JP2011144293A - METHOD FOR PRODUCING POLY-alpha-OLEFIN - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing a poly-α-olefin exhibiting high activity. <P>SOLUTION: The method for producing a polyolefin is provided, comprising conducting a polymerization reaction under the reaction conditions meeting the requirements (a) to (d) described below, using a catalyst prepared by mutually contacting (A) a transition metal compound, (B) a boron compound forming an ion pair with the component (A), and (C) an organoaluminum compound. The requirements (a) to (d) are as follows: (a) 200≤c/a≤4,500, wherein a is the molar amount of the component (A) and c is the molar amount of the component (C); (b) when using a gaseous monomer, the amounts of carbonyl sulfide, carbon dioxide and carbon monoxide contained in the gaseous monomer are 20 mass ppb or less, 0.1 mol.ppm or less, and 0.1 mol.ppm or less, respectively; (c) when using a liquid monomer, the amounts of a monomer oxide(s) and moisture contained in the liquid monomer are 100 mass ppm or less and 10 mass ppm or less, respectively; and (d) when using a solvent, the amount of moisture contained in the solvent is 10 mass ppm or less. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a method for producing a poly α-olefin, and more particularly, a method for producing a poly α-olefin using a specific catalyst and reaction conditions satisfying specific requirements, and producing a poly α-olefin having high activity. Regarding the method.

  Conventionally, in the polymerization reaction of α-olefin, a polymerization catalyst (for example, a metallocene catalyst, a Ziegler catalyst, or the like) containing a transition metal compound and a promoter component has been usually used. It is preferable from an economical viewpoint to improve the activity in these polymerization reactions. Moreover, it is preferable to improve activity also from a viewpoint that the catalyst residue contained in a product can be reduced and product quality improves. Therefore, various technical developments have been made so far for the purpose of improving the activity of the polymerization reaction of α-olefin.

  This technical development includes the specification of transition metal compounds and promoter components, but in addition to this, the reaction conditions have been studied in detail. As a result, it has been found that compounds such as carbon monoxide and carbonyl sulfide are catalyst poisons for the polymerization catalyst, and various production methods have been developed based on this knowledge. For example, a method of performing a reaction by reducing these compounds to a certain amount or less by purifying a solvent, a monomer, or the like is known, and as a specific means, Patent Document 1 discloses an adsorption containing copper, zinc, and zirconium. A purification method using the composition is disclosed. In addition to this, a method of adding a scavenger to detoxify the compound remaining in the reaction system is known. For example, Patent Document 2 discloses an organoaluminum compound as a scavenger.

  Although these methods have been used to increase the polymerization reaction, aiming for higher activation, the degree of purification of solvents and monomers is increased more than before, and the amount of organoaluminum compound added is increased. However, the desired high activation could not be achieved, and conversely the activity was even reduced.

Japanese Patent Laid-Open No. 9-302015 JP 2001-329007 A

  This invention is made | formed in view of the said situation, and it aims at providing the manufacturing method of poly alpha olefin which shows activity higher than before.

As a result of intensive studies, the present inventors have found that the above-mentioned problem can be solved by performing a polymerization reaction under reaction conditions that satisfy a specific requirement using a specific catalyst. The present invention has been completed based on such findings.
That is, the present invention
1. (A) A transition metal compound, (B) a boron compound that forms an ion pair with the component (A), and (C) a polyolefin production method using a catalyst obtained by contacting an organoaluminum compound, wherein the following (a) ) To (d), a method for producing a polyolefin that undergoes a polymerization reaction under reaction conditions,
(A) When the amount of the component (A) is a mole and the amount of the component (C) is c mol,
200 ≦ c / a ≦ 4500
(B) In the case of using a gas monomer, the amount of carbonyl sulfide contained in the gas monomer is 20 mass ppb or less, the amount of carbon dioxide is 0.1 mol ppm or less, and the amount of carbon monoxide is 0.1 mol ppm or less. .
(C) When using a liquid monomer, the monomer oxide contained in the liquid monomer is 100 mass ppm or less and the water content is 10 mass ppm or less.
(D) When using a solvent, the amount of water contained in the solvent is 10 mass ppm or less.
2. The method for producing a polyolefin according to the above 1, wherein the monomer and the solvent are purified by an adsorbent,
3. The method for producing a polyolefin according to 1 or 2 above, wherein the organoaluminum is triisobutylaluminum.

  ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of poly alpha olefin which shows activity higher than before is provided.

[Polymerization catalyst]
The polymerization catalyst used in the present invention is a catalyst obtained by contacting (A) a transition metal compound, (B) a boron compound that forms an ion pair with the component (A), and (C) an organoaluminum compound. As will be described later, the amount ratio of the component (C) to the component (A) is important in the present invention. The component (C) in the present invention refers to the organoaluminum compound used in the polymerization reaction. Even if an organoaluminum compound is used in the prepolymerization reaction, this amount is not considered. This is because the amount of the organoaluminum compound derived from the prepolymerization reaction is small if it is a normal method of use, and it is considered that the effect of the present invention is hardly affected.

Examples of the transition metal compound (A) used in the present invention include chelate-type complexes, uncrosslinked ligands, and metallocene complexes having a crosslinked ligand.
Examples of the chelate-type complex include N, N′-bis (2,6-diisopropylphenyl) -1,2-dimethylethylenediiminonickel dibromide, N, N′-bis (2,6-diisopropylphenyl)- 1,2-dimethylethylenediiminopalladium dibromide and the like.
Examples of the metallocene complex having a non-bridged ligand include biscyclopentadienylzirconium dichloride, bis (n-butylcyclopentadienyl) zirconium dichloride, bis (pentamethylcyclopentadienyl) zirconium dichloride, and bisindene. And nilzirconium dichloride.
In the present invention, a metallocene complex in which a ligand forms a crosslinked structure via a crosslinking group has a higher polymerization activity than a metallocene complex in which a crosslinked structure is not formed.
Accordingly, among metallocene complexes, metallocene complexes in which a ligand forms a crosslinked structure via a crosslinking group are preferred, mono-bridged metallocene complexes and bi-bridged metallocene complexes are more preferred, and bi-bridged metallocene complexes are most preferred.
Examples of mono-bridged metallocene complexes include dimethylsilylene (tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) zirconium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (tert-butylamide) Zirconium dichloride, dimethylsilylenebis (2-methyl-4,5-benzoindenyl) zirconium dichloride, dimethylsilylenebis (2-methyl-4-phenylindenyl) zirconium dichloride, dimethylsilylenebis (2-methyl-4-naphthyl) Indenyl) zirconium dichloride, dimethylsilylene bis (2-methylindenyl) zirconium dichloride, ethylenebis (2-methylindenyl) zirconium dichloride, and the like.

  As the bibridged metallocene complex, the following general formula (I)

[In the formula, M represents a group 3-10 of the periodic table or a lanthanoid series metal element, and E ¹ and E ² represent a substituted cyclopentadienyl group, an indenyl group, a substituted indenyl group, a heterocyclopentadienyl group, respectively. A ligand selected from a substituted heterocyclopentadienyl group, an amide group, a phosphide group, a hydrocarbon group, and a silicon-containing group, which forms a crosslinked structure via A ¹ and A ² They may be the same as or different from each other, X represents a sigma-binding ligand, and when there are a plurality of X, the plurality of X may be the same or different, and other X, E ¹ , It may be cross-linked with E ² or Y. Y represents a Lewis base, and when there are a plurality of Y, the plurality of Y may be the same or different, may be cross-linked with other Y, E ¹ , E ² or X, and A ¹ and A ² are A divalent bridging group that binds two ligands, a hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, a germanium-containing group, a tin-containing group , -O -, - CO -, - S -, - SO 2 -, - Se -, - NR 1 -, - PR 1 -, - P (O) R 1 -, - BR 1 - or -AlR ¹ - R ¹ represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, which may be the same as or different from each other. q represents an integer of 1 to 5 and represents [(M valence) -2], and r represents an integer of 0 to 3. ]
The bibridged metallocene complex represented by these is mentioned.

In the general formula (I), M represents a metal element of Groups 3 to 10 of the periodic table or a lanthanoid series, and specific examples include titanium, zirconium, hafnium, yttrium, vanadium, chromium, manganese, nickel, cobalt, palladium, and Among them, lanthanoid metals are mentioned, and among these, titanium, zirconium and hafnium are preferable from the viewpoint of olefin polymerization activity.
E ¹ and E ² are respectively substituted cyclopentadienyl group, indenyl group, substituted indenyl group, heterocyclopentadienyl group, substituted heterocyclopentadienyl group, amide group (—N <), phosphine group (—P <), Hydrocarbon group [>CR-,> C <] and silicon-containing group [>SiR-,> Si <] (where R is hydrogen, a hydrocarbon group having 1 to 20 carbon atoms, or a heteroatom-containing group. A ligand selected from among (A), and a crosslinked structure is formed via A ¹ and A ² .
E ¹ and E ² may be the same as or different from each other.
As E ¹ and E ² , a substituted cyclopentadienyl group, an indenyl group, and a substituted indenyl group are preferable because the polymerization activity becomes higher.

X represents a σ-bonding ligand, and when there are a plurality of X, the plurality of X may be the same or different and may be cross-linked with other X, E ¹ , E ² or Y. .
Specific examples of X include a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, an amide group having 1 to 20 carbon atoms, and carbon. Examples thereof include a silicon-containing group having 1 to 20 carbon atoms, a phosphide group having 1 to 20 carbon atoms, a sulfide group having 1 to 20 carbon atoms, and an acyl group having 1 to 20 carbon atoms.
On the other hand, Y represents a Lewis base, and when there are a plurality of Y, the plurality of Y may be the same or different, and may be cross-linked with other Y, E ¹ , E ² or X. Specific examples of the Lewis base of Y include amines, ethers, phosphines, thioethers and the like.

