JP4237200B2 - α-olefin / conjugated diene copolymer - Google Patents

Description

The present invention relates to a novel olefin polymerization catalyst, a transition metal compound, and an olefin polymerization method using the olefin polymerization catalyst.
Another object of the present invention is to provide an α-olefin / conjugated diene copolymer that has a narrow molecular weight distribution and is suitably used as a rubber.

  A so-called Kaminsky catalyst is well known as an olefin polymerization catalyst. This catalyst is characterized by extremely high polymerization activity and a polymer having a narrow molecular weight distribution. Examples of the transition metal compound used in such a Kaminsky catalyst include bis (cyclopentadienyl) zirconium dichloride (see JP-A-58-19309, Patent Document 1), ethylene bis (4,5,6). , 7-tetrahydroindenyl) zirconium dichloride (see Japanese Patent Application Laid-Open No. 61-130314, Patent Document 2) and the like are known. It is also known that the olefin polymerization activity and the properties of the resulting polyolefin differ greatly when the transition metal compound used in the polymerization is different. Recently, a transition metal compound having a ligand of diimine structure (see International Patent No. 9623010, Patent Document 3) has been proposed as a new olefin polymerization catalyst.

  By the way, polyolefins are generally used in various fields such as for various molded products because they are excellent in mechanical properties. However, in recent years, physical property requirements for polyolefins are diversified, and polyolefins having various properties are desired. ing. Improvement of productivity is also desired.

Under such circumstances, the appearance of an olefin polymerization catalyst capable of producing a polyolefin having excellent olefin polymerization activity and excellent properties is desired.
It is well known that when a Ziegler-Natta polymerization catalyst is used, copolymerization of several α-olefins and non-conjugated dienes proceeds. Since this copolymer is useful as a rubber, various types are produced. However, since the non-conjugated diene used here is generally expensive and has low reactivity, a low-cost and highly reactive diene component has been demanded.

  Examples of such a diene component include conjugated dienes such as 1,3-butadiene and isoprene. These conjugated dienes are cheaper and more reactive than the conventionally used non-conjugated dienes, but when copolymerization is carried out using a conventional Ziegler-Natta polymerization catalyst, the activity is greatly reduced, There is a problem that only a heterogeneous copolymer having a wide composition distribution and molecular weight distribution can be obtained. In the Ziegler-Natta catalyst system using a vanadium compound, a relatively uniform copolymer was obtained, but the polymerization activity was very low. Therefore, in recent years, active research has been conducted, and the copolymerization of ethylene and butadiene using a so-called metallocene catalyst known to exhibit high polymerization activity has been studied (Japanese Patent Publication No. 1-501633, patent). Reference 4).

  However, in this case, it has been reported that a cyclopentane skeleton is formed in the polymer chain from the diene unit incorporated in the polymer and ethylene, and the proportion thereof is 50% or more of the total diene units. Thus, the conversion of the double bond of the diene unit into a cyclopentane skeleton is extremely disadvantageous in an operation called vulcanization that is indispensable when this copolymer is used as a rubber. Further, this cyclopentane skeleton is an unfavorable skeleton because it has an effect of increasing the glass transition temperature of the copolymer and impairs the low temperature characteristics as a rubber.

Under such circumstances, the appearance of a copolymer of an α-olefin and a conjugated diene that has a narrow molecular weight distribution, a uniform composition, and almost no cyclopentane skeleton in the polymer chain is strongly desired.
JP 58-19309 A JP-A 61-130314 International Patent No. 9623010 JP-T-1-501633

  An object of the present invention is to provide a catalyst for olefin polymerization having excellent olefin polymerization activity, a novel transition metal compound useful for such a catalyst, and a method for polymerizing olefins using the catalyst.

  Another object of the present invention is to provide an α-olefin / conjugated diene copolymer having a narrow molecular weight distribution and containing almost no cyclopentane skeleton in the polymer chain.

  The α-olefin / conjugated diene copolymer according to the present invention has a molecular weight distribution (Mw / Mn) value of 3.5 or less and a content of structural units derived from the α-olefin of 1 to 99.9 mol%. The content of the structural unit derived from the conjugated diene is in the range of 99 to 0.1 mol%, and the content of the 1,2-cyclopentane skeleton derived from the conjugated diene in the polymer chain is 1 It is characterized by not containing a mol% or less, preferably substantially free of a 1,2-cyclopentane skeleton.

  The α-olefin / conjugated diene copolymer according to the present invention has a content of structural units derived from α-olefin in the range of 50 to 99.9 mol%, and a content of structural units derived from conjugated diene. It is preferably in the range of 50 to 0.1 mol%.

  Further, in the α-olefin / conjugated diene copolymer according to the present invention, the α-olefin is preferably ethylene and / or propylene, and the conjugated diene is preferably butadiene and / or isoprene.

The catalyst for olefin polymerization according to the present invention has high polymerization activity for olefins.
According to the olefin polymerization method of the present invention, an olefin (co) polymer having a high polymerization activity and a narrow molecular weight distribution can be produced. Moreover, when an α-olefin and a conjugated diene are copolymerized, a copolymer containing no 1,2-cyclopentane skeleton in the polymer chain can be produced.

The novel transition metal compound according to the present invention is useful as a catalyst for olefin polymerization and provides an olefin (co) polymer having a high polymerization activity and a narrow molecular weight distribution.
The α-olefin / conjugated diene copolymer according to the present invention has a narrow molecular weight distribution and hardly contains a cyclopentane skeleton in the polymer chain.

Hereinafter, the olefin polymerization catalyst and the olefin polymerization method using the catalyst in the present invention will be described in detail.
In the present specification, the term “polymerization” is sometimes used in the meaning including not only homopolymerization but also copolymerization, and the term “polymer” refers not only to homopolymer but also to copolymerization. It may be used in the meaning that also includes coalescence.

First Olefin Polymerization Catalyst The first olefin polymerization catalyst according to the present invention comprises:
(A) a transition metal compound represented by the following general formula (I);
(B) (B-1) Organometallic compound,
(B-2) an organoaluminum oxy compound, and
(B-3) It is formed from at least one compound selected from compounds that react with transition metal compounds to form ion pairs.

First, each catalyst component forming the olefin polymerization catalyst of the present invention will be described.
(A) Transition metal compound The (A) transition metal compound used in the present invention is a compound represented by the following general formula (I).

(Here, N ... M generally indicates coordination, but may or may not be coordinated in the present invention.)
In the formula (I), M represents a transition metal atom of Group 3 to 11 of the periodic table (Group 3 includes lanthanoids), preferably Group 3 to 9 (Group 3 also includes lanthanoids). It is a metal atom, More preferably, it is a metal atom of a 3-5 group, and a 9 group, Most preferably, it is a 4 or 5 group metal atom. Specifically, scandium, titanium, zirconium, hafnium, vanadium, niobium, tantalum, cobalt, rhodium, yttrium, chromium, molybdenum, tungsten, manganese, rhenium, iron, ruthenium, etc., preferably scandium, titanium, zirconium, Hafnium, vanadium, niobium, tantalum, cobalt, rhodium, etc., more preferably titanium, zirconium, hafnium, cobalt, rhodium, vanadium, niobium, tantalum, etc., particularly preferably titanium, zirconium, hafnium.

m represents an integer of 1 to 6, preferably 1 to 4.
R ^{1 to} R ⁶ may be the same or different from each other, and are a hydrogen atom, a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, a sulfur-containing group, phosphorus A containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group, and two or more of these may be linked to each other to form a ring.

Examples of the halogen atom include fluorine, chlorine, bromine and iodine.
Specifically, the hydrocarbon group has 1 to 30 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, neopentyl, n-hexyl, preferably 1-20 linear or branched alkyl groups;
Linear or branched alkenyl groups having 2 to 30, preferably 2 to 20 carbon atoms, such as vinyl, allyl, isopropenyl, etc .;
A linear or branched alkynyl group having 2 to 30, preferably 2 to 20 carbon atoms, such as ethynyl, propargyl, etc .;
A cyclic saturated hydrocarbon group having 3 to 30 carbon atoms, preferably 3 to 20 carbon atoms such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl, etc .; a cyclic aryl group having 5 to 30 carbon atoms such as cyclopentadienyl, indenyl, fluorenyl, etc. Saturated hydrocarbon groups;
Aryl groups having 6 to 30, preferably 6 to 20 carbon atoms, such as phenyl, benzyl, naphthyl, biphenyl, terphenyl, phenanthryl, anthracenyl;
And alkyl-substituted aryl groups such as tolyl, iso-propylphenyl, t-butylphenyl, dimethylphenyl, and di-t-butylphenyl.

  In the above hydrocarbon group, a hydrogen atom may be substituted with a halogen. For example, a halogenated hydrocarbon group having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms such as trifluoromethyl, pentafluorophenyl, chlorophenyl and the like. Can be mentioned.

Moreover, the said hydrocarbon group may be substituted by other hydrocarbon groups, for example, aryl group substituted alkyl groups, such as benzyl and cumyl, etc. are mentioned.
Furthermore, the hydrocarbon group is a heterocyclic compound residue; an alkoxy group, an aryloxy group, an ester group, an ether group, an acyl group, a carboxyl group, a carbonate group, a hydroxy group, a peroxy group, a carboxylic anhydride group, etc. Oxygen-containing group: amino group, imino group, amide group, imide group, hydrazino group, hydrazono group, nitro group, nitroso group, cyano group, isocyano group, cyanate ester group, amidino group, diazo group, amino group is ammonium salt Nitrogen-containing groups such as those; boron-containing groups such as boranediyl group, boranetriyl group, diboranyl group; mercapto group, thioester group, dithioester group, alkylthio group, arylthio group, thioacyl group, thioether group, thiocyanate group , Isothiocyanate ester group, sulfone ester group, Sulfur-containing groups such as sulfonamide groups, thiocarboxyl groups, dithiocarboxyl groups, sulfo groups, sulfonyl groups, sulfinyl groups, sulfenyl groups; phosphorus-containing groups such as phosphide groups, phosphoryl groups, thiophosphoryl groups, phosphato groups, silicon-containing groups , A germanium-containing group, or a tin-containing group.

  Of these, in particular, 1-30 carbon atoms, preferably 1-20, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, neopentyl, n-hexyl, etc. Linear or branched alkyl groups; aryl groups having 6 to 30 carbon atoms, preferably 6 to 20 carbon atoms such as phenyl, naphthyl, biphenyl, terphenyl, phenanthryl, anthracenyl; halogen atoms and carbon atoms for these aryl groups A substituted aryl group substituted with 1 to 5 substituents such as an alkyl group or an alkoxy group having 1 to 30, preferably 1 to 20 carbon atoms, an aryl group or an aryloxy group having 6 to 30 carbon atoms, preferably 6 to 20 carbon atoms, etc. Is preferred.

Examples of the oxygen-containing group, nitrogen-containing group, boron-containing group, sulfur-containing group and phosphorus-containing group are the same as those exemplified above.
Heterocyclic compound residues include residues such as nitrogen-containing compounds such as pyrrole, pyridine, pyrimidine, quinoline, and triazine, oxygen-containing compounds such as furan and pyran, sulfur-containing compounds such as thiophene, and heterocyclic groups thereof. Examples thereof include a group further substituted with a substituent such as an alkyl group or alkoxy group having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, in the compound residue.

Examples of silicon-containing groups include silyl groups, siloxy groups, hydrocarbon-substituted silyl groups, hydrocarbon-substituted siloxy groups, such as methylsilyl, dimethylsilyl, trimethylsilyl, ethylsilyl, diethylsilyl, triethylsilyl, diphenylmethylsilyl, triphenyl. Examples include phenylsilyl, dimethylphenylsilyl, dimethyl-t-butylsilyl, dimethyl (pentafluorophenyl) silyl and the like. Among these, methylsilyl, dimethylsilyl, trimethylsilyl, ethylsilyl, diethylsilyl, triethylsilyl, dimethylphenylsilyl, triphenylsilyl and the like are preferable. In particular, trimethylsilyl, triethylsilyl, triphenylsilyl, and dimethylphenylsilyl are preferable. Specific examples of the hydrocarbon-substituted siloxy group include trimethylsiloxy and the like.

Examples of the germanium-containing group and tin-containing group include those obtained by substituting silicon of the silicon-containing group with germanium and tin.
Next, the examples of R ^{1 to} R ⁶ described above will be described more specifically.

Specific examples of the alkoxy group include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy and the like.
Specific examples of the alkylthio group include methylthio and ethylthio.

Specific examples of the aryloxy group include phenoxy, 2,6-dimethylphenoxy, 2,4,6-trimethylphenoxy and the like.
Specific examples of the arylthio group include phenylthio, methylphenylthio, naphthylthio and the like.

Specific examples of the acyl group include formyl group, acetyl group, benzoyl group, p-chlorobenzoyl group, and p-methoxybenzoyl group.
Specific examples of the ester group include acetyloxy, benzoyloxy, methoxycarbonyl, phenoxycarbonyl, p-chlorophenoxycarbonyl, and the like.

Specific examples of the thioester group include acetylthio, benzoylthio, methylthiocarbonyl, and phenylthiocarbonyl.
Specific examples of the amide group include acetamide, N-methylacetamide, N-methylbenzamide and the like.

Specific examples of the imide group include acetoimide and benzimide.
Specific examples of the amino group include dimethylamino, ethylmethylamino, diphenylamino and the like.

Specific examples of the imino group include methylimino, ethylimino, propylimino, butylimino, and phenylimino.
Specific examples of the sulfone ester group include methyl sulfonate, ethyl sulfonate, and phenyl sulfonate.

Specific examples of the sulfonamido group include phenylsulfonamido, N-methylsulfonamido, N-methyl-p-toluenesulfonamido and the like.
R ⁶ is preferably a substituent other than hydrogen. That is, R ⁶ is preferably a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a boron-containing group, a sulfur-containing group, a silicon-containing group, a germanium-containing group or a tin-containing group. In particular, R ⁶ is a halogen atom, a hydrocarbon group, a heterocyclic compound residue, a hydrocarbon-substituted silyl group, a hydrocarbon-substituted siloxy group, an alkoxy group, an alkylthio group, an aryloxy group, an arylthio group, an acyl group, an ester group, a thioester It is preferably a group, an amide group, an amino group, an imide group, an imino group, a sulfone ester group, a sulfonamide group, a cyano group, a nitro group or a hydroxy group.

Preferred hydrocarbon groups as R ⁶ include 1 to 30 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, thiopentyl, n-hexyl, etc. Is a linear or branched alkyl group having 1 to 20; a cyclic saturated hydrocarbon group having 3 to 30, preferably 3 to 20 carbon atoms such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl; phenyl, benzyl Aryl groups having 6 to 30 carbon atoms, preferably 6 to 20 carbon atoms, such as naphthyl, biphenylyl and triphenylyl; and alkyl groups or alkoxy groups having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, in these groups A halogenated alkyl group having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, 6 to 30 carbon atoms, preferably The properly 6-20 aryl group or an aryloxy group, a halogen, a cyano group, a nitro group, a group having a substituted group is further substituted, such as hydroxy groups are preferably exemplified.

Preferred hydrocarbon-substituted silyl groups as R ⁶ include methylsilyl, dimethylsilyl, trimethylsilyl, ethylsilyl, diethylsilyl, triethylsilyl, diphenylmethylsilyl, triphenylsilyl, dimethylphenylsilyl, dimethyl-t-butylsilyl,
Examples include dimethyl (pentafluorophenyl) silyl. Particularly preferred are trimethylsilyl, triethylphenyl, diphenylmethylsilyl, isophenylsilyl, dimethylphenylsilyl, dimethyl-t-butylsilyl, dimethyl (pentafluorophenyl) silyl and the like.

In the present invention, as R ⁶ , a branched alkyl group having 3 to 30 carbon atoms, preferably 3 to 20 carbon atoms such as isopropyl, isobutyl, sec-butyl, tert-butyl, neopentyl, etc., and hydrogen of these groups Groups having 3 to 30 carbon atoms, such as groups substituted with aryl groups having 6 to 30 carbon atoms, preferably 6 to 20 carbon atoms (cumyl group, etc.), adamantyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc., preferably It is preferably a group selected from 3 to 20 cyclic saturated hydrocarbon groups, or an aryl group having 6 to 30 carbon atoms, preferably 6 to 20 carbon atoms, such as phenyl, naphthyl, fluorenyl, anthranyl and phenanthryl, or a hydrocarbon A substituted silyl group is also preferred.

