JP5773797B2 - Olefin polymerization catalyst and process for producing olefin polymer - Google Patents

Description

  The present invention relates to an olefin polymerization catalyst and a method for producing an olefin polymer using the olefin polymerization catalyst.

  As a catalyst conventionally used for producing an olefin polymer such as an ethylene polymer and an ethylene / α-olefin copolymer, a titanium-based catalyst composed of a titanium compound and an organoaluminum compound, or a vanadium compound and an organoaluminum compound. A vanadium-based catalyst is known.

  A metallocene catalyst comprising a metallocene compound such as zirconocene and an organoaluminum oxy compound (aluminoxane) is known as a catalyst capable of producing an olefin polymer with high polymerization activity.

  In general, olefin polymers are lightweight and inexpensive, and have excellent physical properties and processability, so they are used in various fields such as for various molded products. Diversified and olefin polymers having various physical properties are desired. In addition, improvement in productivity is also desired. Under such circumstances, the appearance of an olefin polymerization catalyst and a method for producing an olefin polymer that can produce an olefin polymer having high olefin polymerization activity and excellent properties has been eagerly desired.

  The present applicant has already reported a catalyst containing a transition metal compound having a pyrrolimine ligand represented by the following general formula (PI) as an olefin polymerization catalyst (for example, Patent Documents 1 and 2 and Non-Patent Documents). 1-8).

(In the formula (PI), M, m, R ^{1 to} R ⁵ , n, and X represent those described in Patent Documents 1 and 2, respectively).

  When olefin polymerization is carried out using an olefin polymerization catalyst containing the transition metal compound, an olefin polymer is obtained with high polymerization activity, and furthermore, high copolymerizability is exhibited in the copolymerization of ethylene and α-olefin. However, in order to achieve the high performance and high productivity expected of recent olefin polymers, development of a catalyst for olefin polymerization having better performance has been demanded.

JP 2001-72706 A JP 2001-181333 A

Chem. Lett. 2000, 1270. . Organometallics 2001, 20, 4793. Isr. J. et al. Chem. 2002, 42, 353. Chem. Commun. 2002, 1298. J. et al. Am. Chem. Soc. 2004, 126, 12023. J. et al. Chem. Soc. Dalton Trans. 2002, 459. J. et al. Organomet. Chem. 2004, 689, 1155. J. et al. Organomet. Chem. 2005, 690, 4382.

  In view of the prior art, the problem to be solved by the present invention is to provide an olefin polymerization catalyst exhibiting high polymerization activity and high copolymerizability, and a method for producing an olefin polymer using the catalyst.

As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that an olefin polymerization catalyst containing a transition metal compound having a specific ligand structure is used for olefin polymerization activity and copolymerization. The present invention was completed by finding that a polymer having excellent polymerization property and a high comonomer content can be produced. In Patent Documents 1 and 2 and Non-Patent Documents 1 to 8, transition metal compounds corresponding to the following general formula (II) (in the general formula (PI), R ¹ and R ² are bonded to form a ring structure). Although there is a general description, there are no examples in which the effect is positively disclosed.

That is, the catalyst for olefin polymerization in the present invention is
(A) a transition metal compound represented by the following general formula (I);
(B) (B-1) an organometallic compound, (B-2) an organoaluminum oxy compound, and (B-3) at least one selected from compounds that react with the transition metal compound (A) to form an ion pair. It is characterized by including these compounds.

(In the formula (I), M represents a transition metal atom of Groups 3 to 11 of the periodic table,
m represents an integer of 1 to 6,
R ^{1 to} R ³ may be the same as 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,
R ⁴ and 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, 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, which may be bonded to each other to form a double bond between a carbon atom and a nitrogen atom,
Z represents a structure represented by the following formula (II)

(The plurality of R may be the same or different from each other, and may be 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 them may be connected to each other to form a ring, and adjacent Rs are bonded to each other to form a double bond You may configure
● indicates the point of attachment with the carbon atom (C), ○ indicates the point of attachment with the nitrogen atom (N),
p shows the integer of 1-6. )
Moreover, when m is 2 or more, two groups out of the groups represented by R ^{1 to} R ³ and R may be linked to each other,
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. To form a ring. ).

R ⁴ and R ^{5 in} the general formula (I) are preferably bonded to each other to form a double bond between the carbon atom and the nitrogen atom.

  In the general formula (I), Z is preferably a structure represented by the following formula (III).

(In formula, R < ⁶ > -R < ⁹ > may mutually be same or different, 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, sulfur A containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group, and two or more of these may be connected to each other to form a ring, and ● represents a carbon atom (C ) Represents the point of attachment to the nitrogen atom (N).

R ¹ and R ^{3 in} the general formula (I) are each a linear or branched aliphatic hydrocarbon group having 1 to 10 carbon atoms, a cyclic hydrocarbon group having 3 to 10 carbon atoms, or a carbon atom. An aromatic hydrocarbon group having 6 to 10 carbon atoms is preferable, an aromatic hydrocarbon group having 6 to 10 carbon atoms is more preferable, and a phenyl group is further preferable.