Next, A ¹ and A ² are divalent bridging groups for bonding two ligands, which are a hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, silicon containing group, a germanium-containing group, a tin-containing group, -O -, - CO -, - S -, - SO 2 -, - Se -, - NR 1 -, - PR 1 -, - P (O) R 1 - , —BR ¹ — or —AlR ¹ —, wherein R ¹ represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, and they are the same as each other But it can be different.
Examples of such a crosslinking group include a general formula

(D is carbon, silicon or tin, R ² and R ³ are each a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, which may be the same as or different from each other, and are bonded to each other to form a ring structure. (E may represent an integer of 1 to 4)
The thing represented by is mentioned.
Specific examples thereof include a methylene group, an ethylene group, an ethylidene group, a propylidene group, an isopropylidene group, a cyclohexylidene group, a 1,2-cyclohexylene group, a vinylidene group (CH ₂ = C =), a dimethylsilylene group, and diphenyl. A silylene group, a methylphenylsilylene group, a dimethylgermylene group, a dimethylstannylene group, a tetramethyldisilylene group, a diphenyldisilylene group, and the like can be given.
Among these, an ethylene group, an isopropylidene group, and a dimethylsilylene group are preferable because the polymerization activity becomes higher.
q represents an integer of 1 to 5 and represents [(M valence) -2], and r represents an integer of 0 to 3.
Among such bibridged metallocene complexes represented by the general formula (I), the general formula (II)

A metallocene complex having a bibridged biscyclopentadienyl derivative represented by the formula as a ligand is preferable because the polymerization activity becomes higher.
In the general formula (II), M, A ¹ , A ² , q and r are the same as described above.
X ¹ represents a σ-bonding ligand, and when plural X ^1, a plurality of X ¹ may be the same or different, may be crosslinked with other X ¹ or Y ^1.
Specific examples of X ¹ include the same examples as those exemplified in the description of X in formula (I).
Y ¹ represents a Lewis base, if Y ¹ is plural, Y ¹ may be the same or different, may be crosslinked with other Y ¹ or X ^1.
Specific examples of Y ¹ are the same as those exemplified in the description of Y in the general formula (I).
R ^{4 to} R ⁹ each represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, or a heteroatom-containing group. One must not be a hydrogen atom.
R ^{4 to} R ⁹ may be the same as or different from each other, and adjacent groups may be bonded to each other to form a ring.
Of these, the polymerization activity becomes higher, R ⁶ and R ⁷ are the possible and R ⁸ form a ring R ⁹ is preferably to form a ring.
As R ⁴ and R ⁵ , a group containing a heteroatom such as oxygen, halogen, or silicon is preferable because of high polymerization activity.
The metallocene complex having the bibridged biscyclopentadienyl derivative as a ligand preferably contains silicon in the bridging group between the ligands.

  Specific examples of the bibridged metallocene complex represented by the general formula (I) include (1,2′-ethylene) (2,1′-ethylene) -bis (indenyl) zirconium dichloride, (1,2′-methylene). ) (2,1′-methylene) -bis (indenyl) zirconium dichloride, (1,2′-isopropylidene) (2,1′-isopropylidene) -bis (indenyl) zirconium dichloride, (1,2′-ethylene) ) (2,1′-ethylene) -bis (3-methylindenyl) zirconium dichloride, (1,2′-ethylene) (2,1′-ethylene) -bis (4,5-benzoindenyl) zirconium dichloride (1,2'-ethylene) (2,1'-ethylene) -bis (4-isopropylindenyl) zirconium dichloride, (1,2'-ethylene) 2,1′-ethylene) -bis (5,6-dimethylindenyl) zirconium dichloride, (1,2′-ethylene) (2,1′-ethylene) -bis (4,7-diisopropylindenyl) zirconium dichloride , (1,2'-ethylene) (2,1'-ethylene) -bis (4-phenylindenyl) zirconium dichloride, (1,2'-ethylene) (2,1'-ethylene) -bis (3- Methyl-4-isopropylindenyl) zirconium dichloride, (1,2'-ethylene) (2,1'-ethylene) -bis (5,6-benzoindenyl) zirconium dichloride, (1,2'-ethylene) ( 2,1′-isopropylidene) -bis (indenyl) zirconium dichloride, (1,2′-methylene) (2,1′-ethylene) -bis (indeni ) Zirconium dichloride, (1,2'-methylene) (2,1'-isopropylidene) -bis (indenyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) bis (indenyl) ) Zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) bis (3-methylindenyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) ) Bis (3-n-butylindenyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) bis (3-isopropylindenyl) zirconium dichloride, (1,2'-dimethyl) Silylene) (2,1′-dimethylsilylene) bis (3-trimethylsilylmethylin) (Denyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) bis (3-phenylindenyl) zirconium dichloride,

(1,2'-dimethylsilylene) (2,1'-dimethylsilylene) bis (4,5-benzoindenyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) bis (4-Isopropylindenyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) bis (5,6-dimethylindenyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1′-dimethylsilylene) bis (4,7-di-isopropylindenyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) bis (4-phenylindenyl) Zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) bis (3-methyl) -4-Isopropylindenyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) bis (5,6-benzoindenyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1′-isopropylidene) -bis (indenyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-isopropylidene) -bis (3-methylindenyl) zirconium dichloride, (1, 2'-dimethylsilylene) (2,1'-isopropylidene) -bis (3-isopropylindenyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-isopropylidene) -bis (3- n-butylindenyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1 -Isopropylidene) -bis (3-trimethylsilylmethylindenyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-isopropylidene) -bis (3-trimethylsilylindenyl) zirconium dichloride, (1, 2'-dimethylsilylene) (2,1'-isopropylidene) -bis (3-phenylindenyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-methylene) -bis (indenyl) zirconium Dichloride, (1,2'-dimethylsilylene) (2,1'-methylene) -bis (3-methylindenyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-methylene) -bis (3-Isopropylindenyl) zirconium dichloride, (1,2'-dimethylsilane) Rylene) (2,1′-methylene) -bis (3-n-butylindenyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-methylene) -bis (3-trimethylsilylmethylindenyl) ) Zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-methylene) -bis (3-trimethylsilylindenyl) zirconium dichloride,

(1,2'-diphenylsilylene) (2,1'-methylene) -bis (indenyl) zirconium dichloride, (1,2'-diphenylsilylene) (2,1'-methylene) -bis (3-methylindenyl) ) Zirconium dichloride, (1,2'-diphenylsilylene) (2,1'-methylene) -bis (3-isopropylindenyl) zirconium dichloride, (1,2'-diphenylsilylene) (2,1'-methylene) -Bis (3-n-butylindenyl) zirconium dichloride, (1,2'-diphenylsilylene) (2,1'-methylene) -bis (3-trimethylsilylmethylindenyl) zirconium dichloride, (1,2'- Diphenylsilylene) (2,1′-methylene) -bis (3-trimethylsilylindenyl) zirconium dimethyl Lido, (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) (3-methylcyclopentadienyl) (3'-methylcyclopentadienyl) zirconium dichloride, (1,2'-dimethylsilylene) ) (2,1′-isopropylidene) (3-methylcyclopentadienyl) (3′-methylcyclopentadienyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-ethylene) ( 3-methylcyclopentadienyl) (3′-methylcyclopentadienyl) zirconium dichloride, (1,2′-ethylene) (2,1′-methylene) (3-methylcyclopentadienyl) (3′- Methylcyclopentadienyl) zirconium dichloride, (1,2'-ethylene) (2,1'-isopropylidene) (3-methylsilane Lopentadienyl) (3′-methylcyclopentadienyl) zirconium dichloride, (1,2′-methylene) (2,1′-methylene) (3-methylcyclopentadienyl) (3′-methylcyclopentadienyl) Zirconium dichloride, (1,2'-methylene) (2,1'-isopropylidene) (3-methylcyclopentadienyl) (3'-methylcyclopentadienyl) zirconium dichloride, (1,2'-isopropylidene ) (2,1′-isopropylidene) (3-methylcyclopentadienyl) (3′-methylcyclopentadienyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) (3,4-Dimethylcyclopentadienyl) (3 ′, 4′-dimethylcyclopentadienyl) zirco Nium dichloride, (1,2'-dimethylsilylene) (2,1'-isopropylidene) (3,4-dimethylcyclopentadienyl) (3 ', 4'-dimethylcyclopentadienyl) zirconium dichloride,

(1,2′-dimethylsilylene) (2,1′-ethylene) (3,4-dimethylcyclopentadienyl) (3 ′, 4′-dimethylcyclopentadienyl) zirconium dichloride, (1,2′- Ethylene) (2,1′-methylene) (3,4-dimethylcyclopentadienyl) (3 ′, 4′-dimethylcyclopentadienyl) zirconium dichloride, (1,2′-ethylene) (2,1 ′ -Isopropylidene) (3,4-dimethylcyclopentadienyl) (3 ′, 4′-dimethylcyclopentadienyl) zirconium dichloride, (1,2′-methylene) (2,1′-methylene) (3 4-dimethylcyclopentadienyl) (3 ′, 4′-dimethylcyclopentadienyl) zirconium dichloride, (1,2′-methylene) (2,1′-isopropyl Ridene) (3,4-dimethylcyclopentadienyl) (3 ′, 4′-dimethylcyclopentadienyl) zirconium dichloride, (1,2′-isopropylidene) (2,1′-isopropylidene) (3 4-dimethylcyclopentadienyl) (3 ′, 4′-dimethylcyclopentadienyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) (3-methyl-5-ethyl) Cyclopentadienyl) (3′-methyl-5′-ethylcyclopentadienyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) (3-methyl-5-ethylcyclohexane) Pentadienyl) (3′-methyl-5′-ethylcyclopentadienyl) zirconium dichloride, (1,2′-dimethyl) Rylene) (2,1′-dimethylsilylene) (3-methyl-5-isopropylcyclopentadienyl) (3′-methyl-5′-isopropylcyclopentadienyl) zirconium dichloride, (1,2′-dimethylsilylene) ) (2,1′-dimethylsilylene) (3-methyl-5-n-butylcyclopentadienyl) (3′-methyl-5′-n-butylcyclopentadienyl) zirconium dichloride, (1,2 ′ -Dimethylsilylene) (2,1′-dimethylsilylene) (3-methyl-5-phenylcyclopentadienyl) (3′-methyl-5′-phenylcyclopentadienyl) zirconium dichloride, (1,2′-dimethyl) Silylene) (2,1′-isopropylidene) (3-methyl-5-ethylcyclopentadienyl) (3′-methyl-5 ′ -Ethylcyclopentadienyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-isopropylidene) (3-methyl-5-isopropylcyclopentadienyl) (3'-methyl-5'- Isopropylcyclopentadienyl) zirconium dichloride,