R ^{1 to} R ⁶ are two or more of these groups, preferably adjacent groups connected to each other to form an aliphatic ring, an aromatic ring, or a hydrocarbon ring containing a hetero atom such as a nitrogen atom. These rings may further have a substituent.

When m is 2 or more, two groups out of the groups represented by R ^{1 to} R ⁶ may be linked. However, R ¹ is not bonded to each other. Further, when m is 2 or more, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , and R ⁶ may be the same or different from each other.

n is a number satisfying the valence of M, specifically 0 to 5, preferably 1 to 4, more preferably an integer of 1 to 3.
X is a hydrogen atom, halogen atom, hydrocarbon group, oxygen-containing group, sulfur-containing group, nitrogen-containing group, boron-containing group, aluminum-containing group, phosphorus-containing group, halogen-containing group, heterocyclic compound residue, silicon-containing Group, germanium-containing group, or tin-containing group. When n is 2 or more, they may be the same or different.

Examples of the halogen atom include fluorine, chlorine, bromine and iodine.
Examples of the hydrocarbon group include the same groups as those exemplified for R ^{1 to} R ⁶ . Specifically, alkyl groups such as methyl, ethyl, propyl, butyl, hexyl, octyl, nonyl, dodecyl, and eicosyl; cycloalkyl groups having 3 to 30 carbon atoms such as cyclopentyl, cyclohexyl, norbornyl, adamantyl; vinyl, Alkenyl groups such as propenyl and cyclohexenyl; arylalkyl groups such as benzyl, phenylethyl, and phenylpropyl; phenyl, tolyl, dimethylphenyl, trimethylphenyl, ethylphenyl, propylphenyl, biphenyl, naphthyl, methylnaphthyl, anthryl, phenanthryl, and the like Examples include, but are not limited to, an aryl group. These hydrocarbon groups also include halogenated hydrocarbons, specifically, groups in which at least one hydrogen of a hydrocarbon group having 1 to 20 carbon atoms is substituted with halogen.

Of these, those having 1 to 20 carbon atoms are preferred.
Examples of the heterocyclic compound residue include the same ones as exemplified for R ^{1 to} R ⁶ .

Examples of the oxygen-containing group include the same groups as those exemplified above for R ^{1 to} R ⁶ , specifically hydroxy groups; alkoxy groups such as methoxy, ethoxy, propoxy, butoxy; phenoxy, methylphenoxy, dimethyl Examples include, but are not limited to, aryloxy groups such as phenoxy and naphthoxy; arylalkoxy groups such as phenylmethoxy and phenylethoxy; acetoxy groups; carbonyl groups and the like.

Examples of the sulfur-containing group include the same groups as those exemplified for R ^{1 to} R ⁶ , specifically, methyl sulfonate, trifluoromethane sulfonate, phenyl sulfonate, benzyl sulfonate, Sulfonate groups such as p-toluene sulfonate, trimethylbenzene sulfonate, triisobutylbenzene sulfonate, p-chlorobenzene sulfonate, pentafluorobenzene sulfonate; methyl sulfinate, phenyl sulfinate, benzyl Examples thereof include, but are not limited to, sulfinate groups such as sulfinate, p-toluene sulfinate, trimethylbenzene sulfinate, pentafluorobenzene sulfinate; alkylthio group; arylthio group.

Specific examples of the nitrogen-containing group include the same groups as those exemplified above for R ^{1 to} R ⁶ , and specific examples include amino groups; methylamino, dimethylamino, diethylamino, dipropylamino, dibutylamino, Examples thereof include, but are not limited to, alkylamino groups such as dicyclohexylamino; arylamino groups such as phenylamino, diphenylamino, ditolylamino, dinaphthylamino, methylphenylamino, and alkylarylamino groups.

Specific examples of the boron-containing group include BR ₄ (R represents hydrogen, an alkyl group, an aryl group which may have a substituent, a halogen atom, or the like).
Specific examples of the phosphorus-containing group include trialkylphosphine groups such as trimethylphosphine, tributylphosphine, and tricyclohexylphosphine; triarylphosphine groups such as triphenylphosphine and tolylphosphine; methyl phosphite, ethyl phosphite, and phenyl phosphite Examples thereof include, but are not limited to, phosphite groups (phosphide groups); phosphonic acid groups; phosphinic acid groups.

Specific examples of the silicon-containing group include the same groups as those exemplified above for R ^{1 to} R ⁶ , and specifically, phenylsilyl, diphenylsilyl, trimethylsilyl, triethylsilyl, tripropylsilyl, tricyclohexylsilyl. Hydrocarbon substituted silyl groups such as triphenylsilyl, methyldiphenylsilyl, tolylsilylsilyl, trinaphthylsilyl; hydrocarbon substituted silyl ether groups such as trimethylsilyl ether; silicon substituted alkyl groups such as trimethylsilylmethyl; silicon substitution such as trimethylsilylphenyl An aryl group etc. are mentioned.

Specific examples of the germanium-containing group include the same groups as those exemplified above for R ^{1 to} R ⁶ , and specific examples include a group in which silicon in the silicon-containing group is replaced with germanium.

Specific examples of the tin-containing group include the same groups as those exemplified above for R ^{1 to} R ⁶ , and more specifically, a group in which silicon in the silicon-containing group is substituted with tin.
Specific examples of the halogen-containing group include fluorine-containing groups such as PF ₆ and BF ₄ , chlorine-containing groups such as ClO ₄ and SbCl _6, and iodine-containing groups such as IO ₄ , but are not limited thereto. Absent.

Specific examples of the aluminum-containing group include, but are not limited to, AlR ₄ (R represents hydrogen, an alkyl group, an aryl group which may have a substituent, a halogen atom, etc.).

When n is 2 or more, a plurality of groups represented by X may be the same or different from each other, and a plurality of groups represented by X may be bonded to each other to form a ring.
Transition metal compounds (Ia)
As such a transition metal compound represented by the formula (I), a compound represented by the following general formula (Ia) is preferable.

In the formula (Ia), M represents a transition metal atom in Groups 3 to 11 of the periodic table, and the same as those described above.
m is an integer of 1 to 3, and is preferably 2.

R ^{1 to} R ⁶ may be the same or different and are each a hydrogen atom, a halogen atom, a hydrocarbon group, a heterocyclic compound residue, a hydrocarbon-substituted silyl group, a hydrocarbon-substituted siloxy group, an alkoxy group, or an alkylthio group. , Aryloxy group, arylthio group, acyl group, ester group, thioester group, amide group, imide group, amino group, imino group, sulfone ester group, sulfonamide group, cyano group, nitro group, carboxyl group, sulfo group, mercapto group Alternatively, it represents a hydroxy group, and two or more of these may be connected to each other to form a ring. Examples of these groups include the same groups as described above.

In addition, when m is 2 or more, two groups out of the groups represented by R ^{1 to} R ⁶ may be linked. However, R ¹ is not bonded to each other.
n is a number that satisfies the valence of M, and is specifically an integer of 0 to 5, preferably 1 to 4, more preferably 1 to 3.

  X is a hydrogen atom, halogen atom, hydrocarbon group, oxygen-containing group, sulfur-containing group, nitrogen-containing group, boron-containing group, aluminum-containing group, phosphorus-containing group, halogen-containing group, heterocyclic compound residue, silicon-containing Group, germanium-containing group, or tin-containing group. Specifically, the same thing as the above is mentioned.

When n is 2 or more, a plurality of groups represented by X may be the same or different from each other, and a plurality of groups represented by X may be bonded to each other to form a ring.
As such a transition metal compound, a compound represented by the following general formula (Ia-1) is particularly preferable.

In formula (Ia-1), examples of R ^{1 to} R ⁶ , M and X include the same as those described above.
In particular, the following are preferable.
M represents a transition metal atom of Groups 3 to 11 of the periodic table, preferably a metal atom of Groups 3 to 5 and 9, preferably scandium, titanium, zirconium, hafnium, vanadium, niobium, tantalum, cobalt, Rhodium and the like, more preferably titanium, zirconium, hafnium, cobalt, rhodium and the like, and particularly preferably titanium, zirconium and hafnium.

m is an integer of 1-3.
R ^{1 to} R ⁶ may be the same or different and are each a hydrogen atom, a halogen atom, a hydrocarbon group, a heterocyclic compound residue, a hydrocarbon-substituted silyl group, a hydrocarbon-substituted siloxy group, an alkoxy group, or an alkylthio group. , Aryloxy group, arylthio group, thioester group, ester group, acyl group, amide group, imide group, amino group, imino group, sulfone ester group, sulfonamide group, cyano group, nitro group, hydroxy group and the like. Among these, a hydrogen atom, a halogen atom, a hydrocarbon group, a hydrocarbon-substituted silyl group, an alkoxy group, an aryloxy group, an ester group, an amide group, an amino group, a sulfonamide group, a cyano group, or a nitro group is particularly preferable.

Examples of the halogen atom include fluorine, chlorine, bromine and iodine.
Specific examples of the hydrocarbon group include straight chain having 1 to 20 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl or the like. Branched alkyl group; linear or branched alkenyl group having 2 to 20 carbon atoms such as vinyl, allyl, isopropenyl, etc .; linear or branched chain having 2 to 20 carbon atoms such as ethynyl, propargyl, etc. An alkynyl group of the above; a cyclic saturated hydrocarbon group having 3 to 20 carbon atoms such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl; an aryl having 6 to 20 carbon atoms such as phenyl, benzyl, naphthyl, biphenylyl, triphenylyl, etc. Groups: cyclopentadienyl, indenyl, fluorenyl and the like having 5 to 20 carbon atoms Sum hydrocarbon groups; and alkyl groups having 1 to 20 carbon atoms, halogenated alkyl groups having 1 to 20 carbon atoms, aryl groups having 6 to 20 carbon atoms, and the number of carbon atoms Examples include a group further substituted with a substituent such as an alkoxy group having 1 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, a halogen, a cyano group, a nitro group, and a hydroxy group. Among these, straight-chain or branched alkyl having 1 to 20 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, etc. An aryl group having 6 to 20 carbon atoms, such as phenyl or naphthyl; an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms; A substituted aryl group substituted with 1 to 5 substituents such as an alkoxy group having 1 to 20 carbon atoms and an aryloxy group having 6 to 20 carbon atoms is preferable.

  Heterocyclic compound residues include residues such as nitrogen-containing compounds such as pyrrole, pyridine, pyrimidine, quinoline, and triazine, oxygen-containing compounds such as furan and pyran, sulfur-containing compounds such as thiophene, and heterocyclic groups thereof. Examples of the compound residue include groups in which a substituent such as an alkyl group having 1 to 20 carbon atoms or an alkoxy group is further substituted.

Specific examples of the hydrocarbon-substituted silyl group include methylsilyl, dimethylsilyl, trimethylsilyl, ethylsilyl, diethylsilyl, triethylsilyl, diphenylmethylsilyl, triphenylsilyl, dimethylphenylsilyl, dimethyl-t-butylsilyl, dimethyl (
Pentafluorophenyl) silyl and the like. Among these, methylsilyl, dimethylsilyl, trimethylsilyl, ethylsilyl, diethylsilyl, triethylsilyl, triphenylsilyl and the like are particularly preferable.

Specific examples of the hydrocarbon-substituted siloxy group include trimethylsiloxy and the like.
Specific examples of the alkoxy group include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy and the like.

  Specific examples of the alkylthio group include methylthio and ethylthio. Specific examples of the aryloxy group include phenoxy, 2,6-dimethylphenoxy, 2,4,6-trimethylphenoxy and the like.

Specific examples of the arylthio group include phenylthio, methylphenylthio, naphthylthio and the like.
Specific examples of the acyl group include formyl group, acetyl group, benzoyl group, p-chlorobenzoyl group, and p-methoxybenzoyl group.

Specific examples of the ester group include acetyloxy, benzoyloxy, methoxycarbonyl, phenoxycarbonyl, p-chlorophenoxycarbonyl, and the like.
Specific examples of the thioester group include acetylthio, benzoylthio, methylthiocarbonyl, and phenylthiocarbonyl.

Specific examples of the amide group include acetamide, N-methylacetamide, N-methylbenzamide and the like.
Specific examples of the imide group include acetoimide and benzimide.

Specific examples of the amino group include dimethylamino, ethylmethylamino, diphenylamino and the like.
Specific examples of the imino group include methylimino, ethylimino, propylimino, butylimino, and phenylimino.

Specific examples of the sulfone ester group include methyl sulfonate, ethyl sulfonate, and phenyl sulfonate.
Specific examples of the sulfonamido group include phenylsulfonamido, N-methylsulfonamido, N-methyl-p-toluenesulfonamido and the like.

R ⁶ is preferably a substituent other than hydrogen. That is, R ⁶ is a halogen atom, hydrocarbon group, heterocyclic compound residue, hydrocarbon-substituted silyl group, hydrocarbon-substituted siloxy group, alkoxy group, alkylthio group, aryloxy group, arylthio group, acyl group, ester group, thioester It is preferably a group, an amide group, an imide group, an amino group, an imino group, a sulfone ester group, a sulfonamide group, a cyano group, a nitro group or a hydroxy group.

Preferred hydrocarbon groups for R ⁶ include straight chain having 1 to 20 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl and the like. Or a branched alkyl group; a cyclic saturated hydrocarbon group having 3 to 20 carbon atoms such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and adamantyl; and 6 to 6 carbon atoms such as phenyl, benzyl, naphthyl, biphenylyl, and triphenylyl. 20 aryl groups; and these groups include alkyl groups having 1 to 20 carbon atoms, halogenated alkyl groups having 1 to 20 carbon atoms, aryl groups having 6 to 20 carbon atoms, alkoxy groups, and aryloxy groups. Preferred is a group further substituted with a substituent such as a group, halogen, cyano group, nitro group or hydroxy group. Can be mentioned.

Preferred hydrocarbon-substituted silyl groups as R ⁶ include methylsilyl, dimethylsilyl, trimethylsilyl, ethylsilyl, diethylsilyl, triethylsilyl, diphenylmethylsilyl, triphenylsilyl, dimethylphenylsilyl, dimethyl-t-butylsilyl,
Examples include dimethyl (pentafluorophenyl) silyl.

In the present invention, as R ⁶ , a branched alkyl group having 3 to 20 carbon atoms such as isopropyl, isobutyl, sec-butyl, tert-butyl, etc., and a hydrogen atom of these groups having 6 to 6 carbon atoms. It is preferably a group selected from a cyclic saturated hydrocarbon group having 3 to 20 carbon atoms, such as a group substituted with 20 aryl groups (such as cumyl group), adamantyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, or the like, or A hydrocarbon-substituted silyl group is also preferred.

R ^{1 to} R ⁶ are two or more of these groups, preferably adjacent groups connected to each other to form an aliphatic ring, an aromatic ring, or a hydrocarbon ring containing a hetero atom such as a nitrogen atom. These rings may further have a substituent.

When m is 2 or more, two groups out of the groups represented by R ^{1 to} R ⁶ may be linked. However, R ¹ is not bonded to each other. Further, when m is 2 or more, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , and R ⁶ may be the same or different from each other.

n is a number satisfying the valence of M, specifically an integer of 1 to 3.
X represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group, a sulfur-containing group, a silicon-containing group, or the like. In the case of two or more, they may be the same or different from each other.

Examples of the halogen atom include fluorine, chlorine, bromine and iodine.
Examples of the hydrocarbon group having 1 to 20 carbon atoms include an alkyl group, a cycloalkyl group, an alkenyl group, an arylalkyl group, an aryl group, and more specifically, methyl, ethyl, propyl, butyl, hexyl. Alkyl groups such as cyclopentyl, cyclohexyl, norbornyl and adamantyl; alkenyl groups such as vinyl, propenyl and cyclohexenyl; arylalkyl groups such as benzyl, phenylethyl and phenylpropyl; Examples include aryl groups such as phenyl, tolyl, dimethylphenyl, trimethylphenyl, ethylphenyl, propylphenyl, biphenyl, naphthyl, methylnaphthyl, anthryl, phenanthryl.

Examples of the halogenated hydrocarbon group having 1 to 20 carbon atoms include groups in which a halogen is substituted for the hydrocarbon group having 1 to 20 carbon atoms.
Examples of the oxygen-containing group include hydroxy groups; alkoxy groups such as methoxy, ethoxy, propoxy, and butoxy; aryloxy groups such as phenoxy, methylphenoxy, dimethylphenoxy, and naphthoxy; arylalkoxy groups such as phenylmethoxy and phenylethoxy.