  M in the general formula (I) is preferably a transition metal atom of Group 4 or 5 of the periodic table, more preferably a transition metal atom of Group 4 of the periodic table, and a hafnium atom. Further preferred.

  Moreover, it is preferable that the catalyst for olefin polymerization in this invention contains a support | carrier (C) further in addition to said (A) and (B).

  The method for producing an olefin polymer of the present invention is characterized in that an olefin is (co) polymerized in the presence of the olefin polymerization catalyst.

  The olefin to be polymerized is preferably ethylene and α-olefin.

  In this specification, the term “polymerization” is used to mean “homopolymerization” and “copolymerization”. Further, the term “polymer” is used in the meaning including “homopolymer” and “copolymer”.

  The olefin polymerization catalyst of the present invention exhibits excellent polymerization activity, and particularly exhibits excellent copolymerizability when copolymerizing two or more olefins. For this reason, when two or more types of olefins are copolymerized in the presence of the olefin polymerization catalyst, an olefin copolymer having a high comonomer content can be obtained in a high yield.

  The reason why the olefin polymerization catalyst of the present invention has the above-mentioned excellent properties is not clear, but the transition metal compound (A) represented by the general formula (I) is a transition metal having a conventional pyrrolimine ligand. It is presumed that this is because the compound (compound represented by the above general formula (PI)) has a wider polymerization reaction field.

  Hereinafter, the catalyst for olefin polymerization and the method for producing an olefin polymer according to the present invention will be described in detail.

The catalyst for olefin polymerization according to the present invention comprises transition metal compounds (A) and (B) (B-1) organometallic compounds, (B-2) organoaluminum oxy compounds, and (B-3) transition metal compounds (A And at least one compound selected from compounds capable of reacting with each other to form ion pairs.
<Transition metal compound (A)>
The transition metal compound (A) of the present invention is represented by the following general formula (I).

  In the above general formula (I), M represents a transition metal atom of Groups 3 to 11 of the Periodic Table (Group 3 includes lanthanoids), preferably Group 3 to 9 (Group 3 also includes lanthanoids). ), More preferably a transition metal atom selected from Group 3 to 5, more preferably a transition metal atom selected from Group 4 or Group 5, particularly preferably a Group 4 transition metal atom. is there. 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., more preferably titanium, zirconium, hafnium, especially Hafnium is preferred.

  In general formula (I), a dotted line connecting N and M generally indicates that N is coordinated to M, but may or may not be coordinated in the present invention. .

  In the said general formula (I), m shows the integer of 1-6, Preferably the integer of 2-4, More preferably, 2 is shown.

In the general formula (I), R ^{1 to} R ³ 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, or boron. A containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group, and two or more of R ^{1 to} R ³ may be linked to each other to form a ring. .

  Examples of the halogen atom include fluorine, chlorine, bromine and iodine.

Examples of the hydrocarbon group include a linear or branched aliphatic hydrocarbon group having 1 to 30 carbon atoms, a cyclic hydrocarbon group having 3 to 30 carbon atoms, or an aromatic group having 6 to 30 carbon atoms. A hydrocarbon group is mentioned. Specifically, the number of carbon atoms such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, neopentyl group, n-hexyl group, etc. 1-30, preferably 1-20, more preferably 1-10 linear or branched alkyl groups;
A linear or branched alkenyl group having 2 to 30, preferably 2 to 20 carbon atoms, such as a vinyl group, an allyl group, or an isopropenyl group;
A linear or branched alkynyl group having 2 to 30, preferably 2 to 20, more preferably 2 to 10 carbon atoms such as an ethynyl group or a propargyl group; a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, A cyclic saturated hydrocarbon group having 3 to 30, preferably 3 to 20, more preferably 3 to 10 carbon atoms, such as an adamantyl group;
A cyclic unsaturated hydrocarbon group having 5 to 30 carbon atoms, such as a cyclopentadienyl group, an indenyl group, a fluorenyl group;
An aryl group having 6 to 30, preferably 6 to 20, more preferably 6 to 10 carbon atoms, such as a phenyl group, a naphthyl group, a biphenyl group, a terphenyl group, a phenanthryl group, and an anthracenyl group;
Alkyl-substituted aryl groups such as a tolyl group, iso-propylphenyl group, t-butylphenyl group, dimethylphenyl group, di-t-butylphenyl group;
Etc.

  The hydrocarbon group may have a hydrogen atom substituted with a halogen, and examples of the hydrocarbon group in which such a hydrogen atom is substituted with a halogen include a trifluoromethyl group, a pentafluorophenyl group, and a chlorophenyl group. Examples thereof include halogenated hydrocarbon groups having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms.