(1,2'-dimethylsilylene) (2,1'-isopropylidene) (3-methyl-5-n-butylcyclopentadienyl) (3'-methyl-5'-n-butylcyclopentadienyl) Zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-isopropylidene) (3-methyl-5-phenylcyclopentadienyl) (3'-methyl-5'-phenylcyclopentadienyl) zirconium dichloride (1,2'-dimethylsilylene) (2,1'-ethylene) (3-methyl-5-ethylcyclopentadienyl) (3'-methyl-5'-ethylcyclopentadienyl) zirconium dichloride, ( 1,2′-dimethylsilylene) (2,1′-ethylene) (3-methyl-5-isopropylcyclopentadienyl) (3′-methyl-5 ′ Isopropylcyclopentadienyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-ethylene) (3-methyl-5-n-butylcyclopentadienyl) (3'-methyl-5'- n-butylcyclopentadienyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-ethylene) (3-methyl-5-phenylcyclopentadienyl) (3'-methyl-5'- Phenylcyclopentadienyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-methylene) (3-methyl-5-ethylcyclopentadienyl) (3'-methyl-5'-ethylcyclo Pendienyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-methylene) (3-methyl-5-isopropylene) Cyclopentadienyl) (3′-methyl-5′-isopropylcyclopentadienyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-methylene) (3-methyl-5-n-butyl) Cyclopentadienyl) (3′-methyl-5′-n-butylcyclopentadienyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-methylene) (3-methyl-5-phenyl) Cyclopentadienyl) (3'-methyl-5'-phenylcyclopentadienyl) zirconium dichloride, (1,2'-ethylene) (2,1'-methylene) (3-methyl-5-isopropylcyclopentadi Enyl) (3′-methyl-5′-isopropylcyclopentadienyl) zirconium dichloride, (1,2′-ethylene) (2,1 ′ -Isopropylidene) (3-methyl-5-isopropylcyclopentadienyl) (3'-methyl-5'-isopropylcyclopentadienyl) zirconium dichloride,

(1,2′-methylene) (2,1′-methylene) (3-methyl-5-isopropylcyclopentadienyl) (3′-methyl-5′-isopropylcyclopentadienyl) zirconium dichloride, (1, 2'-methylene) (2,1'-isopropylidene) (3-methyl-5-isopropylcyclopentadienyl) (3'-methyl-5'-isopropylcyclopentadienyl) zirconium dichloride, (1,1 ' -Dimethylsilylene) (2,2'-dimethylsilylene) bisindenylzirconium dichloride, (1,1'-diphenylsilylene) (2,2'-dimethylsilylene) bisindenylzirconium dichloride, (1,1'-dimethyl Silylene) (2,2′-dimethylsilylene) bisindenylzirconium dichloride, (1,1′-di) Sopropylsilylene) (2,2′-dimethylsilylene) bisindenylzirconium dichloride, (1,1′-dimethylsilylene) (2,2′-diisopropylsilylene) bisindenylzirconium dichloride, (1,1′-dimethyl Silylene indenyl) (2,2′-dimethylsilylene-3-trimethylsilylindenyl) zirconium dichloride, (1,1′-diphenylsilylene indenyl) (2,2′-diphenylsilylene-3-trimethylsilylindenyl) zirconium dichloride , (1,1′-diphenylsilyleneindenyl) (2,2′-dimethylsilylene-3-trimethylsilylindenyl) zirconium dichloride, (1,1′-dimethylsilyleneindenyl) (2,2′-diphenylsilylene- 3-trimethylsilyl Indenyl) zirconium dichloride, (1,1′-diisopropylsilyleneindenyl) (2,2′-dimethylsilylene-3-trimethylsilylindenyl) zirconium dichloride, (1,1′-dimethylsilyleneindenyl) (2,2 ′ -Diisopropylsilylene-3-trimethylsilylindenyl) zirconium dichloride, (1,1'-diisopropylsilyleneindenyl) (2,2'-diisopropylsilylene-3-trimethylsilylindenyl) zirconium dichloride, (1,1'-dimethylsilylene) Indenyl) (2,2′-dimethylsilylene-3-trimethylsilylmethylindenyl) zirconium dichloride, (1,1′-diphenylsilyleneindenyl) (2,2′-diphenylsilylene-3-trimethylsilylmethyl) (Luindenyl) zirconium dichloride, (1,1'-diphenylsilyleneindenyl) (2,2'-dimethylsilylene-3-trimethylsilylmethylindenyl) zirconium dichloride,

(1,1′-dimethylsilyleneindenyl) (2,2′-diphenylsilylene-3-trimethylsilylmethylindenyl) zirconium dichloride, (1,1′-diisopropylsilyleneindenyl) (2,2′-dimethylsilylene- 3-trimethylsilylmethylindenyl) zirconium dichloride, (1,1′-dimethylsilyleneindenyl) (2,2′-diisopropylsilylene-3-trimethylmethylsilylindenyl) zirconium dichloride, (1,1′-diisopropylsilyleneindene) Nyl) (2,2′-diisopropylsilylene-3-trimethylmethylsilylindenyl) zirconium dichloride and the like and those obtained by replacing zirconium in these compounds with titanium or hafnium.
Of course, it is not limited to these.
Further, it may be an analogous compound of another group or a lanthanoid series metal element.
In the above compound, (1,1 ′ −) (2,2′−) may be (1,2 ′ −) (2,1′−), or (1,2 ′ −) (2 , 1'-) may be (1, 1'-) (2, 2'-).

Examples of the component (A) other than the above include the following.
Dichloro [dimethylsilylene (cyclopentadienyl) (2,4-dimethyl-4H-1-azulenyl)] hafnium, dichloro [dimethylsilylene (2-methyl-1-cyclopentadienyl) (2,4-dimethyl-4H -1-azulenyl)] hafnium, dichloro [dimethylsilylene (cyclopentadienyl) (2-methyl-4-phenyl-4H-1-azurenyl)] hafnium, dichloro [dimethylsilylene (cyclopentadienyl) (2-methyl -4-isopropyl-4H-1-azulenyl)] hafnium, dichloro [dimethylsilylene (2-ethyl-1-cyclopentadienyl) (2,4-dimethyl-4H-1-azurenyl)] hafnium, dichloro [dimethylsilylene (9-fluorenyl) (2,4-dimethyl-4H-1-azuleni )] Hafnium, dichloro [dimethylsilylene (cyclopentadienyl) (2-ethyl-4-methyl-4H-1-azulenyl)] hafnium, dichloro [dimethylsilylene (2-methyl-1-cyclopentadienyl) (2 -Ethyl-4-methyl-4H-1-azulenyl)] hafnium, dichloro [dimethylsilylene (cyclopentadienyl) (2-ethyl-4-phenyl-4H-1-azurenyl)] hafnium, dichloro [dimethylsilylene (cyclo Pentadienyl) (2-ethyl-4-isopropyl-4H-1-azurenyl)] hafnium, dichloro [dimethylsilylene (9-fluorenyl) (2-ethyl-4-methyl-4H-1-azurenyl)] hafnium, dichloro [Dimethylsilylene (2,3-dimethyl-1-cyclopentadieny ) (2-Ethyl-4-methyl-4H-1-azurenyl)] hafnium, dichloro [ethylene (cyclopentadienyl) (2,4-dimethyl-4H-1-azurenyl)] hafnium, dichloro [ethylene (2- Methyl-1-cyclopentadienyl) (2,4-dimethyl-4H-1-azurenyl)] hafnium, dichloro [ethylene (cyclopentadienyl) (2-methyl-4-phenyl-4H-1-azurenyl)] Hafnium, dichloro [ethylene (cyclopentadienyl) (2-methyl-4-isopropyl-4H-1-azulenyl)] hafnium, dichloro [ethylene (2-methyl-1-cyclopentadienyl) (2,4-dimethyl -4H-1-azulenyl)] hafnium, dichloro [ethylene (9-fluorenyl) (2,4-dimethyl-4 H-1-azulenyl)] hafnium, dichloro [ethylene (cyclopentadienyl) (2-ethyl-4-methyl-4H-1-azurenyl)] hafnium, dichloro [ethylene (2-methyl-1-cyclopentadienyl) ) (2-Ethyl-4-methyl-4H-1-azurenyl)] hafnium, dichloro [dimethylsilylene (2-methyl-1-cyclopentadienyl) (2-ethyl-4-phenyl-4H-1-azurenyl) ] Hafnium, dichlorodimethylsilylene (2-methyl-1-cyclopentadienyl) (2-ethyl-4-isopropyl-4H-1-azurenyl)] hafnium, dichloro [ethylene (9-fluorenyl) (2-ethyl-4 -Methyl-4H-1-azulenyl)] hafnium, dichloro [ethylene (9-fluorenyl) (2-ethyl Ru-4-isopropyl-4H-1-azulenyl)] hafnium, dichloro [dimethylsilylene (cyclopentadienyl) (2-n-propyl-4-methyl-4H-1-azurenyl)] hafnium, dichloro [dimethylsilylene ( Cyclopentadienyl) (2-isopropyl-4-methyl-4H-1-azurenyl)] hafnium, dichloro [dimethylsilylene (cyclopentadienyl) (2-n-butyl-4-methyl-4H-1-azurenyl) ] Hafnium, dichloro [dimethylsilylene (2-methyl-1-cyclopentadienyl) (2-n-propyl-4-methyl-4H-1-azulenyl)] hafnium, dichloro [dimethylsilylene (2-methyl-1- Cyclopentadienyl) (2-isopropyl-4-methyl-4H-1-azulenyl) Hafnium, dichloro [dimethylsilylene (2-methyl-1-cyclopentadienyl) (2-n-butyl-4-methyl-4H-1-azulenyl)] hafnium, dichloro [dimethylsilylene (cyclopentadienyl) (2 , 4,8-trimethyl-4H-1-azulenyl)] hafnium, dichloro [dimethylsilylene (cyclopentadienyl) (2,4,6-trimethyl-4H-1-azurenyl)] hafnium, dichloro [dimethylsilylene (cyclo Pentadienyl) (2,4,7-trimethyl-4H-1-azurenyl)] hafnium, dichloro [dimethylsilylene (cyclopentadienyl) (2,4-dimethyl-6-isopropyl-4H-1-azurenyl)] Hafnium, dichloro [dimethylsilylene (cyclopentadienyl) (2,4-di Methyl-7-isopropyl-4H-1-azulenyl)] hafnium, dichloro [dimethylsilylene (cyclopentadienyl) (2,4-dimethyl-8-isopropyl-4H-1-azulenyl)] hafnium, dichloro [dimethylsilylene ( Cyclopentadienyl) (2,4-dimethyl-6-ethyl-4H-1-azulenyl)] hafnium, dichloro [dimethylsilylene (cyclopentadienyl) (2,4-dimethyl-7-ethyl-4H-1- Azulenyl)] hafnium, dichloro [dimethylsilylene (cyclopentadienyl) (2,4-dimethyl-8-ethyl-4H-1-azurenyl)] hafnium, dichloro [[di (chloromethyl) silylene] (cyclopentadienyl) ) (2,4-Dimethyl-4H-1-azurenyl)] hafnium, dichroic [[Di (4-chlorophenyl) silylene] (cyclopentadienyl) (2,4-dimethyl-4H-1-azulenyl)] hafnium, dichloro [dimethylmethylene (cyclopentadienyl) (2,4-dimethyl-4H -1-azulenyl)] hafnium,