  The sulfur-containing group includes a substituent in which oxygen of the oxygen-containing group is substituted with sulfur, methyl sulfonate, trifluoromethane sulfonate, phenyl sulfonate, benzyl sulfonate, p-toluene sulfonate, trimethyl. Sulfonate groups such as benzene sulfonate, triisobutyl benzene sulfonate, p-chlorobenzene sulfonate, pentafluorobenzene sulfonate; methyl sulfinate, phenyl sulfinate, benzyl sulfinate, p-toluene Examples thereof include sulfinate groups such as ruffinate, trimethylbenzene sulfinate, and pentafluorobenzene sulfinate.

  Examples of silicon-containing groups include monohydrocarbon-substituted silyl groups such as methylsilyl and phenylsilyl; dihydrocarbon-substituted silyl groups such as dimethylsilyl and diphenylsilyl; trimethylsilyl, triethylsilyl, tripropylsilyl, tricyclohexylsilyl, triphenylsilyl, Trihydrocarbon-substituted silyl groups such as dimethylphenylsilyl, methyldiphenylsilyl, tolylsilylsilyl, trinaphthylsilyl; hydrocarbon-substituted silyl silyl ether groups such as trimethylsilyl ether; silicon-substituted alkyl groups such as trimethylsilylmethyl; trimethylsilylphenyl and the like Examples include silicon-substituted aryl groups.

Of these, the group represented by X is preferably a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a sulfonate group.
When n is 2 or more, the groups represented by X may be the same as or different from each other, or may be linked to each other to form a ring.

In the transition metal compound represented by the general formula (Ia-1), m is 2, and R ^{1 to} R ⁶
A compound in which two groups (excluding R ¹ ) are linked is a compound represented by the following general formula (Ia-2), for example.

In the formula (Ia-2), M, R ^{1 to} R ⁶ and X are the same as those in the general formula (I), and R ^{11 to} R ¹⁶ are the same as R ^{1 to} R ⁶ . Particularly preferred are the following groups.

R ^{1 to} R ¹⁶ may be the same or different and are each a hydrogen atom, a halogen atom, a hydrocarbon group, a heterocyclic compound residue, a hydrocarbon-substituted silyl group, a hydrocarbon-substituted siloxy group, an alkoxy group, or an alkylthio group. , Aryloxy group, arylthio group, acyl group, ester group, thioester group, amide group, imide group, amino group, imino group, sulfone ester group, sulfonamide group, cyano group, nitro group, etc., specifically R ^{1 to} R ⁶ are the same atoms or groups. Two or more groups of R ^{1 to} R ¹⁶ , preferably adjacent groups, may be linked to each other to form an aliphatic ring, an aromatic ring, or a hydrocarbon ring containing a hetero atom such as a nitrogen atom. Good.

Y ′ binds at least one group selected from R ^{1 to} R ⁶ and at least one group selected from R ^{11 to} R ¹⁶ (provided that R ¹ and R ¹¹ bind to each other). Except in cases) A linking group or a single bond.

Examples of the linking group represented by Y ′ include a group containing at least one element selected from oxygen, sulfur, carbon, nitrogen, phosphorus, silicon, selenium, tin, boron, and the like. A chalcogen atom-containing group such as O—, —S—, —Se—; —NH—, —N (CH ₃ ) ₂ —,
Nitrogen or phosphorus atom-containing groups such as —PH— and —P (CH ₃ ) ₂ —; —CH ₂ — and —CH ₂
A hydrocarbon group having 1 to 20 carbon atoms such as —CH ₂ — and —C (CH ₃ ) ₂ —;
Cyclic unsaturated hydrocarbon residues having 6 to 20 carbon atoms such as naphthalene and anthracene; heterocyclic compound residues having 3 to 20 carbon atoms including heteroatoms such as pyridine, quinoline, thiophene and furan; Silicon atom-containing groups such as SiH ₂ — and —Si (CH ₃ ) ₂ —, —Sn
Tin atom-containing groups such as H ₂ —, —Sn (CH ₃ ) ₂ —; —BH—, —B (CH ₃ ) —, —BF
Examples thereof include a boron atom-containing group such as-or a single bond.

Specific examples of the transition metal compound represented by the general formula (Ia-1) are shown below, but are not limited thereto.
In the following specific examples, M is a transition metal element, and each of them is Sc (III), Ti (III), Ti (IV), Zr (III), Zr (IV), Hf (IV), V ( IV), Nb (V), Ta (V), Co (II), Co (III), Rh (II), Rh (III) and Rh (IV) are shown, but not limited thereto. Of these, Ti (IV), Zr (IV), and Hf (IV) are particularly preferable.

  X represents a halogen such as Cl and Br, or an alkyl group such as methyl, but is not limited thereto. Further, when there are a plurality of X, these may be the same or different.

  n is determined by the valence of the metal M. For example, when two monoanion species are bonded to a metal, n = 0 for a divalent metal, n = 1 for a trivalent metal, n = 2 for a tetravalent metal, and n = 3 for a pentavalent metal. . For example, when the metal is Ti (IV), n = 2, when Zr (IV) is n = 2, and when Hf (IV) is n = 2.

In the above examples, Me represents a methyl group, Et represents an ethyl group, iPr represents an i-propyl group, tBu represents a tert-butyl group, and Ph represents a phenyl group.
Further specific examples of the case where Ti is the central metal include the following. Moreover, the compound which replaced titanium in these compounds with zirconium, hafnium, cobalt, or rhodium is also mentioned.

In the olefin polymerization catalyst according to the present invention, it is particularly preferable to use a novel transition metal compound of the general formula (III) as described later as the component (A).
Transition metal compound (Ib)
In the present invention, as the transition metal compound (A), a transition metal compound represented by the following general formula (Ib) can also be used.

In the formula (Ib), M represents a transition metal atom of Group 3 to 11 of the periodic table, preferably a Group 3 to Group 5 or Group 9, particularly preferably a Group 4 or Group 5 transition metal atom. In particular titanium, zirconium, hafnium, cobalt or rhodium.

m is an integer of 1-6, preferably an integer of 1-4.
R ^{1 to} R ⁶ may be the same or different and are each a hydrogen atom, a halogen atom, a hydrocarbon group, a hydrocarbon-substituted silyl group, an alkoxy group, an aryloxy group, an ester group, an amide group, an amino group, or a sulfonamide group. , A cyano group and a nitro group.

  Of these groups, a halogen atom, a hydrocarbon group, a hydrocarbon-substituted silyl group, an alkoxy group, an aryloxy group, an ester group, an amide group, an amino group, a sulfonamide group, a cyano group, and a nitro group are particularly preferable.

Examples of these groups R ^{1 to} R ⁶ include the same groups as those exemplified in the transition metal compounds represented by the general formulas (I) and (Ia).
When m is 2 or more, R ^{1 to} R ⁶ may be formed by connecting two or more of these groups, preferably adjacent groups, to each other. However, R ¹ is not connected to each other.

Specific examples of the transition metal compound represented by the general formula (Ib) are shown below, but are not limited thereto.

  In the present invention, a transition metal compound in which the cobalt metal is replaced with a metal such as titanium, zirconium, hafnium, iron, copper, rhodium in the above-described compound can also be used.

  The above transition metal compounds (A) are used singly or in combination of two or more. Moreover, it can also be used in combination with a transition metal compound other than the transition metal compound (A), for example, a known transition metal compound comprising a ligand containing a hetero atom such as nitrogen, oxygen, sulfur, boron or phosphorus.

Other transition metal compounds As transition metal compounds other than the transition metal compound (A), specifically, the following transition metal compounds can be used, but not limited thereto.
(a-1) Transition metal imide compound represented by the following formula (Ic)

In the formula, M represents a transition metal atom of Groups 8 to 10 of the periodic table, and is preferably nickel, palladium, or platinum.
R ^{21 to} R ²⁴ may be the same as or different from each other, and are a hydrocarbon group having 1 to 50 carbon atoms, a halogenated hydrocarbon group having 1 to 50 carbon atoms, a hydrocarbon-substituted silyl group, or nitrogen, oxygen, phosphorus, A hydrocarbon group substituted with a substituent containing at least one element selected from sulfur and silicon.

Two or more of these groups represented by R ^{21 to} R ²⁴ , preferably adjacent groups may be linked to each other to form a ring.
q shows the integer of 0-4.

X represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group, a sulfur-containing group, a silicon-containing group or a nitrogen-containing group. , Q is 2 or more, the plurality of groups represented by X may be the same as or different from each other.
(a-2) Transition metal amide compound (Id) represented by the following formula

In the formula, M represents a transition metal atom of Groups 3 to 6 of the periodic table, and is preferably titanium, zirconium or hafnium.
R ′ and R ″ may be the same or different from each other, and are a hydrogen atom, a hydrocarbon group having 1 to 50 carbon atoms, a halogenated hydrocarbon group having 1 to 50 carbon atoms, a hydrocarbon-substituted silyl group, or nitrogen. And a substituent having at least one element selected from oxygen, phosphorus, sulfur and silicon.

m is an integer of 0-2.
n is an integer of 1-5.
A represents an atom of Groups 13 to 16 of the periodic table, specifically boron, carbon, nitrogen, oxygen,
Examples thereof include silicon, phosphorus, sulfur, germanium, selenium, and tin, and carbon or silicon is preferable. When n is 2 or more, the plurality of A may be the same as or different from each other.

  E is a substituent having at least one element selected from carbon, hydrogen, oxygen, halogen, nitrogen, sulfur, phosphorus, boron and silicon. When m is 2, two Es may be the same as or different from each other, or may be connected to each other to form a ring.

p is an integer of 0-4.
X represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group, a sulfur-containing group, a silicon-containing group or a nitrogen-containing group. Indicates. When p is 2 or more, the plurality of groups represented by X may be the same as or different from each other. Among these, X is preferably a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a sulfonate group.
(a-3) Transition metal diphenoxy compound represented by the following formula (Ie)

In the formula, M represents a transition metal atom of Groups 3 to 11 of the periodic table, l and m are each an integer of 0 or 1, A and A ′ are a hydrocarbon group having 1 to 50 carbon atoms, carbon 1-5 atoms
A halogenated hydrocarbon of 0, a hydrocarbon group having a substituent containing oxygen, sulfur or silicon, or a halogenated hydrocarbon group having 1 to 50 carbon atoms, and A and A ′ are the same or different. May be.

B is a hydrocarbon group having 0 to 50 carbon atoms, a halogenated hydrocarbon group having 1 to 50 carbon atoms, a group represented by R ¹ R ² Z, oxygen or sulfur, wherein R ¹ and R ² is a hydrocarbon group having 1 to 20 carbon atoms or a hydrocarbon group having 1 to 20 carbon atoms containing at least one hetero atom, and Z represents carbon, nitrogen, sulfur, phosphorus or silicon.

n is a number satisfying the valence of M.
X represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group, a sulfur-containing group, a silicon-containing group or a nitrogen-containing group. When n is 2 or more, a plurality of groups represented by X may be the same or different from each other, or may be bonded to each other to form a ring.
(a-4) Transition metal compound containing a ligand having a cyclopentadienyl skeleton containing at least one heteroatom represented by the following formula (If)

In the formula, M represents a transition metal atom of Groups 3 to 11 of the periodic table.
X represents an atom of Group 13, 14 or 15 of the periodic table, and at least one of X is an element other than carbon.

a represents 0 or 1.
R may be the same or different from each other, and R is at least one selected from a hydrogen atom, a halogen atom, a hydrocarbon group, a halogenated hydrocarbon group, a hydrocarbon group-substituted silyl group, or nitrogen, oxygen, phosphorus, sulfur and silicon. The hydrocarbon group substituted by the substituent containing a seed element is shown, and two or more Rs may be connected to each other to form a ring.

b is an integer of 1 to 4, and when b is 2 or more, each [((R) _a ) ₅ -X ₅ ] group may be the same or different, and R may be cross-linked. Good.
c is a number satisfying the valence of M.

  Y represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group, a sulfur-containing group, a silicon-containing group or a nitrogen-containing group. .

When c is 2 or more, a plurality of groups represented by Y may be the same as or different from each other, and a plurality of groups represented by Y may be bonded to each other to form a ring.
(a-5) Transition metal compound represented by the formula RB (Pz) ₃ MX _{n In the} formula, M represents a group 3-11 transition metal compound in the periodic table, R is a hydrogen atom, 1-20 carbon atoms Or a halogenated hydrocarbon group having 1 to 20 carbon atoms, and Pz represents a pyrazoyl group or a substituted pyrazoyl group.

n is a number satisfying the valence of M.
X represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group, a sulfur-containing group, a silicon-containing group or a nitrogen-containing group. . When n is 2 or more, a plurality of groups represented by X may be the same or different from each other, or may be bonded to each other to form a ring.
(a-6) Transition metal compound (Ig) represented by the following formula

In the formula, Y ₁ and Y ₃ may be the same as or different from each other, and are elements of Group 15 of the Periodic Table, and Y ₂ is an element of Group 16 of the Periodic Table.
R ^{21 to} R ²⁸ may be the same or different from each other, and are a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group, A sulfur-containing group or a silicon-containing group is shown, and two or more of these may be connected to each other to form a ring.
(a-7) A compound of a compound represented by the following formula (Ih) and a group VIII transition metal atom

In the formula, R ^{31 to} R ³⁴ may be the same as or different from each other, and are a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a halogenated hydrocarbon group having 1 to 20 carbon atoms. Two or more of these may be connected to each other to form a ring.
(a-8) Transition metal compound represented by the following formula (Ii)

In the formula, M represents a transition metal atom of Groups 3 to 11 of the periodic table,
m is an integer of 0 to 3,
n is an integer of 0 or 1;
p is an integer of 1 to 3,
q is a number satisfying the valence of M.

R ^{41 to} R ⁴⁸ may be the same or different from each other, and are a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group, A sulfur-containing group, a silicon-containing group or a nitrogen-containing group is shown, and two or more of these may be connected to each other to form a ring.

  X represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group, a sulfur-containing group, a silicon-containing group or a nitrogen-containing group. , Q is 2 or more, a plurality of groups represented by X may be the same or different from each other, or a plurality of groups represented by X may be bonded to each other to form a ring.

Y is a group that bridges the boratabenzene ring, and represents carbon, silicon, or germanium.
A represents an element of Group 14, 15 or 16 of the periodic table.

(B-1) Organometallic compound (B-1) As the organometallic compound used in the present invention, specifically, the following organometallic compounds of Groups 1, 2 and 12, 13 of the periodic table are: Used.

(B-1a) General formula R ^a _m Al (OR ^b ) _n H _p X _q
(In the formula, R ^a and R ^b may be the same or different from each other, each represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, X represents a halogen atom, and m represents 0. <M ≦ 3, n is 0 ≦ n <3, p is 0 ≦ p <3, q is a number of 0 ≦ q <3, and m + n + p + q = 3.)
An organoaluminum compound represented by

(B-1b) General formula M ² AlR ^a ₄
(In the formula, M ² represents Li, Na or K, and R ^a represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms.)
A complex alkylated product of a group 1 metal and aluminum in the periodic table represented by:

(B-1c) General formula R ^a R ^b M ³
(In the formula, R ^a and R ^b may be the same or different from each other, and each represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, and M ³ is Mg, Zn or Cd. .)
A dialkyl compound of a Group 2 or Group 12 metal represented by the following periodic table.