  The hydrocarbon group may be substituted with other hydrocarbon groups, and examples of the hydrocarbon group substituted with such a hydrocarbon group include aryl group-substituted alkyl groups such as a benzyl group and a cumyl group. Etc.

Furthermore, the hydrocarbon group is a heterocyclic compound residue;
Oxygen-containing groups such as alkoxy groups, aryloxy groups, ester groups, ether groups, acyl groups, carboxyl groups, carbonate groups, hydroxy groups, peroxy groups, carboxylic anhydride groups;
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 converted to ammonium salt Nitrogen-containing groups such as;
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 group, sulfone ester group, sulfonamide group, thiocarboxyl group, dithiocarboxyl group, sulfo group Sulfur-containing groups such as sulfonyl group, sulfinyl group, sulfenyl group;
Phosphorus-containing groups such as phosphide groups, phosphoryl groups, thiophosphoryl groups, phosphato groups;
It may have a silicon-containing group; a germanium-containing group; or a tin-containing group.

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

  Examples of the silicon-containing group include silyl group, siloxy group, hydrocarbon-substituted silyl group, hydrocarbon-substituted siloxy group, and more specifically, methylsilyl group, dimethylsilyl group, trimethylsilyl group, ethylsilyl group, diethylsilyl group. Group, triethylsilyl group, diphenylmethylsilyl group, triphenylsilyl group, dimethylphenylsilyl group, dimethyl-t-butylsilyl group, dimethyl (pentafluorophenyl) silyl group and the like. Among these, a methylsilyl group, a dimethylsilyl group, a trimethylsilyl group, an ethylsilyl group, a diethylsilyl group, a triethylsilyl group, a dimethylphenylsilyl group, a triphenylsilyl group and the like are preferable, and in particular, a trimethylsilyl group, a triethylsilyl group, and a triphenylsilyl group. Group, dimethylphenylsilyl group is preferred. Specific examples of the hydrocarbon-substituted siloxy group include a trimethylsiloxy group.

  Examples of the germanium-containing group or the tin-containing group include groups in which silicon of the silicon-containing group is replaced with germanium or tin.

Of the groups listed as groups that the hydrocarbon group may have,
Specific examples of the alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, and a t-butoxy group.
Specific examples of the aryloxy group include a phenoxy group, a 2,6-dimethylphenoxy group, and a 2,4,6-trimethylphenoxy group.
Specific examples of the ester group include an acetyloxy group, a benzoyloxy group, a methoxycarbonyl group, a phenoxycarbonyl group, and a p-chlorophenoxycarbonyl group.
Specific examples of the acyl group include a formyl group, an acetyl group, a benzoyl group, a p-chlorobenzoyl group, and a p-methoxybenzoyl group.
Specific examples of the amino group include a dimethylamino group, an ethylmethylamino group, and a diphenylamino group.
Specific examples of the imino group include a methylimino group, an ethylimino group, a propylimino group, a butylimino group, and a phenylimino group.
Specific examples of the amide group include an acetamide group, an N-methylacetamide group, and an N-methylbenzamide group.
Specific examples of the imide group include an acetimide group and a benzimide group.
Specific examples of the thioester group include an acetylthio group, a benzoylthio group, a methylthiocarbonyl group, and a phenylthiocarbonyl group.
Specific examples of the alkylthio group include a methylthio group and an ethylthio group.
Specific examples of the arylthio group include a phenylthio group, a methylphenylthio group, a naphthylthio group, and the like.
Specific examples of the sulfone ester group include a methyl sulfonate group, an ethyl sulfonate group, and a phenyl sulfonate group.
Specific examples of the sulfonamido group include a phenylsulfonamido group, an N-methylsulfonamido group, and an N-methyl-p-toluenesulfonamido group.

Examples of the hydrocarbon group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, neopentyl group, and n-hexyl group. A linear or branched alkyl group having 1 to 30, preferably 1 to 20 carbon atoms;
An aryl group having 6 to 30 carbon atoms, preferably 6 to 20 carbon atoms, such as a phenyl group, a naphthyl group, a biphenyl group, a terphenyl group, a phenanthryl group, and an anthracenyl group;
These aryl groups have substituents such as halogen atoms, alkyl groups or alkoxy groups having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, aryl groups or aryloxy groups having 6 to 30 carbon atoms, preferably 6 to 20 carbon atoms. A substituted aryl group substituted with 1 to 5 is preferred.

As described above, R ^{1 to} R ³ are a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group. These examples may be the same as those exemplified in the description of the hydrocarbon group.

As described above, two or more groups of R ^{1 to} R ³ in the above general formula (I) may be linked to each other to form a ring. More specifically, two or more groups of R ^{1 to} R ³ , preferably adjacent groups, are linked to each other, an aliphatic ring, an aromatic ring, a hetero ring containing a hetero atom such as a nitrogen atom, etc. These rings may further have a substituent.