Dichloro [dimethylgermylene (cyclopentadienyl) (2,4-dimethyl-4H-1-azurenyl)] hafnium, dichloro [dimethylgermylene (2-methyl-1-cyclopentadienyl) (2,4-dimethyl -4H-1-azulenyl)] hafnium, dichloro [dimethylgermylene (2,3-dimethyl-1-cyclopentadienyl) (2,4-dimethyl-4H-1-azurenyl)] hafnium, dichloro [dimethylgermylene (9-fluorenyl) (2,4-dimethyl-4H-1-azurenyl)] hafnium, dichloro [dimethylgermylene (cyclopentadienyl) (2-ethyl-4-methyl-4H-1-azurenyl)] hafnium, Dichloro [dimethylgermylene (cyclopentadienyl) (2-n-propyl-4-methyl-4 -1-azurenyl)] hafnium, dichloro [dimethylgermylene (cyclopentadienyl) (2-isopropyl-4H-1-azurenyl)] hafnium, dichloro [dimethylgermylene (cyclopentadienyl) (2-n-butyl) -4-methyl-4H-1-azurenyl)] hafnium, dichloro [dimethylgermylene (2-methyl-1-cyclopentadienyl) (2-ethyl-4-methyl-4H-1-azurenyl)] hafnium, dichloro [Dimethylgermylene (2,3-dimethyl-1-cyclopentadienyl) (2-ethyl-4-methyl-4H-1-azurenyl)] hafnium, dichloro [dimethylgermylene (9-fluorenyl) (2-ethyl -4-methyl-4H-1-azulenyl)] hafnium, dichloro [dimethylgermylene ( -Methyl-1-cyclopentadienyl) (2-n-propyl-4-methyl-4H-1-azulenyl)] hafnium, dichloro [dimethylgermylene (2,3-dimethyl-1-cyclopentadienyl) ( 2-n-propyl-4-methyl-4H-1-azurenyl)] hafnium, dichloro [dimethylgermylene (9-fluorenyl) (2-n-propyl-4-methyl-4H-1-azurenyl)] hafnium,

Dichloro [dimethylsilylene (3-trimethylsilyl-1-cyclopentadienyl) (2,4-dimethyl-4H-1-azulenyl)] hafnium, dichloro [dimethylsilylene (3-trimethylsilyl-1-cyclopentadienyl) (2 -Ethyl-4-methyl-4H-1-azulenyl)] hafnium, dichloro [dimethylgermylene (3-trimethylsilyl-1-cyclopentadienyl) (2,4-dimethyl-4H-1-azulenyl)] hafnium, dichloro [Dimethylgermylene (3-trimethylsilyl-1-cyclopentadienyl) (2-ethyl-4-methyl-4H-1-azurenyl)] hafnium, dibromo [dimethylsilylene (cyclopentadienyl) (2,4-dimethyl -4H-1-azulenyl)] hafnium, dibromo [dimethyl] Silylene (2-methyl-1-cyclopentadienyl) (2,4-dimethyl-4H-1-azulenyl)] hafnium, dibromo [dimethylsilylene (2,3-dimethyl-1-cyclopentadienyl) (2, 4-dimethyl-4H-1-azulenyl)] hafnium, dibromo [dimethylsilylene (9-fluorenyl) (2,4-dimethyl-4H-1-azurenyl)] hafnium, diiodo [dimethylsilylene (cyclopentadienyl) (2 , 4-Dimethyl-4H-1-azulenyl)] hafnium, diiodo [dimethylsilylene (2-methyl-1-cyclopentadienyl) (2,4-dimethyl-4H-1-azurenyl)] hafnium, diiodo [dimethylsilylene (2,3-Dimethyl-1-cyclopentadienyl) (2,4-dimethyl-4H-1- Dusenyl)] hafnium, diiodo [dimethylsilylene (9-fluorenyl) (2,4-dimethyl-4H-1-azurenyl)] hafnium, dimethyl [dimethylsilylene (cyclopentadienyl) (2,4-dimethyl-4H-1 -Azulenyl)] hafnium, dimethyl [dimethylsilylene (2-methyl-1-cyclopentadienyl) (2,4-dimethyl-4H-1-azurenyl)] hafnium, dimethyl [dimethylsilylene (2,3-dimethyl-1) -Cyclopentadienyl) (2,4-dimethyl-4H-1-azurenyl)] hafnium, dimethyl [dimethylsilylene (9-fluorenyl) (2,4-dimethyl-4H-1-azurenyl)] hafnium, dihydride [dimethyl Silylene (cyclopentadienyl) (2,4-dimethyl 4H-1-a Dusenyl)] hafnium, dihydrido [dimethylsilylene (2-methyl-1-cyclopentadienyl) (2,4-dimethyl-4H-1-azurenyl)] hafnium, dihydrido [dimethylsilylene (2,3-dimethyl-1- Cyclopentadienyl) (2,4-dimethyl-4H-1-azurenyl)] hafnium, dihydrido [dimethylsilylene (9-fluorenyl) (2,4-dimethyl-4H-1-azurenyl)] hafnium, bis (dimethylamide) ) [Dimethylsilylene (cyclopentadienyl) (2,4-dimethyl-4H-1-azulenyl)] hafnium, bis (dimethylamido) [dimethylsilylene (2-methyl-1-cyclopentadienyl) (2,4 -Dimethyl-4H-1-azulenyl)] hafnium, bis (dimethylamide) [dimethyl Lucylylene (2,3-dimethyl-1-cyclopentadienyl) (2,4-dimethyl-4H-1-azurenyl)] hafnium, bis (dimethylamide) [dimethylsilylene (9-fluorenyl) (2,4-dimethyl -4H-1-azulenyl)] hafnium, bisphenoxy [dimethylsilylene (cyclopentadienyl) (2,4-dimethyl-4H-1-azurenyl)] hafnium, bisphenoxy [dimethylsilylene (2-methyl-1-cyclo Pentadienyl) (2,4-dimethyl-4H-1-azurenyl)] hafnium, bisphenoxy [dimethylsilylene (2,3-dimethyl-1-cyclopentadienyl) (2,4-dimethyl-4H-1- Azulenyl)] hafnium, bisphenoxy [dimethylsilylene (9-fluorenyl) (2,4- Methyl-4H-1-azurenyl)] hafnium, bismethanesulfinato [dimethylsilylene (cyclopentadienyl) (2,4-dimethyl-4H-1-azurenyl)] hafnium, bismethanesulfinato [dimethylsilylene ( 2-methyl-1-cyclopentadienyl) (2,4-dimethyl-4H-1-azulenyl)] hafnium, bismethanesulfinato [dimethylsilylene (2,3-dimethyl-1-cyclopentadienyl) ( 2,4-dimethyl-4H-1-azurenyl)] hafnium, bismethanesulfinato [dimethylsilylene (9-fluorenyl) (2,4-dimethyl-4H-1-azurenyl)] hafnium, bistrifluoromethanesulfinato [Dimethylsilylene (cyclopentadienyl) (2,4-dimethyl-4H-1-a Dusenyl)] hafnium, bistrifluoromethanesulfinato [dimethylsilylene (2-methyl-1-cyclopentadienyl) (2,4-dimethyl-4H-1-azurenyl)] hafnium, bistrifluoromethanesulfinato [dimethyl Silylene (2,3-dimethyl-1-cyclopentadienyl) (2,4-dimethyl-4H-1-azurenyl)] hafnium, bistrifluoromethanesulfinato [dimethylsilylene (9-fluorenyl) (2,4- Dimethyl-4H-1-azurenyl)] hafnium, bis-p-toluenesulfinato [dimethylsilylene (cyclopentadienyl) (2,4-dimethyl-4H-1-azurenyl)] hafnium, bis-p-toluenes Rufinato [dimethylsilylene (2-methyl-1-cyclopentadieny ) (2,4-Dimethyl-4H-1-azulenyl)] hafnium, bis-p-toluenesulfinato [dimethylsilylene (2,3-dimethyl-1-cyclopentadienyl) (2,4-dimethyl-4H -1-azurenyl)] hafnium, bis-p-toluenesulfinato [dimethylsilylene (9-fluorenyl) (2,4-dimethyl-4H-1-azurenyl)] hafnium, dichloro [dimethylsilylene (1-indenyl) ( 2,4-dimethyl-4H-1-azulenyl)] hafnium, dichloro [dimethylsilylene (2-methyl-1-indenyl) (2,4-dimethyl-4H-1-azurenyl)] hafnium, dichloro [dimethylsilylene (1 -Indenyl) (2-ethyl-4-methyl-4H-1-azulenyl)] hafnium, dichloro [dimethyl Lucylylene (2-methyl-1-indenyl) (2-ethyl-4-methyl-4H-1-azurenyl)] hafnium, dibromo [dimethylsilylene (1-indenyl) (2,4-dimethyl-4H-1-azurenyl) ] Hafnium, dibromo [dimethylsilylene (2-methyl-1-indenyl) (2,4-dimethyl-4H-1-azulenyl)] hafnium, dibromo [dimethylsilylene (1-indenyl) (2-ethyl-4-methyl-) 4H-1-azulenyl)] hafnium, dibromo [dimethylsilylene (2-methyl-1-indenyl) (2-ethyl-4-methyl-4H-1-azurenyl)] hafnium, diiodo [dimethylsilylene (1-indenyl) ( 2,4-dimethyl-4H-1-azurenyl)] hafnium, diiodo [dimethylsilylene ( 2-Methyl-1-indenyl) (2,4-dimethyl-4H-1-azurenyl)] hafnium, diiodo [dimethylsilylene (1-indenyl) (2-ethyl-4-methyl-4H-1-azurenyl)] hafnium Diiodo [dimethylsilylene (2-methyl-1-indenyl) (2-ethyl-4-methyl-4H-1-azulenyl)] hafnium, dimethyl [dimethylsilylene (1-indenyl) (2,4-dimethyl-4H- 1-azulenyl)] hafnium, dimethyl [dimethylsilylene (2-methyl-1-indenyl) (2,4-dimethyl-4H-1-azurenyl)] hafnium, dimethyl [dimethylsilylene (1-indenyl) (2-ethyl- 4-methyl-4H-1-azulenyl)] hafnium, dimethyl [dimethylsilylene (2-methyl- -Indenyl) (2-ethyl-4-methyl-4H-1-azulenyl)] hafnium, dichloro [dimethylsilylene (cyclopentadienyl) (2,4-dimethyl4H-5,6,7,8-tetrahydro-1 -Azurenyl)] hafnium, dichloro [dimethylsilylene (2-methyl-1-cyclopentadienyl) (2,4-dimethyl-4H-5,6,7,8-tetrahydro-1-azurenyl)] hafnium, dichloro [ Dimethylsilylene (2-methyl-1-indenyl) (2,4-dimethyl-4H-5,6,7,8-tetrahydro-1-azulenyl)] hafnium, dichloro [dimethylsilylene (9-fluorenyl) (2,4 -Dimethyl-4H-5,6,7,8-tetrahydro-1-azulenyl)] hafnium, dichloro [dimethylsilylene ( Clopentadienyl) (2-chloromethyl-4-methyl-4H-1-azurenyl)] hafnium, dichloro [dimethylsilylene (cyclopentadienyl) (2-methyl-4-chloromethyl-4H-1-azurenyl) ]hafnium