Examples of the organoaluminum compound belonging to (B-1a) include the following compounds.
General formula R ^a _m Al (OR ^b ) _3-m
(In the formula, R ^a and R ^b may be the same or different from each other, and each represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, and m is preferably 1.5 ≦ m ≦ A number of 3.)
An organoaluminum compound represented by
General formula R ^a _m AlX _3-m
(Wherein, R ^a represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, X represents a halogen atom, and m is preferably 0 <m <3). Organoaluminum compounds,
General formula R ^a _m AlH _3-m
(In the formula, Ra represents ^a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, and m is preferably 2 ≦ m <3.)
An organoaluminum compound represented by
General formula R ^a _m Al (OR ^b ) _n X _q
(In the formula, R ^a and R ^b may be the same or different from each other, each represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, X represents a halogen atom, and m represents 0. <M ≦ 3, n is a number 0 ≦ n <3, q is a number 0 ≦ q <3, and m + n + q = 3.)
An organoaluminum compound represented by

More specific examples of organoaluminum compounds belonging to (B-1a) include trimethylaluminum, triethylaluminum, tri-n-butylaluminum, tripropylaluminum, tripentylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum and the like. n-alkyl aluminum;
Triisopropylaluminum, triisobutylaluminum, trisec-butylaluminum, tritert-butylaluminum, tri-2-methylbutylaluminum, tri-3-methylbutylaluminum, tri-2-methylpentylaluminum, tri-3-methylpentylaluminum, tri-4 -Tri-branched alkylaluminums such as methylpentylaluminum, tri-2-methylhexylaluminum, tri-3-methylhexylaluminum, tri-2-ethylhexylaluminum;
Tricycloalkylaluminum such as tricyclohexylaluminum, tricyclooctylaluminum;
Triarylaluminums such as triphenylaluminum and tolylylaluminum;
Dialkylaluminum hydrides such as diisobutylaluminum hydride;
_{(I-C 4 H 9)} x Al y (C 5 H 10) z ( wherein, x, y, z are each a positive number, and z ≧ 2x.) Tri isoprenylaluminum represented by like Trialkenyl aluminum such as;
Alkyl aluminum alkoxides such as isobutyl aluminum methoxide, isobutyl aluminum ethoxide, isobutyl aluminum isopropoxide;
Dialkylaluminum alkoxides such as dimethylaluminum methoxide, diethylaluminum ethoxide, dibutylaluminum butoxide;
Alkylaluminum sesquialkoxides such as ethylaluminum sesquiethoxide and butylaluminum sesquibutoxide;
Partially alkoxylated alkylaluminum having an average composition such as R ^a _2.5 Al (OR ^b ) _0.5 ;
Diethylaluminum phenoxide, diethylaluminum (2,6-di-t-butyl-4-methylphenoxide), ethylaluminum bis (2,6-di-t-butyl-4-methylphenoxide), diisobutylaluminum (2,6- Dialkylaluminum aryloxides such as di-t-butyl-4-methylphenoxide), isobutylaluminum bis (2,6-di-t-butyl-4-methylphenoxide);
Dialkylaluminum halides such as dimethylaluminum chloride, diethylaluminum chloride, dibutylaluminum chloride, diethylaluminum bromide, diisobutylaluminum chloride;
Alkylaluminum sesquichlorides such as ethylaluminum sesquichloride, butylaluminum sesquichloride, ethylaluminum sesquibromide;
Partially halogenated alkylaluminums such as alkylaluminum dihalides such as ethylaluminum dichloride, propylaluminum dichloride, butylaluminum dibromide;
Dialkylaluminum hydrides such as diethylaluminum hydride, dibutylaluminum hydride;
Other partially hydrogenated alkylaluminums such as alkylaluminum dihydrides such as ethylaluminum dihydride, propylaluminum dihydride;
Examples include partially alkoxylated and halogenated alkylaluminums such as ethylaluminum ethoxychloride, butylaluminum butoxychloride, and ethylaluminum ethoxybromide.

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

As the compound belonging to (B-1b),
Examples thereof include LiAl (C ₂ H ₅ ) ₄ and LiAl (C ₇ H ₁₅ ) ₄ .
In addition, (B-1) organometallic compounds include methyl lithium, ethyl lithium, propyl lithium, butyl lithium, methyl magnesium bromide, methyl magnesium chloride, ethyl magnesium bromide, ethyl magnesium chloride, propyl magnesium bromide, propyl magnesium. Chloride, butyl magnesium bromide, butyl magnesium chloride, dimethyl magnesium, diethyl magnesium, dibutyl magnesium, butyl ethyl magnesium and the like can also be used.

  A compound that can form the organoaluminum compound in the polymerization system, for example, a combination of aluminum halide and alkyllithium, or a combination of aluminum halide and alkylmagnesium can also be used.

(B-1) Among organometallic compounds, organoaluminum compounds are preferred.
The (B-1) organometallic compounds as described above are used singly or in combination of two or more.

(B-2) Organoaluminum oxy compound (B-2) The organoaluminum oxy compound used in the present invention may be a conventionally known aluminoxane or as exemplified in JP-A-2-78687. It may be a benzene-insoluble organoaluminum oxy compound.

A conventionally well-known aluminoxane can be manufactured, for example with the following method, and is normally obtained as a solution of a hydrocarbon solvent.
(1) Compounds containing adsorbed water or salts containing water of crystallization, such as magnesium chloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate, first cerium chloride hydrate, etc. A method of reacting adsorbed water or crystal water with an organoaluminum compound by adding an organoaluminum compound such as trialkylaluminum to the above suspension of the hydrocarbon medium.
(2) A method of allowing water, ice or water vapor to act directly on an organoaluminum compound such as trialkylaluminum in a medium such as benzene, toluene, ethyl ether or tetrahydrofuran.
(3) A method in which an organotin oxide such as dimethyltin oxide or dibutyltin oxide is reacted with an organoaluminum compound such as trialkylaluminum in a medium such as decane, benzene, or toluene.

  The aluminoxane may contain a small amount of an organometallic component. Further, after removing the solvent or the unreacted organoaluminum compound from the recovered aluminoxane solution by distillation, it may be redissolved in a solvent or suspended in a poor aluminoxane solvent.

  Specific examples of the organoaluminum compound used when preparing the aluminoxane include the same organoaluminum compounds as those exemplified as the organoaluminum compound belonging to (B-1a).

Of these, trialkylaluminum and tricycloalkylaluminum are preferable, and trimethylaluminum is particularly preferable.
The above organoaluminum compounds are used singly or in combination of two or more.

  Solvents used for the preparation of aluminoxane include aromatic hydrocarbons such as benzene, toluene, xylene, cumene, and cymene, aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, hexadecane, and octadecane, and cyclopentane. , Cycloaliphatic hydrocarbons such as cyclohexane, cyclooctane and methylcyclopentane, petroleum fractions such as gasoline, kerosene and light oil, or halides of the above aromatic hydrocarbons, aliphatic hydrocarbons and alicyclic hydrocarbons, especially chlorine And hydrocarbon solvents such as bromide and bromide. Furthermore, ethers such as ethyl ether and tetrahydrofuran can also be used. Of these solvents, aromatic hydrocarbons or aliphatic hydrocarbons are particularly preferable.

  The benzene-insoluble organoaluminum oxy compound used in the present invention has an Al component dissolved in benzene at 60 ° C. of usually 10% or less, preferably 5% or less, particularly preferably 2% or less in terms of Al atom, That is, those that are insoluble or hardly soluble in benzene are preferred.

  Examples of the organoaluminum oxy compound used in the present invention include organoaluminum oxy compounds containing boron represented by the following general formula (IV).

In the formula, R ¹⁷ represents a hydrocarbon group having 1 to 10 carbon atoms.
R ¹⁸ may be the same as or different from each other, and each represents a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 10 carbon atoms.

The organoaluminum oxy compound containing boron represented by the general formula (IV) includes an alkyl boronic acid represented by the following general formula (V):
R ¹⁷ -B- (OH) ₂ (V)
(In the formula, R ¹⁷ represents the same group as described above.)
It can be produced by reacting an organoaluminum compound in an inert solvent under an inert gas atmosphere at a temperature of −80 ° C. to room temperature for 1 minute to 24 hours.

  Specific examples of the alkyl boronic acid represented by the general formula (V) include methyl boronic acid, ethyl boronic acid, isopropyl boronic acid, n-propyl boronic acid, n-butyl boronic acid, isobutyl boronic acid, n-hexyl boron. Examples include acid, cyclohexyl boronic acid, phenyl boronic acid, 3,5-difluoro boronic acid, pentafluorophenyl boronic acid, 3,5-bis (trifluoromethyl) phenyl boronic acid, and the like. Among these, methyl boronic acid, n-butyl boronic acid, isobutyl boronic acid, 3,5-difluorophenyl boronic acid, and pentafluorophenyl boronic acid are preferable. These may be used alone or in combination of two or more.

  Specific examples of the organoaluminum compound to be reacted with the alkylboronic acid include the same organoaluminum compounds as those exemplified as the organoaluminum compound belonging to (B-1a).

Of these, trialkylaluminum and tricycloalkylaluminum are preferable, and trimethylaluminum, triethylaluminum, and triisobutylaluminum are particularly preferable. These may be used alone or in combination of two or more.

The (B-2) organoaluminum oxy compounds as described above are used singly or in combination of two or more.
(B-3) A compound that reacts with a transition metal compound to form an ion pair A compound that reacts with the transition metal compound used in the present invention to form an ion pair (B-3) (hereinafter referred to as “ionized ionic compound”) Is a compound that reacts with the transition metal compound (A) to form an ion pair. Examples of such compounds include JP-A-1-501950, JP-A-1-502036, Lewis acids, ionic compounds, borane compounds and carboranes described in JP-A-3-179005, JP-A-3-179006, JP-A-3-207703, JP-A-3-207704, USP-5321106 and the like. A compound etc. can be mentioned. Furthermore, heteropoly compounds and isopoly compounds can also be mentioned.

Specifically, as the Lewis acid, a compound represented by BR ₃ (R is a phenyl group which may have a substituent such as fluorine, methyl group, trifluoromethyl group or fluorine) is exemplified. For example, trifluoroboron, triphenylboron, tris (4-fluorophenyl) boron, tris (3,5-difluorophenyl) boron, tris (4-fluoromethylphenyl) boron, tris (pentafluorophenyl) boron, tris Examples include (p-tolyl) boron, tris (o-tolyl) boron, and tris (3,5-dimethylphenyl) boron.

  Examples of the ionic compound include compounds represented by the following general formula (VI).

In the formula, R ¹⁹ includes H ⁺ , carbonium cation, oxonium cation, ammonium cation, phosphonium cation, cycloheptyltrienyl cation, ferrocenium cation having a transition metal, and the like.

R ^{20 to} R ²³ may be the same as or different from each other, and are an organic group, preferably an aryl group or a substituted aryl group.
Specific examples of the carbonium cation include trisubstituted carbonium cations such as triphenylcarbonium cation, tri (methylphenyl) carbonium cation, and tri (dimethylphenyl) carbonium cation.

  Specific examples of the ammonium cation include trialkylammonium cations, triethylammonium cations, tripropylammonium cations, tributylammonium cations, tri (n-butyl) ammonium cations, and the like; N, N-dimethylanilinium cations; N, N-diethylanilinium cation, N, N-dialkylanilinium cation such as N, N-2,4,6-pentamethylanilinium cation; dialkylammonium cation such as di (isopropyl) ammonium cation and dicyclohexylammonium cation Etc.

  Specific examples of the phosphonium cation include triarylphosphonium cations such as triphenylphosphonium cation, tri (methylphenyl) phosphonium cation, and tri (dimethylphenyl) phosphonium cation.

R ¹⁹ is preferably a carbonium cation, an ammonium cation or the like, and particularly preferably a triphenylcarbonium cation, an N, N-dimethylanilinium cation or an N, N-diethylanilinium cation.

  Examples of the ionic compound include trialkyl-substituted ammonium salts, N, N-dialkylanilinium salts, dialkylammonium salts, and triarylphosphonium salts.

Specific examples of the trialkyl-substituted ammonium salt include, for example, triethylammonium tetra (phenyl) boron, tripropylammonium tetra (phenyl) boron, tri (n-butyl) ammonium tetra (phenyl) boron, and trimethylammonium tetra (p-tolyl). Boron, trimethylammonium tetra (o-tolyl) boron, tri (n-butyl) ammonium tetra (pentafluorophenyl) boron, tripropylammonium tetra (o, p-dimethylphenyl) boron, tri (n-butyl) ammonium tetra ( m, m-dimethylphenyl) boron, tri (n-butyl) ammonium tetra (p-trifluoromethylphenyl) boron, tri (n-butyl) ammonium tetra (3,5-ditrifluoromethylphenyl) boron, tri (n -Butyl) Ammoni And umtetra (o-tolyl) boron.

  Specific examples of N, N-dialkylanilinium salts include N, N-dimethylanilinium tetra (phenyl) boron, N, N-diethylanilinium tetra (phenyl) boron, N, N-2,4,6 -Pentamethylanilinium tetra (phenyl) boron and the like.

  Specific examples of the dialkylammonium salt include di (1-propyl) ammonium tetra (pentafluorophenyl) boron and dicyclohexylammonium tetra (phenyl) boron.

Further, as ionic compounds, triphenylcarbenium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, ferrocenium tetra (pentafluorophenyl) borate, triphenylcarbenium pentaphenyl Mention may also be made of cyclopentadienyl complexes, N, N-diethylanilinium pentaphenylcyclopentadienyl complexes, boron compounds represented by the following formula (VII) or (VIII).

(In the formula, Et represents an ethyl group.)

Specific examples of the borane compound include decaborane (14);
Bis [tri (n-butyl) ammonium] nonaborate, bis [tri (n-butyl) ammonium] decaborate, bis [tri (n-butyl) ammonium] undecaborate, bis [tri (n-butyl) ammonium] dodecaborate Salts of anions such as bis [tri (n-butyl) ammonium] decachlorodecaborate and bis [tri (n-butyl) ammonium] dodecachlorododecaborate;
Of metal borane anions such as tri (n-butyl) ammonium bis (dodecahydridododecaborate) cobaltate (III) and bis [tri (n-butyl) ammonium] bis (dodecahydridododecaborate) nickate (III) Examples include salt.

Specific examples of carborane compounds include:
4-carbanonaborane (14), 1,3-dicarbanonarborane (13), 6,9-dicarbadecarborane (14), dodecahydride-1-phenyl-1,3-dicarbanonarborane, dodecahydride- 1-methyl-1,3-dicarbanonaborane, undecahydride-1,3-dimethyl-1,3-dicarbanonaborane, 7,8-dicarbaunaborane (13), 2,7-dicarbaun Decaborane (13), undecahydride-7,8-dimethyl-7,8-dicarboundecaborane, dodecahydride-11-methyl-2,7-dicarboundecarborane, tri (n-butyl) ammonium 1-
Carbadecaborate, tri (n-butyl) ammonium 1-carbaundecaborate, tri (n-butyl) ammonium 1-carbadodecaborate, tri (n-butyl) ammonium 1-trimethylsilyl-1-carbadecaborate, tri ( n-butyl) ammonium bromo-1-carbadodecaborate, tri (n-butyl) ammonium 6-carbadecaborate (14), tri (n-butyl) ammonium 6-carbadecaborate (12), tri (n-butyl) ) Ammonium 7-carbaound decaborate (13), Tri (n-butyl) ammonium 7,8-dicarbaound decaborate (12), Tri (n-butyl) ammonium 2,9-dicarbound decaborate (12), Tri (n-butyl) ammonium dodecahydride-8-methyl-7,9-dicarbaundecaborate, tri (n-butyl) ammonium unde Hydride-8-ethyl-7,9-dicarbaundecaborate, tri (n-butyl) ammonium undecahydride-8-butyl-7,9-dicarbaundecaborate, tri (n-butyl) ammonium undecahydride- 8-allyl-7,9-dicarbaundecaborate, tri (n-butyl) ammonium undecahydride-9-trimethylsilyl-7,8-dicarbaundecaborate, tri (n-butyl) ammonium undecahydride-4, Salts of anions such as 6-dibromo-7-carbaundecaborate;
Tri (n-butyl) ammonium bis (nonahydride-1,3-dicarbanonaborate)
Cobaltate (III), tri (n-butyl) ammonium bis (undecahydride-7,8-
Dicarbaundecaborate) ferrate (III), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarboundecaborate) cobaltate (III), tri (n-butyl) ammonium bis ( Undecahydride-7,8-dicarboundecaborate) nickelate (III), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarbundecaborate) cuprate (III), tri (N-Butyl) ammonium bis (undecahydride-7,8-dicarbaundecaborate) aurate (III), tri (n-butyl) ammonium bis (nonahydride-7,8-dimethyl-7,8- Dicarbaundecaborate) ferrate (III), tri (n-butyl) ammonium bis (nonahydride-7,8-dimethyl-7,8-dicarboundecaborate) chromate (III), tri (n- Butyl) Ammoniu Mubis (tribromooctahydride-7,8-dicarbaundecaborate) cobaltate (III), tris [tri (n-butyl) ammonium] bis (undecahydride-7-carbaundecaborate) chromate ( III), bis [tri (n-butyl) ammonium] bis (undecahydride-7-
Carbundecaborate) manganate (IV), bis [tri (n-butyl) ammonium] bis (undecahydride-7-carbaundecaborate) cobaltate (III), bis [
And salts of metal carborane anions such as tri (n-butyl) ammonium] bis (undecahydride-7-carbaundecaborate) nickelate (IV).