Of R ¹ to R ^{3 in the} general formula (I), R ^{1 and} R ³ are linear or branched having 1 to 10 carbon atoms from the viewpoint of olefin polymerization activity and copolymerization. It is preferably an aliphatic hydrocarbon group, an alicyclic hydrocarbon group having 3 to 10 carbon atoms, or an aromatic hydrocarbon group having 6 to 10 carbon atoms, and an aromatic carbon group having 6 to 10 carbon atoms. A hydrogen group is more preferable, and a phenyl group is particularly preferable.

In the general formula (I), R ⁴ and R ⁵ may be the same as 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, or boron. A containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group, which may be bonded to each other to form a double bond between a carbon atom and a nitrogen atom.

As the halogen atom, hydrocarbon group, heterocyclic compound residue, oxygen-containing group, nitrogen-containing group, boron-containing group, sulfur-containing group, phosphorus-containing group, silicon-containing group, germanium-containing group, tin-containing group, It includes the same as those exemplified in the explanation of R ¹ to R ^3.

The above R ⁴ and R ⁵ are bonded to each other and form a double bond between the carbon atom to which R ⁴ is bonded and the nitrogen atom to which R ⁵ is bonded. Particularly preferred from the viewpoint of the structural stability of the resulting compound.

  In the general formula (I), Z represents a structure represented by the following formula (II).

  In the above formula (II), ● represents a bonding point with the carbon atom (C), and ◯ represents a bonding point with the nitrogen atom (N).

  In said formula (II), p shows the integer of 1-6, Preferably, the integer of 1-4 is shown, More preferably, it is 2.

  In the above formula (II), a plurality of R 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, or a boron-containing group. A group, a sulfur-containing group, a phosphorus-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.

Examples of the hydrocarbon group include a linear or branched aliphatic hydrocarbon group having 1 to 30 carbon atoms, a cyclic hydrocarbon group having 3 to 30 carbon atoms, or an aromatic group having 6 to 30 carbon atoms. A hydrocarbon group is mentioned. Specifically, the number of carbon atoms such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, neopentyl group, n-hexyl group, etc. 1-30, preferably 1-20, more preferably 1-10 linear or branched alkyl groups;
A linear or branched alkenyl group having 2 to 30, preferably 2 to 20 carbon atoms, such as a vinyl group, an allyl group, or an isopropenyl group;
A linear or branched alkynyl group having 2 to 30, preferably 2 to 20, more preferably 2 to 10 carbon atoms such as an ethynyl group or a propargyl group; a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, A cyclic saturated hydrocarbon group having 3 to 30, preferably 3 to 20, more preferably 3 to 10 carbon atoms, such as an adamantyl group;
A cyclic unsaturated hydrocarbon group having 5 to 30 carbon atoms, such as a cyclopentadienyl group, an indenyl group, a fluorenyl group;
An aryl group having 6 to 30, preferably 6 to 20, more preferably 6 to 10 carbon atoms, such as a phenyl group, a naphthyl group, a biphenyl group, a terphenyl group, a phenanthryl group, and an anthracenyl group;
Alkyl-substituted aryl groups such as a tolyl group, iso-propylphenyl group, t-butylphenyl group, dimethylphenyl group, di-t-butylphenyl group;
Etc.

  The hydrocarbon group may have a hydrogen atom substituted with a halogen, and examples of the hydrocarbon group in which such a hydrogen atom is substituted with a halogen include a trifluoromethyl group, a pentafluorophenyl group, and a chlorophenyl group. Examples thereof include halogenated hydrocarbon groups having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms.

  The hydrocarbon group may be substituted with other hydrocarbon groups, and examples of the hydrocarbon group substituted with such a hydrocarbon group include aryl group-substituted alkyl groups such as a benzyl group and a cumyl group. Etc.

Furthermore, the hydrocarbon group is a heterocyclic compound residue;
Oxygen-containing groups such as alkoxy groups, aryloxy groups, ester groups, ether groups, acyl groups, carboxyl groups, carbonate groups, hydroxy groups, peroxy groups, carboxylic anhydride groups;
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 converted to ammonium salt Nitrogen-containing groups such as;
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 group, sulfone ester group, sulfonamide group, thiocarboxyl group, dithiocarboxyl group, sulfo group Sulfur-containing groups such as sulfonyl group, sulfinyl group, sulfenyl group;
Phosphorus-containing groups such as phosphide groups, phosphoryl groups, thiophosphoryl groups, phosphato groups;
It may have a silicon-containing group; a germanium-containing group; or a tin-containing group.