  Further, instead of hafnium in these exemplary compounds, compounds in place of titanium and zirconium can also be exemplified.

Examples of the boron compound that forms an ion pair with the component (A), which is the component (B) used in the present invention, include a coordination complex compound composed of an anion and a cation in which a plurality of groups are bonded to boron.
There are various coordination complex compounds composed of an anion and a cation in which a plurality of groups are bonded to boron. For example, a compound represented by the general formula (III) or (IV) can be preferably used.
([L ¹ −H] ^{s +} ) _t ([BZ ¹ Z ² Z ³ Z ⁴ ] ⁻ ) ₁ (III)
([L ² ] ^{s +} ) _t ([BZ ¹ Z ² Z ³ Z ⁴ ] ⁻ ) ₁ ... (IV)
[In Formula (III) or (IV), L ² is M ¹ , R ¹⁰ R ¹¹ M ² or R ¹² ₃ C described later, L ¹ is a Lewis base, M ¹ is Group ¹ of the periodic table and 8 Metal selected from group 12 to group 12, M ² is a metal selected from group 8 to group 10 of the periodic table, Z ^{1 to} Z ⁴ are hydrogen atom, dialkylamino group, alkoxy group, aryloxy group, carbon number 1 -20 alkyl group, C6-C20 aryl group, alkylaryl group, arylalkyl group, substituted alkyl group, organic metalloid group or halogen atom.
R ¹⁰ and R ¹¹ each represent a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group or a fluorenyl group, and R ¹² represents an alkyl group.
s is an integer of 1 to 7 in terms of ionic valence of L ¹ -H and L ² , t is an integer of 1 or more, and l = t × s). ]

M ¹ is a metal selected from groups 1 and 8 to 12 of the periodic table, specific examples are Ag, Cu, Na, Li and other atoms, and M ² is selected from groups 8 to 10 of the periodic table. Specific examples of metals that can be used include atoms such as Fe, Co, and Ni.
Specific examples of Z ^{1 to} Z ⁴ include, for example, a dimethylamino group and a diethylamino group as a dialkylamino group, a methoxy group, an ethoxy group, and an n-butoxy group as an alkoxy group, a phenoxy group as an aryloxy group, and 2, 6 -As a C1-C20 alkyl group, such as a dimethylphenoxy group and a naphthyloxy group, carbon such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an n-octyl group, and a 2-ethylhexyl group A phenyl group, p-tolyl group, benzyl group, pentafluorophenyl group, 3,5-di (trifluoromethyl) phenyl group, 4-tertiary-butyl as an aryl group, alkylaryl group or arylalkyl group of formula 6-20 Phenyl group, 2,6-dimethylphenyl group, 3,5-dimethylphenyl group, , 4-dimethylphenyl group, 1,2-dimethylphenyl group, halogen such as F, Cl, Br, I, organic metalloid group tetramethylantimony group, trimethylsilyl group, trimethylgermyl group, diphenylarsine group, dicyclohexylantimony group, And diphenylboron group.
Specific examples of the substituted cyclopentadienyl group represented by each of R ¹⁰ and R ¹¹ include a methylcyclopentadienyl group, a butylcyclopentadienyl group, and a pentamethylcyclopentadienyl group.

In the present invention, specific examples of anions in which a plurality of groups are bonded to boron include B (C ₆ F ₅ ) ₄ ⁻ , B (C ₆ HF ₄ ) ₄ ⁻ , and B (C ₆ H ₂ F ₃ ). ₄ ⁻ , B (C ₆ H ₃ F ₂ ) ₄ ⁻ , B (C ₆ H ₄ F) ₄ ⁻ , B (C ₆ CF ₃ F ₄ ) ₄ ⁻ , B (C ₆ H ₅ ) ₄ ⁻ , BF ₄ ^- and the like.
Further, as metal cations, Cp ₂ Fe ⁺ , (MeCp) ₂ Fe ⁺ , (tBuCp) ₂ Fe ⁺ , (Me ₂ Cp) ₂ Fe ⁺ , (Me ₃ Cp) ₂ Fe ⁺ , (Me ₄ Cp) ₂ Fe ⁺ , (Me ₅ Cp) ₂ Fe ⁺ , Ag ⁺ , Na ⁺ , Li ^{+ and the} like can be mentioned, and other cations include pyridinium, 2,4-dinitro-N, N-diethylanilinium, diphenylammonium. , Nitrogen-containing compounds such as p-nitroanilinium, 2,5-dichloroaniline, p-nitro-N, N-dimethylanilinium, quinolinium, N, N-dimethylanilinium, N, N-diethylanilinium, Carbenium compounds such as phenyl carbenium, tri (4-methylphenyl) carbenium, tri (4-methoxyphenyl) carbenium, CH ₃ PH ₃ ⁺ , C ₂ H ₅ PH ₃ ⁺ , C ₃ H ₇ PH ₃ ⁺ , (CH ₃ ) ₂ PH ₂ ⁺ , (C ₂ H ₅ ) ₂ PH ₂ ⁺ , (C ₃ H ₇ ) ₂ PH ₂ ⁺ , (CH ^{_{3) 3 PH +, (C}} 2 H 5) 3 PH +, (C 3 H 7) 3 PH +, (CF 3) 3 PH +, (CH 3) 4 P +, (C 2 H 5) 4 P ⁺ , Alkylphosphonium ions such as (C ₃ H ₇ ) ₄ P ⁺ , and C ₆ H ₅ PH ₃ ⁺ , (C ₆ H ₅ ) ₂ PH ₂ ⁺ , (C ₆ H ₅ ) ₃ PH ⁺ , (C ^{_{6 H 5) 4 P +,}} (C 2 H 5) 2 (C 6 H 5) PH +, (CH 3) (C 6 H 5) PH 2 +, (CH 3) 2 (C 6 H 5) PH ⁺ , Arylphosphonium ions such as (C ₂ H ₅ ) ₂ (C ₆ H ₅ ) ₂ P ⁺ and the like.
In the present invention, a coordination complex compound comprising any combination of the above metal cation and anion is exemplified.

Among the compounds of the general formulas (III) and (IV), specifically, the following can be used particularly preferably.
Examples of the compound of general formula (III) include triethylammonium tetraphenylborate, tri (n-butyl) ammonium tetraphenylborate, trimethylammonium tetraphenylborate, triethylammonium tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) ) Tri (n-butyl) ammonium borate, triethylammonium hexafluoroarsenate, pyridinium tetrakis (pentafluorophenyl) borate, pyrrolonium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, Examples include tetrakis (pentafluorophenyl) methyldiphenylammonium borate.
On the other hand, examples of the compound of the general formula (IV) include, for example, ferrocenium tetraphenylborate, dimethylferrocenium tetrakis (pentafluorophenyl) borate, ferrocenium tetrakis (pentafluorophenyl) borate, decamethylferrous tetrakis (pentafluorophenyl) borate. Cenium, tetrakis (pentafluorophenyl) acetylferrocenium borate, tetrakis (pentafluorophenyl) formylferrocenium borate, tetrakis (pentafluorophenyl) cyanoferrocenium borate, silver tetraphenylborate, tetrakis (pentafluorophenyl) Examples thereof include silver borate, trityl tetraphenylborate, tetrakis (pentafluorophenyl) trityl borate, and silver tetrafluoroborate.
A preferred coordination complex compound is composed of a non-coordinating anion and a substituted triarylcarbenium, and the non-coordinating anion includes, for example, the general formula (V)
^{(BZ 1 Z 2 Z 3 Z} 4) - ··· (V)
[Wherein, Z ^{1 to} Z ⁴ are each a hydrogen atom, a dialkylamino group, an alkoxy group, an aryloxy group, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms (including a halogen-substituted aryl group). , An alkylaryl group, an arylalkyl group, a substituted alkyl group and an organic metalloid group or a halogen atom. ]
The compound represented by these can be mentioned.

On the other hand, examples of the substituted triarylcarbenium include, for example, the general formula (VI)
[CR ¹³ R ¹⁴ R ¹⁵ ] ⁺ ... (VI)
The compound represented by these can be mentioned.
R ¹³ , R ¹⁴ and R ¹⁵ in the general formula (VI) are each an aryl group such as a phenyl group, a substituted phenyl group, a naphthyl group and an anthracenyl group, which may be the same or different from each other. However, at least one of them is a substituted phenyl group, a naphthyl group or an anthracenyl group.

