combination, or generally defined as super strong acid
Is a conjugated base. In addition, the Lewis base is coordinated
May be. Furthermore, L¹Is Lewis base, R¹Is a hydrogen atom
Represents a hydrocarbon group, R ²And R³Each is a cyclopen
A tadienyl group or a substituted cyclopentadienyl group is shown.
Each cyclopentadienyl group may be the same or different
Two or more cyclopentadienyl groups have a crosslinked structure.
You may. R^FourIs hydrocarbon group, hydrocarbon water containing hetero atom
R represents an elementary group or an alkoxy group, and R^FiveIs a porphyrin,
Examples include phthalocyanines and allyl group derivatives. k is
[L¹-R¹], [L²] With an ionic valence of 1 to 3 is an integer,
p is an integer of 1 or more, and q = (p × k). M²Is the cycle
It contains elements of Groups 1 to 11, 11 to 13 and 17 of the Periodic Table.
R, M³Indicates an element belonging to Groups 7 to 12 of the periodic table. ]]
Selected from ionic compounds and boron compounds
And one type, and (C) general formula (IV) R⁶ _rAlQ_r-3      ... (IV) (In the formula, R⁶Is an alkyl group having 1 to 12 carbon atoms, Q is hydrogen
Atom, alkoxy group having 1 to 20 carbon atoms or halogen atom
And r is a number from 1 to 3. ), Carbon number 3
Organic alumini having at least one of the above hydrocarbon groups
Olefin polymerization catalyst consisting of um compounds.