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

  Examples of the silicon-containing group include silyl group, siloxy group, hydrocarbon-substituted silyl group, hydrocarbon-substituted siloxy group, and more specifically, methylsilyl group, dimethylsilyl group, trimethylsilyl group, ethylsilyl group, diethylsilyl group. Group, triethylsilyl group, diphenylmethylsilyl group, triphenylsilyl group, dimethylphenylsilyl group, dimethyl-t-butylsilyl group, dimethyl (pentafluorophenyl) silyl group and the like. Among these, a methylsilyl group, a dimethylsilyl group, a trimethylsilyl group, an ethylsilyl group, a diethylsilyl group, a triethylsilyl group, a dimethylphenylsilyl group, a triphenylsilyl group and the like are preferable, and in particular, a trimethylsilyl group, a triethylsilyl group, and a triphenylsilyl group. Group, dimethylphenylsilyl group is preferred. Specific examples of the hydrocarbon-substituted siloxy group include a trimethylsiloxy group.

  Examples of the germanium-containing group or the tin-containing group include groups in which silicon of the silicon-containing group is replaced with germanium or tin.

Of the groups listed as groups that the hydrocarbon group may have,
Specific examples of the alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, and a t-butoxy group.
Specific examples of the aryloxy group include a phenoxy group, a 2,6-dimethylphenoxy group, and a 2,4,6-trimethylphenoxy group.
Specific examples of the ester group include an acetyloxy group, a benzoyloxy group, a methoxycarbonyl group, a phenoxycarbonyl group, and a p-chlorophenoxycarbonyl group.
Specific examples of the acyl group include a formyl group, an acetyl group, a benzoyl group, a p-chlorobenzoyl group, and a p-methoxybenzoyl group.
Specific examples of the amino group include a dimethylamino group, an ethylmethylamino group, and a diphenylamino group.
Specific examples of the imino group include a methylimino group, an ethylimino group, a propylimino group, a butylimino group, and a phenylimino group.
Specific examples of the amide group include an acetamide group, an N-methylacetamide group, and an N-methylbenzamide group.
Specific examples of the imide group include an acetimide group and a benzimide group.
Specific examples of the thioester group include an acetylthio group, a benzoylthio group, a methylthiocarbonyl group, and a phenylthiocarbonyl group.
Specific examples of the alkylthio group include a methylthio group and an ethylthio group.
Specific examples of the arylthio group include a phenylthio group, a methylphenylthio group, a naphthylthio group, and the like.
Specific examples of the sulfone ester group include a methyl sulfonate group, an ethyl sulfonate group, and a phenyl sulfonate group.
Specific examples of the sulfonamido group include a phenylsulfonamido group, an N-methylsulfonamido group, and an N-methyl-p-toluenesulfonamido group.

Examples of the hydrocarbon group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, neopentyl group, and n-hexyl group. A linear or branched alkyl group having 1 to 30, preferably 1 to 20 carbon atoms;
An aryl group having 6 to 30 carbon atoms, preferably 6 to 20 carbon atoms, such as a phenyl group, a naphthyl group, a biphenyl group, a terphenyl group, a phenanthryl group, and an anthracenyl group;
These aryl groups have substituents such as halogen atoms, alkyl groups or alkoxy groups having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, aryl groups or aryloxy groups having 6 to 30 carbon atoms, preferably 6 to 20 carbon atoms. A substituted aryl group substituted with 1 to 5 is preferred.

  R can be a heterocyclic compound residue, oxygen-containing group, nitrogen-containing group, boron-containing group, sulfur-containing group, phosphorus-containing group, silicon-containing group, germanium-containing group or tin-containing group as described above, Examples of these are the same as those exemplified in the description of the hydrocarbon group.

In the general formula (II), when m is 2 or more, two groups out of the groups represented by R ^{1 to} R ³ and R may be linked. More specifically, two or more groups of R ^{1 to} R ³ , preferably adjacent groups, are linked to each other, an aliphatic ring, an aromatic ring, a hetero ring containing a hetero atom such as a nitrogen atom, etc. These rings may further have a substituent.

  In the formula (II), adjacent Rs may be bonded to each other to form a double bond. When adjacent Rs in Z are bonded to form a double bond, the structure represented by Z and the structure including the carbon atom and nitrogen atom to which Z is bonded are specifically pyrrole. Examples include a skeleton, a pyridine skeleton, an azepine skeleton, an azocine skeleton, an azonin skeleton, and an azesin skeleton. Among these, Preferably, a pyrrole skeleton and a pyridine skeleton are mentioned, More preferably, a pyridine skeleton is mentioned.

  Z preferably has a structure represented by the following formula (III) (that is, the pyridine skeleton shown above).

  In the above formula (III), ● represents the point of attachment to the carbon atom (C), and ○ represents the point of attachment to the nitrogen atom (N).

In the above formula (III), R ^{6 to} R ⁹ may be the same as 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, or a boron-containing group. A group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group, and two or more of R ^{6 to} R ⁹ may be linked to each other to form a ring.

  Examples of the halogen atom include fluorine, chlorine, bromine and iodine.