The substituted phenyl group is, for example, represented by the general formula (VII)
C ₆ H _5-k R ¹⁶ _k (VII)
It can be expressed as
R ¹⁶ in the general formula (VII) represents a hydrocarbyl group having 1 to 10 carbon atoms, an alkoxy group, an aryloxy group, a thioalkoxy group, a thioaryloxy group, an amino group, an amide group, a carboxyl group, and a halogen atom, and k is It is an integer of 1-5.
When k is 2 or more, the plurality of R ¹⁶ may be the same or different.

  Specific examples of the non-coordinating anion represented by the general formula (V) include tetra (fluorophenyl) borate, tetrakis (difluorophenyl) borate, tetrakis (trifluorophenyl) borate, tetrakis (tetrafluorophenyl) borate, Tetrakis (pentafluorophenyl) borate, tetrakis (trifluoromethylphenyl) borate, tetra (toluyl) borate, tetra (xylyl) borate, (triphenyl, pentafluorophenyl) borate, [tris (pentafluorophenyl), phenyl] borate And tridecahydride-7,8-dicarboundeborate.

  Specific examples of the substituted triarylcarbenium represented by the general formula (VI) include tri (toluyl) carbenium, tri (methoxyphenyl) carbenium, tri (chlorophenyl) carbenium, tri (fluorophenyl) carbenium, tri ( Xylyl) carbenium, [di (toluyl), phenyl] carbenium, [di (methoxyphenyl), phenyl] carbenium, [di (chlorophenyl), phenyl] carbenium, [toluyl, di (phenyl)] carbenium, [methoxyphenyl, di (Phenyl)] carbenium, [chlorophenyl, di (phenyl)] carbenium and the like.

The organoaluminum compound (C) used in the present invention is represented by the general formula (VIII)
R ¹⁷ _v AlJ _3-v (VIII)
[In the formula, R ¹⁷ represents an alkyl group having 1 to 10 carbon atoms, J represents a hydrogen atom, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a halogen atom, and v represents 1 to 3 carbon atoms. (It is an integer)
The compound represented by these is mentioned.
Specific examples of the compound represented by the general formula (VIII) include trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, dimethylaluminum chloride, diethylaluminum chloride, methylaluminum dichloride, ethylaluminum dichloride, dimethylaluminum fluoride, Examples thereof include diisobutylaluminum hydride, diethylaluminum hydride, and ethylaluminum sesquichloride.
These organoaluminum compounds may be used alone or in combination of two or more.

  In addition, as the organoaluminum compound of component (C), general formula (IX)

(Wherein R ¹⁸ represents a hydrocarbon group such as an alkyl group, alkenyl group, aryl group, arylalkyl group or the like having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms, or a halogen atom, and w represents an average degree of polymerization. In general, it is an integer of 2 to 50, preferably 2 to 40. Note that each R ¹⁸ may be the same or different.
A chain aluminoxane represented by the general formula (X)

(Wherein R ¹⁸ and w are the same as those in the general formula (IX)).
The cyclic aluminoxane represented by these can be mentioned.
The compounds represented by the general formulas (IX) and (X) include linear or cyclic tetramethyl dialumoxane, tetraisobutyl dialumoxane, methylalumoxane, ethylalumoxane, butylalumoxane, isobutylalumoxane. And alumoxane.
Examples of the method for producing aluminoxane include a method in which an alkylaluminum is brought into contact with a condensing agent such as water, but the means thereof is not particularly limited and may be reacted according to a known method.
These aluminoxanes may be used alone or in combination of two or more.
As said organoaluminum compound, the compound represented by general formula (VIII) is preferable from an active viewpoint, and triisobutylaluminum is especially preferable.

In the polymerization catalyst used in the present invention, when the amount of the component (A) is a mol and the amount of the component (C) is c mol,
200 ≦ c / a ≦ 4500
It satisfies.
High activity is not obtained both when c / a is less than 200 and when c / a exceeds 4500. From this viewpoint, preferably 240 ≦ c / a ≦ 3500, more preferably 250 ≦ c / a ≦ 3000.

In addition, the polymerization catalyst used in the present invention has the above-mentioned (B) component amount of b mol,
0.5 ≦ b / a ≦ 20
It is preferable to satisfy.
When b / a is 0.5 or more, it is possible to avoid a significant decrease in activity, and when it is 20 or less, an effect commensurate with the amount of component (B) added can be obtained. From this viewpoint, more preferably, 1 ≦ b / a ≦ 10, and further preferably 1 ≦ b / a ≦ 5.

The method for preparing the polymerization catalyst used in the present invention is not particularly limited as long as it satisfies the regulations regarding the molar ratio of the component (A) and the component (C), and a conventionally known method can be used.
For example, after (C) an organoaluminum compound is added to a hydrocarbon solvent, (A) a transition metal compound, and (B) a boron compound that forms an ion pair with the component (A) are added to the present invention. The polymerization catalyst to be used can be prepared. Moreover, you may change the addition order of this (A)-(C) component. Furthermore, the polymerization catalyst may be prepared by adding each catalyst component in a polymerization reaction vessel, and preparing a catalyst solution by mixing each catalyst component in another vessel in advance, and then subjecting the obtained catalyst solution to a polymerization reaction. A polymerization reaction may be performed in addition to the container. In addition, examples of the hydrocarbon solvent used in the preparation of the polymerization catalyst include the solvents exemplified below for the polymerization reaction.

  Furthermore, the polymerization catalyst used in the present invention was obtained by carrying out prepolymerization using one or more unsaturated hydrocarbon compounds selected from α-olefin, internal olefin and polyene as component (D). Things can be used. At this time, 0.005 to 1.0 MPa of hydrogen can also coexist.

The temperature at the time of contact (preliminary polymerization) is preferably 20 to 80 ° C, more preferably 30 to 60 ° C, and particularly preferably 35 to 50 ° C. If the temperature at the time of contact deviates from the above range, the activity of the polymerization catalyst may not be sufficiently improved.
The contact (preliminary polymerization) time is usually 10 minutes to 30 days, preferably 1 hour to 15 days. The component (A) and the component (B) react while dissolving in a solvent to form an active site. For this reason, the effect of homogenizing the catalyst system on the improvement of the catalyst activity is great. Therefore, if the contact (preliminary polymerization) time is too short, the activity improving effect is not sufficient. On the other hand, if the contact (preliminary polymerization) time is too long, the catalytic activity may be lowered.
In addition, it is preferable to use what used the refinement | purification process as the solvent used in preparation of a catalyst, and (D) component as mentioned later.

[Polymerization reaction]
In the production method of the poly α-olefin of the present invention, ethylene or α-olefin is reacted using the polymerization catalyst. The α-olefin is preferably an α-olefin having 3 to 30 carbon atoms, such as propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1 -Dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicocene and the like can be mentioned, and one or more of these can be used.

The polymerization temperature is usually −100 to 250 ° C., preferably −50 to 200 ° C., more preferably 0 to 130 ° C.
The polymerization pressure is preferably normal pressure to 20 MPa (gauge), more preferably normal pressure to 10 MPa (gauge).
The polymerization time is usually 5 minutes to 15 hours.
(A) component [molar ratio] in C3-C30 alpha olefin / polymerization catalyst becomes like this. Preferably it is 1-1000, More preferably, it is 5-500.
Furthermore, examples of the method for adjusting the molecular weight of the poly-α-olefin include selection of the type of each catalyst component, the amount used and the polymerization temperature, and further polymerization in the presence of hydrogen.
As the polymerization method, bulk polymerization, solution polymerization, and suspension polymerization are used.
The polymerization solvent is not particularly limited, and examples thereof include aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene, cycloaliphatic hydrocarbons such as cyclopentane, cyclohexane, methylcyclohexane, decalin, and tetralin, pentane, hexane, and heptane. And aliphatic hydrocarbons such as octane, halogenated hydrocarbons such as chloroform and dichloromethane, etc., and toluene, xylene and decalin are preferred.
These solvents may be used alone or in combination of two or more. A monomer such as α-olefin may be used as a solvent.

  In the production method of the poly α-olefin of the present invention, the concentration of the component (C) is preferably 0.01 to 2 mmol / L. Good activity is obtained by being in this range. From this viewpoint, the concentration of the component (C) is more preferably 0.1 to 1.5 mmol / L, and further preferably 0.4 to 1.2 mmol / L. In addition, the density | concentration of this (C) component means the density | concentration of the (C) component in a polymerization liquid. Therefore, in the case of a reaction system using a solvent and a liquid monomer, it is the amount of the component (C) relative to the total amount of these, and when reacting the liquid monomer without using a solvent, it is the amount of the component (C) relative to the liquid monomer. When the gaseous monomer is reacted using a solvent, it represents the amount of the component (C) relative to the solvent.

In the present invention, the impurities contained in the solvent or monomer are used in a reduced manner as follows.
The amount of water in the solvent used is 10 mass ppm or less, preferably 5 mass ppm or less. When it exceeds 10 ppm by mass, the activity decreases.
When the monomer used is a liquid at normal temperature and pressure, the water content is 10 mass ppm or less, preferably 5 mass ppm or less. When it exceeds 10 ppm by mass, the activity decreases. The amount of monomer oxide is 100 mass ppm or less, preferably 50 mass ppm or less. When it exceeds 100 ppm by mass, the activity decreases. The monomer oxide is a compound formed by oxidizing a monomer, and examples thereof include an epoxy compound, a carbonyl group-containing compound, and a peroxide compound.
Examples of the method for removing dissolved oxygen and moisture in the solvent and liquid monomer include a method in which an inert gas such as nitrogen or argon is circulated in the solvent or monomer. Furthermore, as a method for removing moisture in the hydrocarbon solvent, a method of distilling in an inert gas atmosphere after adding sodium or potassium metal may be used.

The amount of impurities when the monomer used is a gas at normal temperature and pressure is as follows.
The amount of carbonyl sulfide is 20 mass ppb or less, preferably 10 mass ppb or less. The amount of carbon dioxide is 0.1 mol ppm or less, preferably 0.05 mol ppm or less. The amount of carbon monoxide is 0.1 mol ppm or less, preferably 0.05 mol ppm or less. If these regulations are not met, the activity is reduced.
As a purification method for satisfying these regulations and the regulations regarding the monomer oxide in the liquid monomer, a method using an adsorbent can be mentioned. Examples of the adsorbent include nickel, nickel oxide, zinc oxide, copper sulfide, cupric oxide, silica, molecular sieves, activated carbon, activated alumina, and the like.