  The heteropoly compound is composed of atoms composed of silicon, phosphorus, titanium, germanium, arsenic or tin and one or more atoms selected from vanadium, niobium, molybdenum and tungsten. Specifically, phosphovanadic acid, germanovanadic acid, arsenic vanadic acid, phosphoniobic acid, germanoniobic acid, siliconomolybdic acid, phosphomolybdic acid, titanium molybdic acid, germanomolybdic acid, arsenic molybdic acid, tin molybdic acid, phosphorus Tungstic acid, germanotungstic acid, tin tungstic acid, phosphomolybdovanadic acid, phosphotungstovanadic acid, germanotungstovanadic acid, phosphomolybdotungstovanadic acid, germanomolybdo tungstovanadate, phosphomolybdo Tungstic acid, phosphomolybdoniobic acid, salts of these acids, such as metals of group Ia or IIa of the periodic table, specifically lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium ,barium Salts with and organic salts such as triphenylethyl salt, and isopoly compound can be used but not limited thereto.

The heteropoly compound and the isopoly compound are not limited to one of the above compounds, and two or more of them can be used.
The above (B-3) ionized ionic compounds may be used alone or in combination of two or more.

When the transition metal compound according to the present invention is used as a catalyst, when it is used in combination with an organoaluminum oxy compound (B-2) such as methylaluminoxane as a promoter component, it exhibits a very high polymerization activity for an olefin compound. When an ionized ionic compound (B-3) such as triphenylcarbonium tetrakis (pentafluorophenyl) borate is used as a promoter component, an olefin polymer having a good activity and a very high molecular weight can be obtained.

  Further, the olefin polymerization catalyst according to the present invention comprises the above transition metal compound (A), (B-1) an organometallic compound, (B-2) an organoaluminum oxy compound, and (B-3) an ionized ionic compound. A carrier (C) as described later can be used together with at least one selected compound (B), if necessary.

(C) Carrier The carrier (C) used in the present invention is an inorganic or organic compound and is a granular or particulate solid.

Among these, as the inorganic compound, porous oxides, inorganic chlorides, clays, clay minerals or ion-exchangeable layered compounds are preferable.
Specific examples of the porous oxide include SiO ₂ , Al ₂ O ₃ , MgO, ZrO, TiO ₂ and B _2.
O ₃ , CaO, ZnO, BaO, ThO ₂ etc., or composites or mixtures containing these are used, for example natural or synthetic zeolite, SiO ₂ —MgO, SiO ₂ —Al ₂ O ₃ , SiO ₂ —TiO ₂ , SiO _{2 -V 2 O 5, SiO 2} -Cr 2 O 3, etc. can be used SiO ₂ -TiO ₂ -MgO. Of these, those containing SiO ₂ and / or Al ₂ O ₃ as main components are preferred.

The inorganic oxide includes a small amount of Na ₂ CO ₃ , K ₂ CO ₃ , CaCO ₃ , MgCO ₃ , Na ₂ SO ₄ , Al ₂ (SO ₄ ) ₃ , BaSO ₄ , KNO ₃ , Mg (NO ₃ ). ₂ , Al (NO ₃ ) ₃ , Na ₂ O, K ₂ O, Li ₂ O and other carbonates, sulfates, nitrates, and oxide components may be contained.

Such porous oxides have different properties depending on the type and production method, but the carrier preferably used in the present invention has a particle size of 10 to 300 μm, preferably 20 to 200 μm, and a specific surface area of 50 to 1000 m. ² / g, preferably in the range of 100 to 700 m ² / g, and the pore volume is in the range of 0.3 to 3.0 cm ³ / g. Such carriers are
If necessary, it is baked at 100 to 1000 ° C, preferably 150 to 700 ° C.

As the inorganic chloride, MgCl ₂ , MgBr ₂ , MnCl ₂ , MnBr ₂ or the like is used. The inorganic chloride may be used as it is or after being pulverized by a ball mill or a vibration mill. Moreover, after dissolving inorganic chloride in solvents, such as alcohol, what precipitated with the precipitation agent in the shape of fine particles can also be used.

  The clay used in the present invention is usually composed mainly of clay minerals. The ion-exchangeable layered compound used in the present invention is a compound having a crystal structure in which surfaces formed by ionic bonds and the like are stacked in parallel with each other with a weak binding force, and the contained ions can be exchanged. . Most clay minerals are ion-exchangeable layered compounds. In addition, these clays, clay minerals, and ion-exchange layered compounds are not limited to natural products, and artificial synthetic products can also be used.

Further, as clay, clay mineral or ion-exchangeable layered compound, clay, clay mineral, ionic crystalline compound having a layered crystal structure such as hexagonal fine packing type, antimony type, CdCl ₂ type, CdI ₂ type, etc. It can be illustrated.

Examples of such clays and clay minerals include kaolin, bentonite, kibushi clay, gyrome clay, allophane, hysinger gel, pyrophyllite, ummo group, montmorillonite group, vermiculite, ryokdeite group, palygorskite, kaolinite, nacrite, dickite , And halloysite, and the ion-exchangeable layered compound includes α-Zr (
HAsO ₄ ) ₂ · H ₂ O, α-Zr (HPO ₄ ) ₂ , α-Zr (KPO ₄ ) ₂ · 3H ₂ O, α-Ti (HPO ₄ ) ₂ , α-Ti (HAsO ₄ ) ₂ · H ₂ O, α-Sn (HPO ₄ ) ₂ .H ₂ O, γ-Zr (HPO ₄ ) ₂ , γ-Ti (HPO ₄ ) ₂ , γ-Ti (NH ₄ PO ₄ ) ₂ .H ₂ O, etc. Examples thereof include crystalline acid salts of polyvalent metals.

Such a clay, clay mineral or ion-exchange layered compound preferably has a pore volume of not less than 0.1 cc / g and not less than 0.3 cc / g, as measured by mercury porosimetry. Is particularly preferred. Here, the pore volume is measured in the range of pore radius of 20 to 3 × 10 ⁴ Å by mercury porosimetry using a mercury porosimeter.

When a carrier having a pore volume with a radius of 20 mm or more and smaller than 0.1 cc / g is used as a carrier, high polymerization activity tends to be difficult to obtain.
The clay and clay mineral used in the present invention are preferably subjected to chemical treatment. As the chemical treatment, any of a surface treatment that removes impurities adhering to the surface and a treatment that affects the crystal structure of clay can be used. Specific examples of the chemical treatment include acid treatment, alkali treatment, salt treatment, and organic matter treatment. In addition to removing impurities on the surface, the acid treatment increases the surface area by eluting cations such as Al, Fe, and Mg in the crystal structure. Alkali treatment destroys the crystal structure of the clay, resulting in a change in the structure of the clay. In the salt treatment and the organic matter treatment, an ion complex, a molecular complex, an organic derivative, and the like can be formed, and the surface area and interlayer distance can be changed.

The ion-exchangeable layered compound used in the present invention may be a layered compound in a state where the layers are expanded by exchanging the exchangeable ions between the layers with other large and bulky ions using the ion-exchange property. . Such bulky ions play a role of supporting pillars to support the layered structure and are usually called pillars. Moreover, introducing another substance between the layers of the layered compound in this way is called intercalation. Examples of guest compounds to be intercalated include cationic inorganic compounds such as TiCl ₄ and ZrCl ₄ , metal alkoxides such as Ti (OR) ₄ , Zr (OR) ₄ , PO (OR) ₃ , and B (OR) ₃ ( R is a hydrocarbon group), metal hydroxide ions such as [Al ₁₃ O ₄ (OH) ₂₄ ] ⁷⁺ , [Zr ₄ (OH) ₁₄ ] ²⁺ , [Fe ₃ O (OCOCH ₃ ) ₆ ] ⁺ Etc. These compounds are used alone or in combination of two or more. Further, when these compounds were intercalated, they were obtained by hydrolysis of metal alkoxides such as Si (OR) ₄ , Al (OR) ₃ , Ge (OR) ₄ (R is a hydrocarbon group, etc.). Polymer, Si
A colloidal inorganic compound such as O ₂ can coexist. Examples of the pillar include oxides generated by heat dehydration after intercalation of the metal hydroxide ions between layers.

  The clay, clay mineral, and ion-exchangeable layered compound used in the present invention may be used as they are, or may be used after a treatment such as ball milling or sieving. Further, it may be used after newly adsorbing and adsorbing water or after heat dehydration treatment. Furthermore, you may use individually or in combination of 2 or more types.

Among these, preferred are clays or clay minerals, and particularly preferred are montmorillonite, vermiculite, pectolite, teniolite and synthetic mica.
Examples of the organic compound include granular or fine particle solids having a particle size in the range of 10 to 300 μm. Specifically, ethylene, propylene, 1-butene, 4-methyl-1-
(Co) polymer produced mainly from α-olefins having 2 to 14 carbon atoms such as pentene, or (co) polymer produced mainly from vinylcyclohexane, styrene, and their modified products Can be illustrated.

  The first olefin polymerization catalyst according to the present invention includes the transition metal compound (A), (B-1) an organometallic compound, (B-2) an organoaluminum oxy compound, and (B-3) an ionized ionic compound. A specific organic compound (D) as described later can be included as needed together with at least one compound (B) selected from the above, and, if necessary, the carrier (C).

(D) Organic Compound Component In the present invention, the (D) organic compound component is used for the purpose of improving the polymerization performance and the physical properties of the produced polymer, if necessary. Examples of such organic compounds include, but are not limited to, alcohols, phenolic compounds, carboxylic acids, phosphorus compounds, and sulfonates.

As alcohols and phenolic compounds, those represented by R ³¹ —OH are usually used, wherein R ³¹ is a hydrocarbon group having 1 to 50 carbon atoms or a halogenated group having 1 to 50 carbon atoms. A hydrocarbon group is shown.

As the alcohol, R ³¹ is preferably a halogenated hydrocarbon. Further, as the phenolic compound, those in which the α, α′-position of the hydroxyl group is substituted with a hydrocarbon having 1 to 20 carbon atoms are preferable.

As the carboxylic acid, one represented by R ³² —COOH is usually used. R ³² represents a hydrocarbon group having 1 to 50 carbon atoms or a halogenated hydrocarbon group having 1 to 50 carbon atoms, and a halogenated hydrocarbon group having 1 to 50 carbon atoms is particularly preferable.

As the phosphorus compound, phosphoric acid having P—O—H bond, P—OR, phosphate having P═O bond, and phosphine oxide compound are preferably used.
As the sulfonate, those represented by the following general formula (IX) are used.

In the formula, M is an element belonging to Group 1-14 of the Periodic Table.
R ³³ is hydrogen, a hydrocarbon group having 1 to 20 carbon atoms, or a halogenated hydrocarbon group having 1 to 20 carbon atoms.

X is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a halogenated hydrocarbon group having 1 to 20 carbon atoms.
m is an integer of 1 to 7, and n is 1 ≦ n ≦ 7.

In FIG. 1, the preparation process of the 1st olefin polymerization catalyst which concerns on this invention is shown.
In the polymerization, the usage method and the order of addition of each component are arbitrarily selected, and the following methods are exemplified.
(1) Component (A) and (B-1) an organometallic compound, (B-2) an organoaluminum oxy compound and (B-3) an ionized ionic compound (B) (below) And simply adding “component (B)”) to the polymerization vessel in any order.
(2) A method in which a catalyst in which the component (A) and the component (B) are contacted in advance is added to the polymerization vessel.
(3) A method in which the catalyst component in which the component (A) and the component (B) are contacted in advance, and the component (B) are added to the polymerization vessel in an arbitrary order. In this case, the component (B) may be the same or different.
(4) A method in which the catalyst component having component (A) supported on carrier (C) and component (B) are added to the polymerization vessel in any order.
(5) A method in which a catalyst in which component (A) and component (B) are supported on a carrier (C) is added to a polymerization vessel.
(6) A method in which the catalyst component in which the component (A) and the component (B) are supported on the carrier (C), and the component (B) are added to the polymerization vessel in an arbitrary order. In this case, the component (B) may be the same or different.
(7) A method in which the catalyst component having component (B) supported on carrier (C) and component (A) are added to the polymerization vessel in any order.
(8) A method in which the catalyst component having component (B) supported on carrier (C), component (A), and component (B) are added to the polymerization vessel in any order. In this case, the component (B) may be the same or different.
(9) A method in which the component carrying component (A) on carrier (C) and the component carrying component (B) on carrier (C) are added to the polymerization vessel in any order.
(10) A method in which component (A) is supported on carrier (C), component (B) is supported on carrier (C), and component (B) is added to any sequential polymerization vessel. In this case, the component (B) may be the same or different.
(11) A method in which component (A), component (B), and organic compound component (D) are added to the polymerization vessel in any order.
(12) A method in which component (B) and component (D) are contacted in advance, and component (A) are added to the polymerization vessel in any order.
(13) A method in which component (B) and component (D) are supported on carrier (C), and component (A) are added to the polymerization vessel in any order.
(14) A method in which the catalyst component in which the component (A) and the component (B) are contacted in advance, and the component (D) are added to the polymerization vessel in an arbitrary order.
(15) A method in which the component (A) and the component (B) are contacted in advance, and the component (B) and the component (D) are added to the polymerization vessel in an arbitrary order.
(16) A method in which the catalyst component in which the component (A) and the component (B) have been contacted in advance, and the component in which the component (B) and the component (D) have been contacted in advance are added to the polymerization vessel in any order.
(17) A method in which the component (A) supported on the carrier (C), the component (B), and the component (D) are added to the polymerization vessel in any order.
(18) A method in which a component having component (A) supported on carrier (C) and a component in which component (B) and component (D) are contacted in advance are added to the polymerization vessel in any order.
(19) A method in which a catalyst component obtained by bringing the component (A), the component (B) and the component (D) into contact in advance in an arbitrary order is added to the polymerization vessel.
(20) A method in which the catalyst component in which the component (A), the component (B) and the component (D) are contacted in advance, and the component (B) are added to the polymerization vessel in an arbitrary order. In this case, the component (B) may be the same or different.
(21) A method in which a catalyst having components (A), (B) and (D) supported on a carrier (C) is added to a polymerization vessel.
(22) A method in which the component (A), the component (B) and the component (D) supported on the carrier (C) and the component (B) are added to the polymerization vessel in any order. In this case, the component (B) may be the same or different.

The solid catalyst component in which the component (A) and the component (B) are supported on the carrier (C) may be prepolymerized with an olefin.
In the first olefin polymerization method according to the present invention, an olefin polymer is obtained by polymerizing or copolymerizing an olefin in the presence of the olefin polymerization catalyst as described above.

In the present invention, the polymerization can be carried out by either a liquid phase polymerization method such as solution polymerization or suspension polymerization or a gas phase polymerization method.
Specific examples of the inert hydrocarbon medium used in the liquid phase polymerization method include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; cyclopentane, cyclohexane, and methylcyclopentane. Alicyclic hydrocarbons such as benzene, toluene, xylene and the like aromatic hydrocarbons; halogenated hydrocarbons such as ethylene chloride, chlorobenzene, dichloromethane and the like, and mixtures thereof. The olefin itself is used as a solvent. You can also.

When the olefin polymerization is carried out using the above olefin polymerization catalyst, the component (A) is usually 10 ⁻¹² to 10 ⁻² mol, preferably 10 ⁻¹⁰ to 10 ⁻³ , per liter of reaction volume. It is used in such an amount that it becomes a mole. In the present invention, the olefin can be polymerized with high polymerization activity even when the component (A) is used at a relatively low concentration.

Component (B-1) has a molar ratio [(B-1) / M] of the component (B-1) and the transition metal atom (M) in the component (A) of usually 0.01 to 100,000, Preferably it is used in an amount of 0.05 to 50000. Component (B-2) has a molar ratio [(B-2) / M] of the aluminum atom in component (B-2) and the transition metal atom (M) in component (A) of usually 10 to 10. The amount used is 500,000, preferably 20 to 100,000. Component (B-3) has a molar ratio [(B-3) / M] of component (B-3) to transition metal atom (M) in component (A) of usually 1 to 10, preferably 1 to
It is used in such an amount that it becomes 5.

In the case of component (B-1), component (D) has a molar ratio [(D) / (B-1)] of usually 0.01 to 10, preferably 0.1 to component (B-1). In the case of the component (B-2), the component (D
) And the aluminum atom in component (B-2) in such an amount that the molar ratio [(D) / (B-2)] is usually 0.001 to 2, preferably 0.005 to 1. In the case of (B-3), the molar ratio [(D)
/ (B-3)] is usually used in an amount of 0.01 to 10, preferably 0.1 to 5.