Examples of the hydrocarbon group include a linear or branched aliphatic hydrocarbon group having 1 to 30 carbon atoms, a cyclic hydrocarbon group having 3 to 30 carbon atoms, or an aromatic group having 6 to 30 carbon atoms. A hydrocarbon group is mentioned. Specifically, the number of carbon atoms such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, neopentyl group, n-hexyl group, etc. 1-30, preferably 1-20, more preferably 1-10 linear or branched alkyl groups;
A linear or branched alkenyl group having 2 to 30, preferably 2 to 20 carbon atoms, such as a vinyl group, an allyl group, or an isopropenyl group;
A linear or branched alkynyl group having 2 to 30, preferably 2 to 20, more preferably 2 to 10 carbon atoms such as an ethynyl group or a propargyl group; a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, A cyclic saturated hydrocarbon group having 3 to 30, preferably 3 to 20, more preferably 3 to 10 carbon atoms, such as an adamantyl group;
A cyclic unsaturated hydrocarbon group having 5 to 30 carbon atoms, such as a cyclopentadienyl group, an indenyl group, a fluorenyl group;
An aryl group having 6 to 30, preferably 6 to 20, more preferably 6 to 10 carbon atoms, such as a phenyl group, a naphthyl group, a biphenyl group, a terphenyl group, a phenanthryl group, and an anthracenyl group;
Alkyl-substituted aryl groups such as a tolyl group, iso-propylphenyl group, t-butylphenyl group, dimethylphenyl group, di-t-butylphenyl group;
Etc.

  The hydrocarbon group may have a hydrogen atom substituted with a halogen, and examples of the hydrocarbon group in which such a hydrogen atom is substituted with a halogen include a trifluoromethyl group, a pentafluorophenyl group, and a chlorophenyl group. Examples thereof include halogenated hydrocarbon groups having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms.

  The hydrocarbon group may be substituted with other hydrocarbon groups, and examples of the hydrocarbon group substituted with such a hydrocarbon group include aryl group-substituted alkyl groups such as a benzyl group and a cumyl group. Etc.

Furthermore, the hydrocarbon group is a heterocyclic compound residue;
Oxygen-containing groups such as alkoxy groups, aryloxy groups, ester groups, ether groups, acyl groups, carboxyl groups, carbonate groups, hydroxy groups, peroxy groups, carboxylic anhydride groups;
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 converted to ammonium salt Nitrogen-containing groups such as;
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 group, sulfone ester group, sulfonamide group, thiocarboxyl group, dithiocarboxyl group, sulfo group Sulfur-containing groups such as sulfonyl group, sulfinyl group, sulfenyl group;
Phosphorus-containing groups such as phosphide groups, phosphoryl groups, thiophosphoryl groups, phosphato groups;
It may have a silicon-containing group; a germanium-containing group; or a tin-containing group.

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

  Examples of the silicon-containing group include silyl group, siloxy group, hydrocarbon-substituted silyl group, hydrocarbon-substituted siloxy group, and more specifically, methylsilyl group, dimethylsilyl group, trimethylsilyl group, ethylsilyl group, diethylsilyl group. Group, triethylsilyl group, diphenylmethylsilyl group, triphenylsilyl group, dimethylphenylsilyl group, dimethyl-t-butylsilyl group, dimethyl (pentafluorophenyl) silyl group and the like. Among these, a methylsilyl group, a dimethylsilyl group, a trimethylsilyl group, an ethylsilyl group, a diethylsilyl group, a triethylsilyl group, a dimethylphenylsilyl group, a triphenylsilyl group and the like are preferable, and in particular, a trimethylsilyl group, a triethylsilyl group, and a triphenylsilyl group. Group, dimethylphenylsilyl group is preferred. Specific examples of the hydrocarbon-substituted siloxy group include a trimethylsiloxy group.

  Examples of the germanium-containing group or the tin-containing group include groups in which silicon of the silicon-containing group is replaced with germanium or tin.

Of the groups listed as groups that the hydrocarbon group may have,
Specific examples of the alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, and a t-butoxy group.
Specific examples of the aryloxy group include a phenoxy group, a 2,6-dimethylphenoxy group, and a 2,4,6-trimethylphenoxy group.
Specific examples of the ester group include an acetyloxy group, a benzoyloxy group, a methoxycarbonyl group, a phenoxycarbonyl group, and a p-chlorophenoxycarbonyl group.
Specific examples of the acyl group include a formyl group, an acetyl group, a benzoyl group, a p-chlorobenzoyl group, and a p-methoxybenzoyl group.
Specific examples of the amino group include a dimethylamino group, an ethylmethylamino group, and a diphenylamino group.
Specific examples of the imino group include a methylimino group, an ethylimino group, a propylimino group, a butylimino group, and a phenylimino group.
Specific examples of the amide group include an acetamide group, an N-methylacetamide group, and an N-methylbenzamide group.
Specific examples of the imide group include an acetimide group and a benzimide group.
Specific examples of the thioester group include an acetylthio group, a benzoylthio group, a methylthiocarbonyl group, and a phenylthiocarbonyl group.
Specific examples of the alkylthio group include a methylthio group and an ethylthio group.
Specific examples of the arylthio group include a phenylthio group, a methylphenylthio group, a naphthylthio group, and the like.
Specific examples of the sulfone ester group include a methyl sulfonate group, an ethyl sulfonate group, and a phenyl sulfonate group.
Specific examples of the sulfonamido group include a phenylsulfonamido group, an N-methylsulfonamido group, and an N-methyl-p-toluenesulfonamido group.