  The method for producing a poly-α-olefin of the present invention uses a polymerization catalyst that satisfies the definition of the molar ratio (c / a) of the catalyst component, and performs a polymerization reaction under the reaction conditions that satisfy the above-mentioned requirements regarding impurities contained in the solvent and monomer. Is to do. The amount of impurities specified in the present invention is considerably lower than the target amount of impurities in normal polymerization. In such a case, when the amount of the component (C) that has been conventionally used is added, it not only does not contribute to the activity improvement, but also the activity may decrease. However, high activity can be expressed by defining the amount of component (C) to be added based on the c / a ratio.

  EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by these examples.

[Measuring method]
The method for quantifying impurities in the examples is as follows.
1. Method for quantification of oxide in liquid monomer (1-hexadecene) Perform gas chromatography measurement, and compare each oxide to 10 μg / ml by absolute calibration curve by comparing the area with 2-hexadecanol heptane standard solution (lower limit of quantification) : 10 μg / ml) quantified, and the total was defined as total oxide.
<GC measurement conditions>
Measuring device: Gas chromatography 6890N (G1530N) manufactured by Agilent Technologies
Control analysis software: GC ChemStation (Rev. B.03.02)
Autosampler: 7683 series
Column: DB-1701 30 m × 0.25 mm ID × film thickness; 0.25 μm
Temperature rise condition: 40 ° C. → 10 ° C./min temperature rise → 270 ° C.
Inlet (split) temperature: 330 ° C
Detector (FID) temperature: 270 ° C
Carrier gas: He (140 kPa)
Split flow rate: 50 ml / min
Injection volume: 0.5 μl

2. Quantitative determination method of carbonyl sulfide in gaseous monomer (propylene) Gas chromatographic measurement is performed with a sample gas injection amount of 5 ml, and the absolute calibration curve method is used from the peak height of carbonyl sulfide detected by a flame photometric detector (FPD). The amount of carbonyl sulfide was determined.
<GC measurement conditions>
Measuring device: GC-2014 manufactured by Shimadzu Corporation
Detector: FPD detector (S interference filter: 394 nm)
Column: Stainless steel packed column (length 2m x inner diameter 3mmφ)
(Filler: Sunpak-S)
Sample introduction unit: Gas sampler MGS-4 manufactured by Shimadzu Corporation, metering tube switch (by 6-way valve), metering tube with 5 ml capacity, metering tube data processing device with 0.3 ml capacity: manufactured by Shimadzu Corporation GC solution
Sample collection container: 1.0L tedlar bag (CCK1) manufactured by GL Sciences Inc.
Carrier gas: Nitrogen (130 kPa)
Hydrogen: Purity 99.99 vol% or more filled in a cylinder was used.
Standard gas: Carbonyl sulfide 20 mol ppm / N ₂ base (manufactured by Takachiho Chemical Co., Ltd.)
GC oven temperature: 70 ° C

3. Quantitative determination method of carbon monoxide and carbon dioxide in gaseous monomer (propylene) Gas chromatographic measurement was performed with a sample gas injection amount of 5 ml. At this time, CO and CO ₂ separated by the column are introduced into the methanizer, converted to methane by hydrogenation with hydrogen using a nickel catalyst under high temperature conditions, and the amount of methane is detected by FID. , CO and CO ₂ were quantified by the absolute calibration curve method.

<GC measurement conditions>
Measuring device: GC-14A manufactured by Shimadzu Corporation
Detector: Hydrogen flame ionization detector (FID)
Metanizer: MTN-1 manufactured by Shimadzu Corporation
Data processing device: C-R4A (manufactured by Shimadzu Corporation) (network with GC-14A in current loop)
Gas sampler: MGS-4 manufactured by Shimadzu Corporation
Column: Stainless steel packed column (column length 8m x inner diameter 3mmφ)
(Filler: Polapack Q (50/80 mesh))
Carrier gas: Nitrogen (290 kPa)
Hydrogen: Purity 99.99 vol% or more filled in a cylinder was used.
Standard gas: CO and CO ₂ adjusted to 10 mol ppm (base is nitrogen balance)
GC oven temperature: 60 ° C

[Production Example 1] Synthesis of (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) -bis (3-trimethylsilylmethylindenyl) zirconium dichloride (1,2'-dimethylsilylene) ( Lithium salt of 2,1′-dimethylsilylene) -bis (indene) (3.0 g, 6.97 mmol) was dissolved in 50 ml of tetrahydrofuran (THF) and cooled to −78 ° C. 2.1 ml (14.2 mmol) of iodomethyltrimethylsilane was slowly added dropwise and stirred at room temperature for 12 hours.
The solvent was distilled off, 50 ml of ether was added, and the mixture was washed with a saturated ammonium chloride solution. After liquid separation, the organic phase was dried to remove the solvent, and 3.04 g (5.88 mmol) of (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) -bis (3-trimethylsilylmethylindene) was obtained. Obtained (yield 84%).
Next, 3.04 g (5.88 mmol) of (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) -bis (3-trimethylsilylmethylindene) obtained above in a Schlenk bottle under a nitrogen stream. And 50 ml of ether. It cooled at -78 degreeC and the hexane solution (1.54 mol / L, 7.6 ml (11.7 mmol)) of n-butyltylium (n-BuLi) was dripped. After raising to room temperature and stirring for 12 hours, ether was distilled off. The obtained solid was washed with 40 ml of hexane to obtain 3.06 g (5.07 mmol) of the lithium salt as an ether adduct (yield 73%).
The results of measurement by ¹ H-NMR (90 MHz, THF-d ₈ ) are as follows.
δ: 0.04 (s, 18H, trimethylsilyl), 0.48 (s, 12H, dimethylsilylene), 1.10 (t, 6H, methyl), 2.59 (s, 4H, methylene), 3.38 (q, 4H, methylene), 6.2- 7.7 (m, 8H, Ar-H)

Under a nitrogen stream, the lithium salt obtained above was dissolved in 50 ml of toluene. The mixture was cooled to -78 ° C, and a suspension of 1.2 g (5.1 mmol) of zirconium tetrachloride, which had been cooled to -78 ° C in advance, in toluene (20 ml) was added dropwise thereto. After dropping, the mixture was stirred at room temperature for 6 hours. The solvent of the reaction solution was distilled off. The obtained residue was recrystallized from dichloromethane to obtain 0.9 g of (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) -bis (3-trimethylsilylmethylindenyl) zirconium dichloride (1. 33 mmol) was obtained (yield 26%).
The results of measurement by ¹ H-NMR (90 MHz, CDCl ₃ ) are as follows.
δ: 0.0 (s, 18H, trimethylsilyl), 1.02, 1.12 (s, 12H, dimethylsilylene), 2.51 (dd, 4H, methylene), 7.1-7.6 (m, 8H, Ar-H)

[Purification treatment]
(Purification of n-heptane)
Into a 5 L round bottom flask equipped with a distillation apparatus, 5 L of n-heptane and 5 g of metallic sodium were added, and 2 g of benzophenone was further added, followed by heating under reflux in a nitrogen atmosphere to confirm that the solvent had turned blue. And sodium treatment n-heptane was obtained by distilling n-heptane under nitrogen atmosphere.
(Propylene purification)
Purge about 1/10 of an unused 50 kg propylene cylinder, and perform polymerization using a carbonyl sulfide amount of 20 mass ppb or less, a carbon monoxide amount and a carbon dioxide amount of 0.1 mol ppm or less, respectively. It was.

[Example 1]
(Preparation of catalyst 1: prepolymerization)
Toluene (196 mL) sufficiently bubbled with nitrogen was added to a 1 L autoclave with a stirrer at room temperature under a nitrogen stream. Thereafter, while stirring, 4.5 mL (9 mmol) of a 2M heptane solution of triisobutylaluminum, (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) -bis (3 -Trimethylsilylmethylindenyl) zirconium dichloride 30 mM toluene slurry 40 mL (1.2 mmol) and dimethylanilinium tetrakis (pentafluorophenyl) borate 30 mM toluene slurry 60 mL (1.8 mmol) were sequentially added. Thereafter, propylene was introduced to 0.05 MPa, the temperature was raised to 30 ° C., and prepolymerization was started. After 15 minutes, the introduction of propylene was stopped, and the mixture was further stirred for 30 minutes to obtain a catalyst solution containing the catalyst 1 (catalyst concentration: 4 mmol / L). When calculated from the consumed propylene flow rate of 8.7 L, the propylene polymer is 16.3 g.

(Polymerization reaction)
To a 1 L autoclave, heptane (400 mL) was added at 25 ° C. under a nitrogen stream, and 0.05 mL (0.1 mmol) of a 2 M heptane solution of triisobutylaluminum was added. After stirring for 1 minute, catalyst 1 (0.05 mL, 0.2 μmol) obtained by the method described above was added. Next, hydrogen was introduced to 0.04 MPa and propylene to a total pressure of 0.74 MPa, and the temperature was raised to 70 ° C. over about 3 minutes while stirring. Polymerization was carried out for 15 minutes after the introduction of propylene. Thereafter, ethanol (5 mL) was added to stop the polymerization reaction. After depressurization, the resulting polymerization solution was dried at 80 ° C. under reduced pressure to obtain a propylene polymer.

[Example 2]
The reaction was conducted in the same manner as in Example 1 except that the addition amount of the 2M heptane solution of triisobutylaluminum was changed to 0.1 mL (0.2 mol) in the polymerization reaction.

[Example 3]
The reaction was conducted in the same manner as in Example 1 except that the addition amount of the 2M heptane solution of triisobutylaluminum was changed to 0.3 mL (0.6 mmol) in the polymerization reaction.

[Example 4]
In the polymerization reaction, the reaction was performed in the same manner as in Example 3 except that 2 μL (equivalent to 8 mass ppm) of water was added using a microsyringe before adding 0.3 mL of a 2M heptane solution of triisobutylaluminum to the autoclave.

[Comparative Example 1]
The reaction was conducted in the same manner as in Example 1 except that the addition amount of the 2M heptane solution of triisobutylaluminum was changed to 0.5 mL (1.0 mmol) in the polymerization reaction.

[Comparative Example 2]
The reaction was conducted in the same manner as in Example 1 except that the addition amount of the 2M heptane solution of triisobutylaluminum was changed to 1 mL (2.0 mmol) in the polymerization reaction.