Moreover, the polymerization temperature of the olefin using such an olefin polymerization catalyst is usually in the range of −50 to + 200 ° C., preferably 0 to 170 ° C. The polymerization pressure is usually from normal pressure to 100 kg / cm ² , preferably from normal pressure to 50 kg / cm ² , and the polymerization reaction can be carried out in any of batch, semi-continuous and continuous methods. it can. Further, the polymerization can be carried out in two or more stages having different reaction conditions.

  The molecular weight of the resulting olefin polymer can be adjusted by the presence of hydrogen in the polymerization system or by changing the polymerization temperature. Furthermore, it can also adjust by the difference in the component (B) to be used.

Examples of the olefin that can be polymerized by such an olefin polymerization catalyst include linear or branched α-olefins having 2 to 30 carbon atoms, preferably 2 to 20 carbon atoms, such as ethylene, propylene, 1-butene, 2-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1- Tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene;
Cyclic olefins having 3 to 30, preferably 3 to 20 carbon atoms, such as cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene, 2-methyl 1,4,5,8-dimethano- 1,2,3,4,4a, 5,8,8a-octahydronaphthalene;
Polar monomers, for example, α, such as acrylic acid, methacrylic acid, fumaric acid, maleic anhydride, itaconic acid, itaconic anhydride, bicyclo (2,2,1) -5-heptene-2,3-dicarboxylic anhydride β-unsaturated carboxylic acids and metal salts thereof such as sodium salt, potassium salt, lithium salt, zinc salt, magnesium salt, calcium salt; methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, N-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, etc. Α, β-unsaturated carboxylic acid esters of: vinyl acetate, vinyl propionate, caproic acid It can be mentioned glycidyl acrylate, glycidyl methacrylate, and the like unsaturated glycidyl such as itaconic acid monoglycidyl ester; alkenyl, vinyl caprate, vinyl laurate, vinyl stearate, vinyl esters such as vinyl trifluoroacetate. Also, vinylcyclohexane, diene, polyene, or the like can be used. As the diene or polyene, a cyclic or chain compound having 4 to 30, preferably 4 to 20 carbon atoms and having two or more double bonds is used. Specifically, butadiene, isoprene, 4-methyl-1,3-pentadiene, 1,3-pentadiene, 1,4-pentadiene, 1,5-hexadiene, 1,4-hexadiene, 1,3-hexadiene, 1 , 3-octadiene, 1,4-octadiene, 1,5-octadiene, 1,6-octadiene, 1,7-octadiene, ethylidene norbornene, vinyl norbornene, dicyclopentadiene;
7-methyl-1,6-octadiene, 4-ethylidene-8-methyl-1,7-nonadiene, 5,9-dimethyl-1,4,8-decatriene;
In addition, aromatic or vinyl compounds such as styrene, o-methyl styrene, m-methyl styrene, p-methyl styrene, o, p-dimethyl styrene, o-ethyl styrene, m-ethyl styrene, p-ethyl styrene etc. Alkyl styrene;
Functional group-containing styrene derivatives such as methoxystyrene, ethoxystyrene, vinyl benzoic acid, methyl vinyl benzoate, vinyl benzyl acetate, hydroxystyrene, o-chlorostyrene, p-chlorostyrene, divinylbenzene; and
Examples include 3-phenylpropylene, 4-phenylpropylene, and α-methylstyrene.

  The first olefin polymerization catalyst according to the present invention exhibits a high polymerization activity and can provide a polymer having a narrow molecular weight distribution. Furthermore, when two or more olefins are copolymerized, an olefin copolymer having a narrow composition distribution can be obtained.

The olefin polymerization catalyst according to the present invention can also be used for copolymerization of an α-olefin and a conjugated diene.
Examples of the α-olefin used here include linear or branched α-olefins having 2 to 30 carbon atoms, preferably 2 to 20 carbon atoms, as described above. Of these, ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene and 1-octene are preferable, and ethylene and propylene are particularly preferable. These α-olefins can be used alone or in combination of two or more.

Examples of conjugated dienes include 1,3-butadiene, isoprene, chloroprene, 1,3-cyclohexadiene, 1,3-pentadiene, 4-methyl-1,3-pentadiene, 1,3-hexadiene, 1,3- Examples thereof include aliphatic conjugated dienes having 4 to 30, preferably 4 to 20 carbon atoms such as octadiene. These conjugated dienes can be used alone or in combination of two or more.

  In the present invention, when the α-olefin and the conjugated diene are copolymerized, a non-conjugated diene or polyene can be further used. Examples of the non-conjugated diene or polyene include 1,4-pentadiene, 1,5-hexadiene, 1 , 4-Hexadiene, 1,4-octadiene, 1,5-octadiene, 1,6-octadiene, 1,7-octadiene, ethylidene norbornene, vinyl norbornene, dicyclopentadiene, 7-methyl-1,6-octadiene, 4 -Ethylidene-8-methyl-1,7-nonadiene, 5,9-dimethyl-1,4,8-decatriene and the like.

Second Olefin Polymerization Catalyst Next, the second olefin polymerization catalyst according to the present invention will be described.
The second olefin polymerization catalyst according to the present invention is:
(A ′) a transition metal compound represented by the following general formula (II):
(B) (B-1) Organometallic compound,
(B-2) an organoaluminum oxy compound, and
(B-3) It is formed from at least one compound selected from compounds that react with the transition metal compound (A ′) to form ion pairs.

First, each component which forms the olefin polymerization catalyst of the present invention will be described.
(A ′) Transition Metal Compound The (A ′) transition metal compound used in the present invention is a transition metal compound represented by the following general formula (II).

(In the formula, M represents a transition metal atom of Groups 3 to 11 of the periodic table,
R ^{1 to} R ¹⁰ may be the same or different from each other, and are a hydrogen atom, a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, a sulfur-containing group, phosphorus A containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group, and two or more of these may be linked to each other to form a ring,
n is a number that satisfies the valence of M;
X is a hydrogen atom, halogen atom, hydrocarbon group, oxygen-containing group, sulfur-containing group, nitrogen-containing group, boron-containing group, aluminum-containing group, phosphorus-containing group, halogen-containing group, heterocyclic compound residue, silicon-containing A group, a germanium-containing group, or a tin-containing group, and when n is 2 or more, a plurality of groups represented by X may be the same or different from each other, and a plurality of groups represented by X are bonded to each other. And Y may represent a divalent linking group containing at least one element selected from the group consisting of oxygen, sulfur, carbon, nitrogen, phosphorus, silicon, selenium, tin and boron. In the case of a hydrocarbon group, it is a group consisting of 3 or more carbon atoms.

In general formula (II), at least one of R ⁶ or R ¹⁰ , particularly both, is a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, a sulfur-containing group, It is preferably a phosphorus-containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group.

In the general formula (II), as M, R ^{1 to} R ¹⁰ and X, the same groups as M, R ^{1 to} R ⁶ and X mentioned for the compound of the general formula (I) can be used. Specific examples of Y will be described later.

  The transition metal compound represented by the general formula (II) is preferably a transition metal compound represented by the following general formula (II-a).

  In the formula, M represents a transition metal atom of Groups 3 to 11 of the periodic table, preferably Group 4 or Group 5, more preferably Group 4, such as titanium, zirconium, hafnium, etc., particularly titanium. .

R ^{1 to} R ¹⁰ may be the same as or different from each other, and are a hydrogen atom, a halogen atom, a hydrocarbon group, a hydrocarbon-substituted silyl group, an alkoxy group, an aryloxy group, an ester group, an amide group,
An amino group, a sulfonamide group, a nitrile group or a nitro group is shown, and two or more of these, preferably adjacent groups, may be linked to each other to form a ring.

n is a number that satisfies the valence of M, and is generally an integer of 0 to 4, preferably 1 to 4, more preferably 1 to 3.
X represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group, a sulfur-containing group, or a silicon-containing group, and n is In the case of two or more, a plurality of groups represented by X may be the same or different from each other, and two or more Xs may be connected to each other to form a ring.

  Y represents a divalent linking group containing at least one element selected from the group consisting of oxygen, sulfur, carbon, nitrogen, phosphorus, silicon, selenium, tin and boron, and when it is a hydrocarbon group A group consisting of 3 or more carbon atoms.

  These linking groups preferably have a structure in which the main chain is composed of 3 or more atoms, more preferably 4 or more and 20 or less, and particularly preferably 4 or more and 10 or less. These linking groups may have a substituent.

In general formula (II-a), at least one of R ⁶ or R ¹⁰ , particularly both, is a halogen atom, hydrocarbon group, hydrocarbon-substituted silyl group, alkoxy group, aryloxy group, ester group, amide group, amino group, A sulfonamide group, a nitrile group or a nitro group is preferred.

In the general formula (II-a), specific examples of X and R ^{1 to} R ¹⁰ include the same groups as X and R ^{1 to} R ⁶ described in the general formulas (I) and (Ia). X is particularly preferably a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a sulfonate group. When n is 2 or more, the ring formed by connecting two or more Xs to each other may be an aromatic ring or an aliphatic ring.

Specific examples of the divalent linking group (Y) include chalcogen atoms such as —O—, —S—, and —Se—; —NH—, —N (CH ₃ ) —, —PH—, and —P (CH ₃₎ - nitrogen or phosphorus atom-containing groups such _{as; -SiH 2 -, - Si (} CH 3) 2 - silicon atom-containing groups such _{as; -SnH 2 -, - Sn (} CH 3) 2 - containing tin atoms, such as Groups; boron-containing groups such as —BH—, —B (CH ₃ ) —, —BF— and the like. Examples of the hydrocarbon group include a saturated hydrocarbon group having 3 to 20 carbon atoms such as — (CH ₂ ) ₄ —, — (CH ₂ ) ₅ —, and — (CH ₂ ) ₆ —, a cyclohexylidene group, and cyclohexylene. Cyclic saturated hydrocarbon groups such as a group, a part of these saturated hydrocarbon groups is 1 to 10 hydrocarbon groups, halogen such as fluorine, chlorine, bromine, oxygen, sulfur, nitrogen, phosphorus, silicon, selenium, tin , Groups substituted with heteroatoms such as boron, residues of cyclic hydrocarbons having 6 to 20 carbon atoms such as benzene, naphthalene and anthracene, and the number of carbon atoms including heteroatoms such as pyridine, quinoline, thiophene and furan Is a residue of a cyclic compound having 3-20.

  Specific examples of the transition metal compound represented by the general formula (II) are shown below, but are not limited thereto.

In the above examples, Me represents a methyl group, and Ph represents a phenyl group.
In the present invention, a transition metal compound in which the titanium metal is replaced with a metal other than titanium, such as zirconium or hafnium, in the above compound can also be used.

In the second olefin polymerization catalyst according to the present invention, the transition metal compound (A ′) can be used in combination with other transition metal compounds as in the case of the transition metal compound (A). Specific examples include the compounds (a-1) to (a-8) exemplified above.

Further, the organometallic compound (B-1) used for the second olefin polymerization catalyst according to the present invention,
Examples of the compound (B-3) that reacts with the organoaluminum oxy compound (B-2) and the transition metal compound (A ′) to form an ion pair include those described above.

Further, in the second olefin polymerization catalyst according to the present invention, as in the first olefin polymerization catalyst, the transition metal compound (A ′), (B-1) organometallic compound, (B-2) A support (C) as described above can be used together with at least one compound (B) selected from an organoaluminum oxy compound and (B-3) an ionized ionic compound, if necessary. Furthermore, the specific organic compound (D) as described above can be used as necessary.

In FIG. 2, the preparation process of the 2nd olefin polymerization catalyst which concerns on this invention is shown.
The second olefin polymerization catalyst according to the present invention can be used for the polymerization of similar monomers under the same conditions as described for the first olefin polymerization catalyst according to the present invention.

In the second olefin polymerization method according to the present invention, the method of using each component and the order of addition are arbitrarily selected, and the same method as in the case of the first olefin polymerization method is exemplified.
Novel transition metal compound The novel transition metal compound according to the present invention is represented by the following general formula (III).

In the formula (III), M represents a transition metal atom of Group 4 or 5 of the periodic table,
m represents an integer of 1 to 3,
R ¹ represents a hydrocarbon group, a hydrocarbon-substituted silyl group, a hydrocarbon-substituted siloxy group, an alkoxy group, an alkylthio group, an aryloxy group, an arylthio group, an ester group, a thioester group, a sulfone ester group, or a hydroxy group,
R ^{2 to} R ⁵ may be the same or different from each other, and are a hydrogen atom, a halogen atom, a hydrocarbon group, a heterocyclic compound residue, a hydrocarbon-substituted silyl group, a hydrocarbon-substituted siloxy group, an alkoxy group, or an alkylthio group. , Aryloxy group, arylthio group, ester group, thioester group, amide group, imide group, amino group, imino group, sulfone ester group, sulfonamide group, cyano group, nitro group, carboxyl group, sulfo group, mercapto group or hydroxy group Indicate
R ⁶ is a halogen atom, hydrocarbon group, hydrocarbon-substituted silyl group, hydrocarbon-substituted siloxy group, alkoxy group, alkylthio group, aryloxy group, arylthio group, ester group, thioester group, amide group, imide group, imino group, A sulfone ester group, a sulfonamide group or a cyano group;
Two or more of R ^{1 to} R ⁶ may be linked to each other to form a ring;
When m is 2 or more, two groups represented by R ^{1 to} R ⁶ may be linked (however, R ¹ are not bonded to each other),
n is a number that satisfies the valence of M;
X is a halogen atom, hydrocarbon group, oxygen-containing group, sulfur-containing group, nitrogen-containing group, boron-containing group, aluminum-containing group, phosphorus-containing group, halogen-containing group, heterocyclic compound residue, silicon-containing group, germanium In the case where n is 2 or more, a plurality of groups represented by X may be the same or different from each other, and a plurality of groups represented by X are bonded to each other to form a ring. It may be formed.

  Of the transition metal compounds of the general formula (III), those represented by the following general formula (III-a) are preferred.

In formula (III-a), M represents a transition metal atom of Group 4 or 5 of the periodic table, and specifically, titanium, zirconium, hafnium, vanadium, niobium, and tantalum.
m represents an integer of 1 to 3, preferably 2.
R ^{1 to} R ⁵ may be the same as or different from each other, and each represents a hydrocarbon group, an alkoxy group, or a hydrocarbon-substituted silyl group;
R ⁶ represents a halogen atom, a hydrocarbon group, a hydrocarbon-substituted silyl group, an alkoxy group, an alkylthio group or a cyano group,
Two or more of R ^{1 to} R ⁶ may be linked to each other to form a ring;
When m is 2 or more, two groups represented by R ^{1 to} R ⁶ may be linked (however, R ¹ are not bonded to each other),
n is a number that satisfies the valence of M;
X represents a halogen atom, a hydrocarbon group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a halogen-containing group or a silicon-containing group. When n is 2 or more, a plurality of groups represented by X are the same as each other However, they may be different, and a plurality of groups represented by X may be bonded to each other to form a ring. Among these, X is preferably a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group, a sulfur-containing group, or a silicon-containing group.

Specific examples of R ^{1 to} R ⁶ and X in the general formula (III-a) include the same groups as those described in the general formula (I).
The following are illustrated as a novel transition metal compound.

General Production Method of Transition Metal Compound The transition metal compound represented by the general formulas (I), (II) and (III) is not particularly limited and can be produced, for example, as follows.

First, the ligand constituting the transition metal compound according to the present invention is a salicylaldehyde compound, a primary amine compound of the formula R ¹ —NH ₂ (R ¹ has the above meaning), such as anilines. It can be obtained by reacting with a compound or an alkylamine compound. Specifically, both starting compounds are dissolved in a solvent. As the solvent, those commonly used in such a reaction can be used, and among them, alcohol solvents such as methanol and ethanol, and hydrocarbon solvents such as toluene are preferable. The resulting solution is then stirred from room temperature under reflux conditions for about 1 to 48 hours to give the corresponding ligand in good yield.

When synthesizing the ligand compound, an acid catalyst such as formic acid, acetic acid, and toluenesulfonic acid may be used as a catalyst. Further, when molecular sieves, magnesium sulfate or sodium sulfate is used as a dehydrating agent, or dehydration is performed by Dean Stark, it is effective for the progress of the reaction.