Examples of the hydrocarbon group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, neopentyl group, and n-hexyl group. A linear or branched alkyl group having 1 to 30, preferably 1 to 20 carbon atoms;
An aryl group having 6 to 30 carbon atoms, preferably 6 to 20 carbon atoms, such as a phenyl group, a naphthyl group, a biphenyl group, a terphenyl group, a phenanthryl group, and an anthracenyl group;
These aryl groups have substituents such as halogen atoms, alkyl groups or alkoxy groups having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, aryl groups or aryloxy groups having 6 to 30 carbon atoms, preferably 6 to 20 carbon atoms. A substituted aryl group substituted with 1 to 5 is preferred.

R ^{6 to} R ⁹ are, as described above, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group. These examples may be the same as those exemplified in the description of the hydrocarbon group.

As described above, two or more groups of R ^{6 to} R ^{9 in} the general formula (III) may be linked to each other to form a ring. More specifically, two or more groups of R ^{6 to} R ⁹ , preferably adjacent groups, are linked to each other, an aliphatic ring, an aromatic ring, or a hetero ring containing a hetero atom such as a nitrogen atom, etc. These rings may further have a substituent.

  In the general formula (I), X represents a hydrogen atom, a halogen atom, a hydrocarbon group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a boron-containing group, an aluminum-containing group, a phosphorus-containing group, a halogen-containing group, or a heterocyclic ring. A formula compound residue, a silicon-containing group, a germanium-containing group, or a tin-containing group is shown.

  Examples of the halogen atom include fluorine, chlorine, bromine and iodine.

Examples of the hydrocarbon group, the same ones as exemplified in the description of the R ¹ to R ³ and the like. Specifically, alkyl groups such as methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, nonyl group, dodecyl group, and eicosyl group;
A cycloalkyl group having 3 to 30 carbon atoms, such as a cyclopentyl group, a cyclohexyl group, a norbornyl group, an adamantyl group;
Alkenyl groups such as vinyl, propenyl, cyclohexenyl and the like;
Arylalkyl groups such as benzyl, phenylethyl and phenylpropyl;
Examples thereof include aryl groups such as phenyl group, tolyl group, dimethylphenyl group, trimethylphenyl group, ethylphenyl group, propylphenyl group, biphenyl group, naphthyl group, methylnaphthyl group, anthryl group, and phenanthryl group.

  However, the said hydrocarbon group is not limited to these. In addition, these hydrocarbon groups include halogenated hydrocarbon groups, specifically, groups in which at least one hydrogen of a hydrocarbon group having 1 to 20 carbon atoms is substituted with halogen. Of these, the halogenated hydrocarbon group is preferably a halogenated hydrocarbon group having 1 to 10 carbon atoms.

As the oxygen-containing group, a hydroxy group;
Alkoxy groups such as methoxy, ethoxy, propoxy, butoxy;
Aryloxy groups such as phenoxy group, methylphenoxy group, dimethylphenoxy group, naphthoxy group;
Arylalkoxy groups such as phenylmethoxy group and phenylethoxy group;
An acetoxy group;
A carbonyl group etc. are mentioned. However, the oxygen-containing group is not limited to these.

Examples of the sulfur-containing group include those exemplified in the description of R ^{1 to} R ³ , specifically, methyl sulfonate group, trifluoromethane sulfonate group, phenyl sulfonate group. Sulfonate groups such as benzyl sulfonate group, p-toluene sulfonate group, trimethylbenzene sulfonate group, triisobutyl benzene sulfonate group, p-chlorobenzene sulfonate group, pentafluorobenzene sulfonate group ;
Sulfinate groups such as methyl sulfinate group, phenyl sulfinate group, benzyl sulfinate group, p-toluene sulfinate group, trimethylbenzene sulfinate group, pentafluorobenzene sulfinate group; alkylthio group; arylthio group Etc. However, the sulfur-containing group is not limited to these.

Specific examples of the nitrogen-containing group include the same groups as those exemplified in the description of R ^{1 to} R ³ above. Specifically, an amino group;
Alkylamino groups such as methylamino group, dimethylamino group, diethylamino group, dipropylamino group, dibutylamino group, dicyclohexylamino group;
Examples thereof include arylamino groups such as phenylamino group, diphenylamino group, ditolylamino group, dinaphthylamino group, and methylphenylamino group, and alkylarylamino groups. However, the nitrogen-containing group is not limited to these.

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 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, or the like). .