[Comparative Example 3]
The reaction was conducted in the same manner as in Example 1 except that the addition amount of the 2M heptane solution of triisobutylaluminum was changed to 0.015 mL (0.03 mmol) in the polymerization reaction.

[Comparative Example 4]
In the polymerization reaction, the reaction was performed in the same manner as in Example 2 except that 4.8 μL (equivalent to 19 mass ppm) of water was added using a microsyringe before adding 0.1 mL of a 2M heptane solution of triisobutylaluminum to the autoclave. It was.

  The yield and polymerization activity are shown in Table 1 for the polymerization reactions of Examples 1-4 and Comparative Examples 1-4.

[Example 5]
(Preparation of catalyst 2: prepolymerization)
To 50 mL Schlenk with a stirrer, 2 mL (1.5 g) of toluene (13 mL) sufficiently bubbled with nitrogen and Idemitsu Kosan Co., Ltd. linearene 18 (1-octadecene) were added at 30 ° C. in a nitrogen stream. Thereafter, while stirring, 0.2 mL (0.4 mmol) of a 2M heptane solution of triisobutylaluminum, (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) -bis produced in Production Example 1 was used. 2 mL (40 μmol) of 20 mM toluene slurry of (3-trimethylsilylmethylindenyl) zirconium dichloride and 3 mL (60 μmol) of 20 mM toluene slurry of dimethylanilinium tetrakis (pentafluorophenyl) borate were sequentially added. By stirring for 12 hours, a catalyst solution containing the catalyst 2 was obtained (catalyst concentration: 2 mmol / L).

(polymerization)
In a 1 L autoclave, 400 mL of linearene 18 (1-octadecene) manufactured by Idemitsu Kosan Co., Ltd. is added to a 1 L autoclave, and a heptane solution of triisobutylaluminum (2M, 0.25 mmol, 0.125 mL) is added at 90 ° C. The temperature was raised to. Catalyst 2 (0.5 mL, 1 μmol, 2 mmol / L) was added. Next, polymerization was started by introducing 0.15 MPa of hydrogen. After 60 minutes, ethanol (5 mL) was added. After the temperature was lowered to 50 ° C., the polymerization solution was put into 400 mL of acetone, and then the supernatant was discarded. Further, 400 mL of acetone was added, and the mixture was allowed to stand with stirring, and then the supernatant was discarded. The obtained polymer was dried at 140 ° C. under reduced pressure to obtain the desired polymer. The linearene 18 is left in the air to oxidize 1-octadecene and produce its oxide. In Example 5, the amount of oxide in the linearene 18 was 5 ppm by mass.

[Example 6]
The reaction was performed in the same manner as in Example 5 except that the addition amount of the 2M heptane solution of triisobutylaluminum was changed to 0.25 mL (0.5 mmol) in the polymerization reaction. The amount of oxide in linearene 18 was 5 ppm by mass.

[Example 7]
The reaction was conducted in the same manner as in Example 5 except that the addition amount of the triisobutylaluminum heptane solution was changed to 0.75 mL (1.5 mmol) in the polymerization reaction. The oxide amount of linearene 18 was 50 mass ppm.

[Comparative Example 5]
The reaction was conducted in the same manner as in Example 5 except that the addition amount of the triisobutylaluminum heptane solution was changed to 0.05 mL (0.1 mmol) in the polymerization reaction. The amount of oxide in linearene 18 was 5 ppm by mass.

[Comparative Example 6]
The reaction was performed in the same manner as in Example 5 using linearene 18 having an oxide amount of 100 mass ppm.

[Comparative Example 7]
The reaction was performed in the same manner as in Example 5 except that the addition amount of the 2M heptane solution of triisobutylaluminum was changed to 5.0 mL (10 mmol) in the polymerization reaction. The amount of oxide in linearene 18 was 5 ppm by mass.

  The yield and polymerization activity are shown in Table 2 for the polymerization reactions of Examples 5 to 7 and Comparative Examples 5 to 7.

[Example 8]
(Preparation of catalyst 3: prepolymerization)
To 50 mL Schlenk with a stirrer, 2 mL (1.5 g) of toluene (13 mL) sufficiently bubbled with nitrogen and Idemitsu Kosan Co., Ltd. linearene 18 (1-octadecene) were added at 30 ° C. in a nitrogen stream. Then, 0.2 mL (0.4 mmol) of a 2M heptane solution of triisobutylaluminum with stirring, 2 mL (40 μmol) of 20 mM toluene slurry of ethylene bisindenylzirconium dichloride made by Strem, dimethylanilinium tetrakis (pentafluorophenyl) 3 mL (60 μmol) of 20 mM toluene slurry of borate was added in order. By stirring for 12 hours, a catalyst solution containing the catalyst 3 was obtained (catalyst concentration: 2 mmol / L).

(Preparation of monomer)
“Linearene 26+” (mainly a mixture of α-olefins having 26 or more carbon atoms) manufactured by Idemitsu Kosan Co., Ltd. was distilled under reduced pressure (0.85 kPa) to obtain a fraction having a distillation temperature of 240 to 250 ° C. The composition ratio of this fraction was as follows: C24 compound (compound having 24 carbon atoms): 35.9%, C26 compound: 36.4%, C28 compound: 17.8%, compound having 30 or more carbon atoms: 9.8% Met.
(polymerization)
To a 1 L autoclave, the monomer prepared in the above method (the amount of oxide in the monomer is 80 ppm by mass) (400 mL) is added to a 1 L autoclave, and a heptane solution of triisobutylaluminum (2 M, 0.4 mmol, 0.2 mL) The temperature was raised to 90 ° C. Catalyst 3 (0.5 mL, 1 μmol, 2 mmol / L) was added. Next, polymerization was started by introducing 0.15 MPa of hydrogen. After 60 minutes, ethanol (5 mL) was added. After the temperature was lowered to 50 ° C., the polymerization solution was put into 400 mL of acetone, and then the supernatant was discarded. Further, 400 mL of acetone was added, and the mixture was allowed to stand with stirring, and then the supernatant was discarded. The obtained polymer was dried at 140 ° C. under reduced pressure to obtain the desired polymer.

[Comparative Example 8]
The reaction was conducted in the same manner as in Example 8 except that the addition amount of the 2M heptane solution of triisobutylaluminum was changed to 1.5 mL (3 mmol) in the polymerization reaction. The amount of oxide in the monomer was 80 ppm by mass.

[Example 9]
(Preparation of catalyst 4)
To a 50 mL Schlenk equipped with a stirrer, 2 ml (1.5 g) of toluene (13 mL) sufficiently bubbled with nitrogen and Idemitsu Kosan Co., Ltd. linearene 18 (1-octadecene) were added at 30 ° C. in a nitrogen stream. Thereafter, 0.2 mL (0.4 mmol) of a 2M heptane solution of triisobutylaluminum with stirring, 2 mL (40 μmol) of 20 mM toluene slurry of bis (tetramethylcyclopentadienyl) zirconium dichloride manufactured by Kanto Chemical Co., Ltd., dimethylanilinium tetrakis 3 mL (60 μmol) of 20 mM heptane slurry of (pentafluorophenyl) borate was added in order. By stirring at room temperature for 12 hours, a catalyst solution containing the catalyst 4 was obtained (catalyst concentration: 2 mmol / L).

(polymerization)
In a 1 L autoclave, under a nitrogen stream, Idemitsu Kosan Co., Ltd. linearene 18 (1-octadecene) (400 mL) is added, and a heptane solution of triisobutylaluminum (2 M, 0.4 mmol, 0.2 mL) is added. The temperature was raised to 90 ° C. Catalyst 4 (0.5 mL, 1 μmol, 2 mmol / L) was added. Next, polymerization was started by introducing 0.15 MPa of hydrogen. After 60 minutes, ethanol (5 mL) was added. After the temperature was lowered to 50 ° C., the polymerization solution was put into 400 mL of acetone, and then the supernatant was discarded. Further, 400 mL of acetone was added, and the mixture was allowed to stand with stirring, and then the supernatant was discarded. The obtained polymer was dried at 140 ° C. under reduced pressure to obtain the desired polymer. The amount of oxide in linearene 18 was 45 ppm by mass.

[Comparative Example 9]
In a 1 L autoclave, linearlen 18 (1-octadecene) (400 mL) manufactured by Idemitsu Kosan Co., Ltd. is added under a nitrogen stream, and a heptane solution of triisobutylaluminum (2 M, 10 mmol, 5 mL) is added, and the temperature is increased to 90 ° C. Warm up. Catalyst 4 (0.5 mL, 1 μmol, 2 mmol / L) was added. Next, polymerization was started by introducing 0.15 MPa of hydrogen. After 60 minutes, ethanol (5 mL) was added. After the temperature was lowered to 50 ° C., the polymerization solution was put into 400 mL of acetone, and then the supernatant was discarded. Further, 400 mL of acetone was added, and the mixture was allowed to stand with stirring, and then the supernatant was discarded. The obtained polymer was dried at 140 ° C. under reduced pressure to obtain the desired polymer. The amount of oxide in linearene 18 was 80 ppm by mass.

  Table 3 shows the yield and polymerization activity for the polymerization reactions of Examples 8 and 9 and Comparative Examples 8 and 9.

  The method for producing a polyolefin of the present invention exhibits higher activity than before, and is preferable from an economical viewpoint. Moreover, a high quality poly alpha olefin can be manufactured.

Claims (3)

(A) A transition metal compound, (B) a boron compound that forms an ion pair with the component (A), and (C) a polyolefin production method using a catalyst obtained by contacting an organoaluminum compound, wherein the following (a) ) To (d), a method for producing a polyolefin, in which a polymerization reaction is performed under reaction conditions.
(A) When the amount of the component (A) is a mole and the amount of the component (C) is c mol,
200 ≦ c / a ≦ 4500
(B) In the case of using a gas monomer, the amount of carbonyl sulfide contained in the gas monomer is 20 mass ppb or less, the amount of carbon dioxide is 0.1 mol ppm or less, and the amount of carbon monoxide is 0.1 mol ppm or less. .
(C) When using a liquid monomer, the monomer oxide contained in the liquid monomer is 100 mass ppm or less and the water content is 10 mass ppm or less.
(D) When using a solvent, the amount of water contained in the solvent is 10 mass ppm or less. The method for producing a polyolefin according to claim 1, wherein the monomer and the solvent are purified by an adsorbent. The method for producing a polyolefin according to claim 1 or 2, wherein the organoaluminum is triisobutylaluminum.