  Next, the corresponding transition metal compound can be synthesized by reacting the thus obtained ligand with the transition metal M-containing compound. Specifically, the synthesized ligand is dissolved in a solvent and contacted with a base as necessary to prepare a phenoxide salt, and then mixed with a metal compound such as a metal halide or metal alkylate at a low temperature. The mixture is stirred for about 1 to 48 hours at -78 ° C to room temperature or under reflux conditions. As the solvent, those commonly used for such a reaction can be used. Among them, polar solvents such as ether and tetrahydrofuran (THF), hydrocarbon solvents such as toluene and the like are preferably used. In addition, as the base used in preparing the phenoxide salt, a metal salt such as a lithium salt such as n-butyllithium, a sodium salt such as sodium hydride, or an organic base such as triethylamine or pyridine is preferable. Not as long.

Depending on the properties of the compound, the corresponding transition metal compound can be synthesized by directly reacting the ligand with the metal compound without going through the preparation of the phenoxide salt.
Further, the metal M in the synthesized transition metal compound can be exchanged with another transition metal by a conventional method. For example, when any of R ^{1 to} R ⁶ is H, a substituent other than H can be introduced at any stage of the synthesis.

The novel transition metal compound according to the present invention represented by the general formula (III), preferably the general formula (III-a), can be suitably used as, for example, a catalyst for olefin polymerization.
When a novel transition metal compound is used as an olefin polymerization catalyst, an olefin (co) polymer having a high polymerization activity and a narrow molecular weight distribution can be synthesized.

α-Olefin / Conjugated Diene Copolymer The α-olefin / conjugated diene copolymer according to the present invention has 1 to 99.9 mol% of structural units derived from an α-olefin and a structural unit derived from a conjugated diene. Is 99 to 0.1 mol%, preferably 50 to 99.9 mol% of structural units derived from α-olefin, and 50 to 0.1 mol% of structural units derived from conjugated diene. .

  In the polymer chain of the α-olefin / conjugated diene copolymer according to the present invention, the content of the 1,2-cyclopentane skeleton derived from the conjugated diene is 1 mol% or less, preferably substantially not included. Content (less than 0.1 mol%). In addition, when the content of the 1,2-cyclopentane skeleton is less than 0.1 mol%, it is regarded as below the detection limit and is not included in the calculation of all conjugated diene units.

Examples of the α-olefin used here include linear or branched α-olefins having 2 to 30 carbon atoms, preferably 2 to 20 carbon atoms, as described above. Of these, ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene and 1-octene are preferable, and ethylene and propylene are particularly preferable. These α-olefins can be used alone or in combination of two or more.

Examples of conjugated dienes include 1,3-butadiene, isoprene, chloroprene, 1,3-cyclohexadiene, 1,3-pentadiene, 4-methyl-1,3-pentadiene, 1,3-hexadiene, 1,3- Examples thereof include aliphatic conjugated dienes having 4 to 30, preferably 4 to 20 carbon atoms such as octadiene. These conjugated dienes can be used alone or in combination of two or more.

In the present invention, when the α-olefin and the conjugated diene are copolymerized, a non-conjugated diene or polyene can be further used. Examples of the non-conjugated diene or polyene include 1,4-pentadiene, 1,5-hexadiene, 1 , 4-Hexadiene, 1,4-octadiene, 1,5-octadiene, 1,6-octadiene, 1,7-octadiene, ethylidenenorbornene, vinylnorbornene, dicyclopentadiene, 7-methyl-1,6-octadiene, 4 -Ethylidene-8-methyl-1,7-nonadiene, 5,9-dimethyl-1,4,8-decatriene and the like.

Further, in the polymer chain of the α-olefin / conjugated diene copolymer according to the present invention, the ratio of the 1,2-cyclopentane skeleton to the total diene unit content is 20 mol% or less, preferably 10 mol% or less. Further, the ratio of the other diene insertion format (1,4-cis, 1,4-trans, 1,2-vinyl) in the α-olefin / conjugated diene copolymer is arbitrary. This ratio can be measured by ¹³ C-NMR and ¹ H-NMR by the method described in Die Makromolekulare Chemie, Vol. 192, page 2591 (1991).

  The α-olefin / conjugated diene copolymer has a molecular weight distribution (Mw / Mn) of 3.5 or less, has a uniform composition distribution, and the molecular weight is 1000 or more in terms of weight average molecular weight (Mw). Preferably it is 5000 or more.

  In the present invention, the α-olefin / conjugated diene copolymer can be variously modified by having a double bond in the main chain or side chain. For example, a double bond can be epoxidized by peroxide modification to introduce a highly reactive epoxy group into the copolymer. Thereby, utilization as a thermosetting resin or utilization as a reactive resin is also possible. Furthermore, double bonds can be used for Diels-Alder reaction, Michael addition reaction, and the like. In addition, when the main chain has a double bond, heat resistance and ozone resistance are further improved by selectively hydrogenating and saturating the double bond.

  In the present invention, a part or all of the α-olefin / conjugated diene copolymer may be modified with an unsaturated carboxylic acid, a derivative thereof, or an aromatic vinyl compound, and the modification amount is 0.01 to 30% by weight. % Is preferable.

Examples of the monomer used for modification (hereinafter referred to as “graft monomer”) include unsaturated carboxylic acids, derivatives thereof, and aromatic vinyl compounds. Specific examples of the unsaturated carboxylic acid include acrylic acid, methacrylic acid, maleic acid, fumaric acid, and itaconic acid. Examples of unsaturated carboxylic acid derivatives include acid anhydrides, esters, amides, imides, metal salts, and the like. Specific examples include maleic anhydride, citraconic anhydride, itaconic anhydride, methyl acrylate, and methacrylic acid. Methyl, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, glycidyl acrylate, glycidyl methacrylate, maleic acid monoethyl ester, maleic acid diethyl ester, fumaric acid monomethyl ester, fumaric acid dimethyl ester, itaconic acid monomethyl Ester, itaconic acid diethyl ester, acrylamide, methacrylamide, maleic acid monoamide, maleic acid diamide, maleic acid-N-monoethylamide, maleic acid-N, N-diethylamide, maleic acid-N-monobutylamide, maleic acid- N, N- Dibutylamide, fumaric acid monoamide, fumaric acid diamide, fumaric acid-N-monoethylamide, fumaric acid-N, N-diethylamide, fumaric acid-N-monobutylamide, fumaric acid-N, N-dibutylamide, maleimide, Examples thereof include N-butylmaleimide, N-phenylmaleimide, sodium acrylate, sodium methacrylate, potassium acrylate, potassium methacrylate and the like. Among these graft monomers, maleic anhydride is preferably used.

Specific examples of the aromatic vinyl compound include styrene;
mono- or polyalkylstyrenes such as o-methylstyrene, m-methylstyrene, p-methylstyrene, o, p-dimethylstyrene, o-ethylstyrene, m-ethylstyrene, p-ethylstyrene;
Functional group-containing styrene derivatives such as methoxystyrene, ethoxystyrene, vinyl benzoic acid, methyl vinyl benzoate, vinyl benzyl acetate, hydroxystyrene, o-chlorostyrene, p-chlorostyrene, divinylbenzene;
Examples include 3-phenylpropylene, 4-phenylbutene, and α-methylstyrene. Of these, styrene or 4-methoxystyrene is preferred.

  In order to produce a modified copolymer by graft copolymerization of a graft monomer with an α-olefin / conjugated diene copolymer, various known methods can be employed. For example, a method of performing graft copolymerization by heating an α-olefin / conjugated diene copolymer and a graft monomer in the presence or absence of a solvent with or without a radical initiator at a high temperature. There is. In the reaction, two or more graft monomers may be used in combination.

  In order to produce a graft-modified α-olefin / conjugated diene copolymer having a graft ratio of 0.01 to 30% by weight partially or wholly modified, a graft having a higher graft ratio is required for industrial production. A modified α-olefin / conjugated diene copolymer is produced, and then this unmodified α-olefin / conjugated diene copolymer is mixed with the graft-modified α-olefin / conjugated diene copolymer to graft. The method of adjusting the rate is preferable because the concentration of the graft monomer in the composition can be adjusted appropriately. From the beginning, the α-olefin / conjugated diene copolymer is graft-modified with a predetermined amount of graft monomer. There is no problem.

  The amount of modification with the graft monomer to the α-olefin / conjugated diene copolymer is such that the graft ratio in the whole resin composition as described above is in the range of 0.01 to 30% by weight, particularly 0.05 to 10% by weight. Preferably there is.

The α-olefin / conjugated diene copolymer (including the modified product) according to the present invention includes (i)
A resin composition can be blended with a polyolefin resin and, if necessary, (ii) a filler and used for various applications.

(i) Polyolefin resin The (i) polyolefin resin that can be blended with the α-olefin / conjugated diene copolymer according to the present invention may be a crystalline polyolefin, an amorphous polyolefin, or a plurality of polyolefin resins. It may be a mixture of seed polyolefin resins.

  As crystalline polyolefin, the homopolymer or copolymer of a C2-C20 alpha olefin or cyclic olefin is mentioned. In addition, examples of the amorphous polyolefin include a copolymer of one or more α-olefins having 2 to 20 carbon atoms and one or more cyclic olefins.

Examples of the α-olefin having 2 to 20 carbon atoms include ethylene, propylene, 1-butene, 2-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, and 4,4-dimethyl-1-pentene. 3-methyl-1-pentene, 4-methyl-1-hexene, 3-ethyl-1-hexene, 4-ethyl-1-hexene, 4,4-dimethyl-1-hexene, 1-octene, 3-methyl Examples include 1-butene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene and the like.

  Cyclic olefins include cyclopentene, cycloheptene, cyclohexene, norbornene, 5-ethyl-2-norbornene, tetracyclododecene, 2-ethyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene and the like.

Specific examples of the crystalline polyolefin resin include (co) polymers as shown in the following (1) to (11), and the following (3) and (5) are particularly preferable.
(1) Ethylene homopolymer (the production method may be either a low pressure method or a high pressure method)
(2) Copolymer of ethylene and other α-olefin or vinyl monomer (eg vinyl acetate, ethyl acrylate, etc.) or cyclic olefin of 20 mol% or less (3) Propylene homopolymer (4) Propylene and 20 Random Copolymer with Other α-Olefins up to Mol% (5) Block Copolymer with Propylene and Other α-Olefins up to 30 mol% (6) 1-Butene Homopolymer (7) 1- Random copolymer of butene and 20 mol% or less of other α-olefin (8) 4-methyl-1-pentene homopolymer (9) 4-methyl-1-pentene and other α of 20 mol% or less of other α -Random copolymer with olefin (10) Cyclopentene homopolymer (11) Random copolymer of cyclopentene and other α-olefins of 20 mol% or less.

The “other α-olefin” in the above (1) to (11) is preferably ethylene, propylene, 1-butene, 4-methyl-1-pentene, 1-hexene among the α-olefins exemplified above. 1-octene is used. As the cyclic olefin, cyclopentene, cyclohexene, norbornene, or tetracyclododecene is preferably used.

  Such crystalline polyolefin resin has a melt flow rate (measured in accordance with ASTM D1238-65T at 230 ° C. under a load of 2.16 kg) of 0.01 to 100 g / 10 min, preferably 0.3 to 70 g / 10. It is desirable to be in the range of minutes. The crystallinity obtained by X-ray diffraction is usually 5 to 100%, preferably 20 to 80%.

Such a crystalline polyolefin resin can be produced by a conventionally known method.
Specific examples of the amorphous polyolefin resin include the following (co) polymers.
(1) Norbornene homopolymer (2) Copolymer of ethylene and norbornene, or Copolymer of ethylene, norbornene and other α-olefin (3) Copolymer of ethylene and tetracyclododecene, or ethylene And a copolymer of tetracyclododecene and other α-olefins.

(ii) Filler It can be blended with the α-olefin / conjugated diene copolymer according to the present invention. (ii) As the filler, those generally used without particular limitation can be used as necessary.

Specific examples of inorganic fillers include silicates such as fine powder talc, kaolinite, calcined clay, pyrophyllite, sericite, and wollastonite, carbonates such as precipitated calcium carbonate, heavy calcium carbonate, and magnesium carbonate. Powders such as hydrous aluminum, magnesium hydroxide and other hydroxides, zinc oxide, zinc oxide, magnesium oxide and other oxides, hydrous calcium silicate, hydrous aluminum silicate, hydrous silicic acid, and anhydrous silicic acid Fillers;
Flaky filler such as mica;
Basic magnesium sulfate whisker, calcium titanate whisker, aluminum borate whisker, sepiolite, PMF (Processed Mineral Fiber), zonotlite,
Fibrous fillers such as potassium titanate and elestadite;
Balun fillers such as glass balun, fly ash balun;
And so on.

These fillers can be used alone or in combination of two or more.
When the (i) polyolefin resin and (ii) filler are blended with the α-olefin / conjugated diene copolymer according to the present invention, when the total amount of the resulting composition is 100 parts by weight, The olefin / conjugated diene copolymer is desirably contained in an amount of 10 to 90 parts by weight, preferably 15 to 80 parts by weight, and more preferably 20 to 75 parts by weight.

  When the α-olefin / conjugated diene copolymer is used in an amount within the above range, it provides a molded article having excellent impact resistance, weather resistance and thermal stability, as well as excellent rigidity, strength and heat resistance. An α-olefin / conjugated diene copolymer composition excellent in moldability is obtained.

(i) When the total amount of the resulting composition is 100 parts by weight,
It is desirable to contain 99 parts by weight, preferably 10 to 85 parts by weight, more preferably 20 to 80 parts by weight.

(i) α-olefin / conjugated diene polymer composition having excellent impact resistance and cold resistance as well as rigidity, strength, heat resistance and moldability when the polyolefin resin is used in an amount within the above range. Is obtained.

  (ii) The filler is desirably contained in an amount in the range of 0 to 40 parts by weight, preferably 0 to 30 parts by weight, when the total amount of the resulting composition is 100 parts by weight. When the filler (ii) is used in such an amount, a composition excellent in rigidity, surface appearance, heat resistance and the like can be obtained.

  Furthermore, the α-olefin / conjugated diene copolymer according to the present invention includes a nucleating agent, an antioxidant, a hydrochloric acid absorbent, a heat stabilizer, a light stabilizer, and an ultraviolet absorber as long as the object of the present invention is not impaired. Agents, lubricants, antistatic agents, flame retardants, pigments, dyes, dispersants, copper damage inhibitors, neutralizing agents, foaming agents, plasticizers, antifoaming agents, crosslinking agents, crosslinking aids, crosslinking accelerators, peroxides Additives such as flowability improvers such as products, weld strength improvers, processing aids, weathering stabilizers, antiblooming agents may be added. These optional additives may be used in combination of two or more.

[Example]
EXAMPLES Hereinafter, although this invention is demonstrated concretely based on an Example, this invention is not limited to these Examples.

The structure of the compound obtained in the synthesis example is 270 MHz ¹ H-NMR (JEOL GSH-270), FT-IR (SHIMAZU FTIR-8200D), FD-mass spectrometry (JEOL SX-102A), metal content It was determined by analysis (analyzing by dry ashing / diluted nitric acid, then analysis by ICP method; SHIMAZU ICPS-8000), carbon, hydrogen, nitrogen content analysis (CHNO type, Heraus).

  Further, the structures of Compound A-1 and Compound B-1 obtained in Synthesis Examples 1 and 2 were further determined by X-ray crystal structure analysis. The measurement was performed by Mo-Kα ray irradiation using a Rigaku AFC7R four-axis diffractometer. In addition, the direct method (SIR92) was used for the structural analysis, and the structural optimization was performed using the TeXan crystal structure analysis program.

  In this example, intrinsic viscosity [η] was measured in 135 ° C. decalin. The molecular weight distribution (Mw / Mn) was determined by measuring by gel permeation chromatography (GPC) at 140 ° C. using o-dichlorobenzene as a solvent.

Specific examples of ligand synthesis are shown below.
[Ligand synthesis example 1]
Synthesis of Ligand (L1) A 100 ml reactor fully purged with nitrogen was charged with 40 ml of ethanol, 0.71 g (7.62 mmol) of aniline and 1.35 g (7.58 mmol) of 3-t-butylsalicylaldehyde at room temperature. Stirring was continued for hours. The reaction solution was concentrated under reduced pressure to remove the solvent, 40 ml of ethanol was added again and stirring was continued at room temperature for 12 hours. The reaction solution was concentrated under reduced pressure to obtain 1.83 g (7.23 mmol, yield 95%) of an orange oil compound represented by L1.

¹ H-NMR (CDCl ₃ ): 1.47 (s, 9H) 6.88 (dd, 1H) 7.24-7.31 (m, 4H) 7.38-7.46 (m, 3H) 8.64 (s, 1H) 13.95 (s, 1H )
IR (neat): 1575, 1590, 1610 cm ^-1
FD-mass spectrometry: 253
[Ligand synthesis example 2]
Synthesis of Ligand (L2) A 100 ml reactor fully purged with nitrogen was charged with 30 ml of ethanol, 1.43 g (9.99 mmol) of α-naphthylamine and 1.40 g (7.86 mmol) of 3-t-butylsalicylaldehyde, and molecular. After adding 5 g of Sieves 3A, the mixture was stirred for 8 hours under reflux, and further stirred at room temperature for 12 hours. The reaction solution was concentrated under reduced pressure and purified by a silica gel column to obtain 2.35 g (7.75 mmol, yield 98%) of an orange oil compound represented by L2.

¹ H-NMR (CDCl ₃ ): 1.50 (s, 9H) 6.90-7.90 (m, 11H) 8.30-8.50 (m, 1H) 13.90 (s, 1H)
FD-mass spectrometry: 303
[Ligand synthesis example 3]
Synthesis of Ligand (L3) A 100 ml reactor thoroughly purged with nitrogen was charged with 30 ml of ethanol, 0.90 g (12.0 mmol) of t-butylamine and 1.78 g (10.0 mmol) of 3-t-butylsalicylaldehyde, and molecular. After adding 5 g of Sieves 3A, stirring was continued at room temperature for 12 hours. The reaction solution was concentrated under reduced pressure and purified by a silica gel column to obtain 2.17 g (9.3 mmol, yield 93%) of a fluorescent yellow oil compound represented by L3.

¹ H-NMR (CDCl ₃ ): 1.20 (s, 9H) 1.42 (s, 9H) 6.50-7.50 (m, 3H) 8.38 (s, 1H) 13.80 (s, 1H)
FD-mass spectrometry: 233
[Ligand synthesis examples 4 to 42]
The following ligands L4 to L42 were synthesized by the same method as in the above ligand synthesis example.

The structure was identified by ¹ H-NMR and FD-mass spectrometry.

Specific synthesis examples of the transition metal compound according to the present invention are shown below.
[Synthesis Example 1]
Synthesis of Compound A-1 :
In a 300 ml reactor thoroughly dried and purged with argon, 1.785 g (7.05 mmol) of compound L1 and 100 ml of diethyl ether were charged, cooled to -78 ° C., and stirred. N-Butyllithium 4.78ml
(1.55 mmol / ml n-hexane solution, 7.40 mmol) was added dropwise over 5 minutes, then the temperature was slowly raised to room temperature, and stirring was continued at room temperature for 4 hours to prepare a lithium salt solution. This solution is
The solution was gradually added dropwise to a mixed solution of 7.05 ml (0.5 mmol / ml heptane solution, 3.53 mmol) of titanium tetrachloride solution cooled to 40 ml of diethyl ether.

After completion of the dropping, stirring was continued while slowly raising the temperature to room temperature. After further stirring at room temperature for 8 hours, the reaction solution was filtered through a glass filter, and the obtained solid was dissolved and washed with 50 ml of methylene chloride to remove insoluble matters. The filtrate was concentrated under reduced pressure, the precipitated solid was dissolved in 10 ml of methylene chloride, and 70 ml of pentane was slowly added with stirring. The mixture was allowed to stand at room temperature to precipitate reddish brown crystals. The crystals were filtered off with a glass filter, washed with pentane, and dried under reduced pressure to obtain 1.34 g (2.15 mmol) of reddish brown crystal compound A-1 represented by the following formula.
Yield 61%).

¹ H-NMR (CDCl ₃ ): 1.35 (s, 18H) 6.82-7.43 (m, 16H) 8.07 (s, 2H)
IR (KBr): 1550, 1590, 1600 cm ^-1
FD-mass spectrometry: 622 (M +)
Elemental analysis: Ti; 7.7% (7.7)
C; 65.8% (65.5) H; 6.0% (5.8) N; 4.5% (4.5) (): Calculated melting point: 265 ° C
X-ray crystal structure analysis: FIG. 3 shows the structure of the obtained compound A-1.

[Synthesis Example 2]
Synthesis of Compound B-1 :
Compound L1; 1.53 g (6.04 mmol) and 60 ml of tetrahydrofuran were charged into a 200 ml reactor thoroughly dried and purged with argon, and cooled to -78 ° C and stirred. To this, 4.1 ml of n-butyllithium (1.55 mmol / ml n-hexane solution, 6.34 mmol) was added dropwise over 5 minutes, and then slowly warmed to room temperature and further stirred at room temperature for 4 hours. A mixed solution obtained by adding 10 ml of tetrahydrofuran to this was gradually added to a solution of 0.70 g of zirconium tetrachloride (purity 99.9%, 3.02 mmol) in 30 ml of tetrahydrofuran cooled to −78 ° C. After the addition, the temperature was slowly raised to room temperature. After stirring at room temperature for 2 hours, stirring was continued for 4 hours under reflux.

The reaction solution was concentrated under reduced pressure, the precipitated solid was washed with 50 ml of methylene chloride, and insoluble matters were removed with a glass filter. The filtrate was concentrated under reduced pressure, and the precipitated solid was dissolved in 30 ml of diethyl ether and allowed to stand at −20 ° C. for 1 day under nitrogen to precipitate yellow crystals. The solid was filtered off, washed with hexane, and dried under reduced pressure to obtain 1.09 g (1.63 mmol, yield 54%) of compound B-1 having a fluorescent yellow crystal represented by the following formula.

¹ H-NMR (CDCl ₃ ): 1.33 (s, 18H) 6.78-7.42 (m, 16H) 8.12 (s, 2H)
IR (KBr): 1550, 1590, 1605 cm ^-1
FD-mass spectrometry: 664 (M +)
Elemental analysis: Zr; 13.5% (13.7)
C; 61.0% (61.2) H; 5.5% (5.4) N; 4.2% (4.2) (): Calculated melting point: 287 ° C
X-ray crystal analysis: The structure of the obtained compound B-1 is shown in FIG.

¹ H-NMR (CDCl ₃ ): 1.34 (s, 18H) 6.75-7.75 (m, 14H) 8.10 (s, 2H)
FD-mass spectrometry: 758 (M +)
Elemental analysis: Ti; 6.5% (6.3) Figures in parentheses are calculated values [Synthesis Example 43]
Synthesis of Compound B-21 :
In a 100 ml reactor thoroughly dried and purged with argon, Compound L21; 1.03 g (3.20 mmol) and 10 ml of diethyl ether were charged, cooled to −78 ° C. and stirred. To this, 2.0 ml of n-butyllithium (1.61 mmol / ml n-hexane solution, 3.22 mmol) was added dropwise over 5 minutes, then the temperature was slowly raised to -15 ° C, and stirring was continued at -15 ° C for 2 hours. A lithium salt solution was prepared. This solution was added dropwise to a 10 ml tetrahydrofuran solution of zirconium tetrachloride (0.36 g, 1.54 mmol) cooled to −78 ° C. After completion of the dropping, stirring was continued while slowly raising the temperature to room temperature. Further, after stirring at room temperature for 15 hours, the reaction solution was evaporated. This was dissolved in 20 ml of toluene, and the reaction was continued for another 3 hours under reflux conditions. The solvent was distilled off from the reaction solution, the resulting solid was dissolved in 50 ml of methylene chloride, and the insoluble material was removed with a glass filter. The filtrate was concentrated under reduced pressure, and the precipitated solid was reprecipitated with diethyl ether and hexane and dried under reduced pressure to obtain 0.33 g (0.41 mmol, 27% yield) of compound B-21 represented by the following formula. It was.

¹ H-NMR (CDCl ₃ ): 1.24 (s, 18H) 6.80-7.78 (m, 14H) 8.15 (s, 2H)
FD-mass spectrometry: 802 (M +)
Elemental analysis: Zr; 11.7% (11.4) Figures in parentheses are calculated values [Synthesis Example 44]
Synthesis of Compound A-22 :
A 100 ml reactor thoroughly dried and purged with argon was charged with Compound L22; 0.50 g (1.77 mmol) and 40 ml of diethyl ether, cooled to -78 ° C. and stirred. To this, 1.20 ml of n-butyllithium (1.55 mmol / ml n-hexane solution 1.86 mmol) was added dropwise over 5 minutes, then slowly warmed to room temperature, and stirred for 4 hours at room temperature to prepare a lithium salt solution. did. This solution was gradually added dropwise to a mixture of 1.77 ml (0.5 mmol / ml heptane solution, 0.89 mmol) of titanium tetrachloride solution cooled to −78 ° C. and 50 ml of diethyl ether.

  Specific examples of the polymerization method according to the present invention are shown below.

[ Reference Example 150]
To a glass autoclave having an internal volume of 500 ml sufficiently purged with nitrogen, 250 ml of toluene was charged, and 100 liter / h of ethylene and 20 liter / h of butadiene were circulated in the system. Ten minutes later, 5.0 mmol of methylaluminoxane in terms of aluminum atom and then 0.01 mmol of titanium compound A-1 were added to initiate polymerization. The reaction was carried out at 25 ° C. for 20 minutes while flowing a mixed gas of ethylene and butadiene at normal pressure, and then a small amount of methanol was added to stop the polymerization. The reaction product was poured into a large amount of hydrochloric acid-methanol to precipitate the whole amount of the polymer, followed by filtration with a glass filter. When dried under reduced pressure at 80 ° C. for 10 hours, 0.53 g of an ethylene / butadiene copolymer was obtained.

The polymerization activity per 1 mmol of titanium was 149 g, and the intrinsic viscosity of the obtained copolymer [
η] was 1.46 dl / g. From the NMR analysis, the copolymer has a total butadiene unit content of 0.9 mol% (0.8 mol% of 1,4-cis and 1,4-trans isomers, 0 for 1,2-vinyl isomers). 0.1 mol% and the cyclopentane skeleton was less than 0.1 mol% (below the detection limit)).

[ Reference Example 151]
Polymerization was carried out in the same manner as in Reference Example 150, except that zirconium compound B-1 was used instead of titanium compound A-1, and the polymerization time was 5 minutes. The yield of the obtained copolymer was 2.65 g.

  The polymerization activity per 1 mmol of zirconium was 3180 g, and the intrinsic viscosity [η] of the obtained copolymer was 0.70 dl / g. From the NMR analysis, the copolymer has a total butadiene unit content of 1.2 mol% (1.1 mol% of 1,4-cis and 1,4-trans isomers combined, and 0.12 of 1,2-vinyl isomers is 0.1 mol%). 1 mol% and the cyclopentane skeleton was less than 0.1 mol% (below the detection limit)).

[ Reference Example 152]
Polymerization was carried out in the same manner as in Reference Example 151 except that the polymerization time was 20 minutes, the ethylene flow rate was 20 liter / h, and the butadiene flow rate was 80 liter / h. The yield of the obtained copolymer was 0.74 g.

  The polymerization activity per 1 mmol of zirconium was 446 g, and the intrinsic viscosity [η] of the obtained copolymer was 0.87 dl / g. The NMR analysis revealed that the copolymer had a butadiene unit content of 5.3 mol% (1,4-cis isomer and 1,4-trans isomer combined 4.7 mol%, 1,2-vinyl isomer 0.6%. Mol% and cyclopentane skeleton was less than 0.1 mol% (below the detection limit)).

[ Reference Example 153]
Polymerization was carried out in the same manner as in Reference Example 151 except that the polymerization time was 5 minutes in Reference Example 151, the flow rate of ethylene was 50 liter / h, and the flow rate of butadiene was 50 liter / h. The yield of the obtained copolymer was 0.57 g.

  The polymerization activity per 1 mmol of zirconium was 342 g, and the intrinsic viscosity [η] of the obtained copolymer was 0.34 dl / g. The NMR analysis revealed that the content of butadiene units in the copolymer was 2.4 mol% (1,4-cis and 1,4-trans isomers combined were 2.3 mol%, 1,2-vinyl isomers were 0.1 Mol% and cyclopentane skeleton was less than 0.1 mol% (below the detection limit)).

[ Reference Example 154]
In Reference Example 153, polymerization was carried out in the same manner as in Reference Example 153 except that the polymerization temperature was 50 ° C. The yield of the obtained copolymer was 0.627 g.

The polymerization activity is 1488 g / mmol-Zr · hr, and the intrinsic viscosity [η] of the obtained copolymer is 0.
It was 16 dl / g. From the NMR analysis, the content of the butadiene unit in the copolymer was 3.3 mol% (3.2 mol% of the 1,4-cis and 1,4-trans isomers combined, 0.1% of the 1,2-vinyl isomer was 0.1%). Mol% and cyclopentane skeleton were less than 0.1 mol% (below the detection limit)).

[ Reference Example 155]
In Reference Example 153, polymerization was carried out in the same manner as in Reference Example 153, except that the polymerization temperature was 50 ° C., the ethylene flow rate was 40 liter / hr, and the butadiene flow rate was 60 liter / hr. The yield of the obtained copolymer was 0.37 g.

The polymerization activity is 888 g / mmol-Zr · hr, and the intrinsic viscosity [η] of the obtained copolymer is 0.1.
It was 7 dl / g. From the NMR analysis, the content of the butadiene unit in the copolymer was 4.8 mol% (the combined amount of 1,4-cis and 1,4-trans isomers was 4.6 mol%, and the 1,2-vinyl isomer was 0.2%. Mol% and cyclopentane skeleton was less than 0.1 mol% (below the detection limit)).

[Example 156]
In Reference Example 153, polymerization was carried out in the same manner as in Reference Example 153, except that the polymerization temperature was 60 ° C., the flow rate of ethylene was 40 liter / hr, and the flow rate of butadiene was 60 liter / hr. The yield of the obtained copolymer was 0.417 g.

The polymerization activity was 984 g / mmol-Zr · hr, and the intrinsic viscosity [η] of the obtained copolymer was 0.1
2 dl / g. From the NMR analysis, the content of butadiene units in the copolymer was 5.8 mol% (1,4-cis and 1,4-trans isomers were combined at 5.6 mol%, and 1,2-vinyl isomers were 0.2. Mol% and cyclopentane skeleton was less than 0.1 mol% (below the detection limit)). The molecular weight distribution (Mw / Mn) measured by GPC was 1.85.

[Example 157]
In Reference Example 153, polymerization was carried out in the same manner as in Reference Example 153, except that the polymerization temperature was 50 ° C., the ethylene flow rate was 30 liter / hr, and the butadiene flow rate was 70 liter / hr. The yield of the obtained copolymer was 0.24 g.

The polymerization activity is 576 g / mmol-Zr · hr, and the intrinsic viscosity [η] of the obtained copolymer is 0.1.
It was 4 dl / g. The NMR analysis revealed that the copolymer had a butadiene unit content of 6.6 mol% (combined 1,4-cis and 1,4-trans 6.3 mol%, 1,2-vinyl isomer 0.2%). Mol% and cyclopentane skeleton was less than 0.1 mol% (below the detection limit)). The molecular weight distribution (Mw / Mn) measured by GPC was 2.05.

FIG. 1 shows a process for preparing a first catalyst for olefin polymerization according to the present invention. FIG. 2 shows a process for preparing the second olefin polymerization catalyst according to the present invention. FIG. 3 shows the structure obtained from the X-ray crystal structure analysis of transition metal compound A-1 produced in Synthesis Example 1. FIG. 4 shows the structure obtained from the X-ray crystal structure analysis of the transition metal compound B-1 produced in Synthesis Example 2.

Claims (2)

  The molecular weight distribution (Mw / Mn) is 3.5 or less, and the content of structural units derived from a linear or branched α-olefin having 2 to 20 carbon atoms is 50 to 99.9 mol%. The content of structural units derived from an aliphatic conjugated diene having 4 to 20 carbon atoms is in the range of 50 to 0.1 mol%, and 1,2 derived from the conjugated diene in the polymer chain An α-olefin / conjugated diene copolymer having a cyclopentane skeleton content of 1 mol% or less. The α-olefin / conjugated diene copolymer according to claim 1, wherein the α-olefin is ethylene and / or propylene, and the conjugated diene is butadiene and / or isoprene.

Images