Specific examples of the phosphorus-containing group include trialkylphosphine groups such as a trimethylphosphine group, a tributylphosphine group, and a tricyclohexylphosphine group;
A triarylphosphine group such as a triphenylphosphine group or a tolylylphosphine group;
Phosphite groups (phosphide groups) such as methyl phosphite group, ethyl phosphite group, phenyl phosphite group;
A phosphonic acid group;
Examples thereof include, but are not limited to, phosphinic acid groups.

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. is not.

Examples of the heterocyclic compound residue include the same as those exemplified in the description of R ^{1 to} R ³ above.

Specific examples of the silicon-containing group include the same groups as those exemplified in the description of R ^{1 to} R ³ , specifically, phenylsilyl group, diphenylsilyl group, trimethylsilyl group, triethylsilyl group, Hydrocarbon-substituted silyl groups such as tripropylsilyl group, tricyclohexylsilyl group, triphenylsilyl group, methyldiphenylsilyl group, tolylsilylsilyl group, trinaphthylsilyl group;
Hydrocarbon-substituted silyl ether groups such as trimethylsilyl ether groups;
Silicon-substituted alkyl groups such as trimethylsilylmethyl groups;
And silicon-substituted aryl groups such as a trimethylsilylphenyl group.

Specific examples of the germanium-containing group include the same groups as those exemplified in the description of R ^{1 to} R ³ , and specific examples include groups in which silicon in the silicon-containing group is replaced with germanium. .

Specific examples of the tin-containing group include those exemplified in the description of R ^{1 to} R ³ above, and more specifically, a group in which silicon in the silicon-containing group is substituted with tin. It is done.

  In the above general formula (I), n is a number satisfying the valence of M, usually an integer of 0 to 5, preferably an integer of 1 to 4, more preferably an integer of 1 to 3, particularly preferably. 2. When n is 2 or more, a plurality of Xs may be the same or different from each other. A plurality of groups represented by X may be bonded to each other to form a ring.

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

In the above examples, Ph represents a phenyl group, iPr represents an isopropyl group, and tBu represents a tert-butyl group. In the above examples, transition metal compounds in which hafnium is replaced with titanium or zirconium can also be mentioned as examples of transition metal compounds (A). Further, in the above examples, can be mentioned as examples of the (CH 2 _Ph), transition metal compounds is replaced with a substituent exemplified as X in the general formula (I) is also a transition metal compound (A).

  The method for producing such a transition metal compound (A) is not particularly limited and can be produced, for example, as follows.

  First, the ligand can be synthesized by a previously reported method (Organic Letters, 2002, 4, 435.). Next, by reacting the obtained ligand with a compound containing a transition metal atom M, a corresponding transition metal compound can be synthesized. Specifically, the ligand is dissolved in a solvent, mixed with a metal compound such as a metal alkylated product, a metal arylated product, or a metal arylalkylated product in a temperature range of −78 ° C. to room temperature, and a temperature of −78 ° C. to room temperature. Stir for about 10 minutes to 48 hours under range or reflux conditions. As the solvent, those commonly used for such a reaction can be used, and among them, polar solvents such as ether and tetrahydrofuran (THF), hydrocarbon solvents such as toluene and the like are preferably used.

Moreover, the transition metal compound obtained by such a manufacturing method can also use the reaction solution of a ligand and a metal compound for olefin polymerization as it is, without isolating.
<Olefin polymerization catalyst>
Hereinafter, the olefin polymerization catalyst of the present invention will be described in detail.

  The catalyst for olefin polymerization of the present invention comprises the transition metal compound (A) represented by the general formula (I), and further comprises (B) (B-1) an organometallic compound and (B-2) an organoaluminum oxy compound. And (B-3) it preferably contains at least one compound selected from the group consisting of compounds that react with the transition metal compound (A) to form ion pairs.

  As the transition metal compound (A) constituting the olefin polymerization catalyst of the present invention, the aforementioned transition metal compound (A) is used.

Hereinafter, the compound (B) group will be described in detail.
[Compound (B)]
Reaction with (B-1) organometallic compound, (B-2) organoaluminum oxy compound, and (B-3) transition metal compound (A), which are constituents of the olefin polymerization catalyst of the present invention, ion pairs The compound which forms is described.
<(B-1) Organometallic compound>
As the (B-1) organometallic compound used in the present invention, specifically, an organoaluminum compound represented by the following general formula (B-1a), a periodic table first represented by the general formula (B-1b) And a complex alkylated product of a group metal and aluminum, and a dialkyl compound of a group 2 or group 12 metal represented by the general formula (B-1c). The (B-1) organometallic compound does not include the (B-2) organoaluminum oxy compound described later.

^{_{R a p Al (OR b)}} q H r Y s ··· (B-1a)
(In the general formula (B-1a), 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 Y represents a halogen atom. P is 0 <p ≦ 3, q is 0 ≦ q <3, r is 0 ≦ r <3, s is 0 ≦ s <3, and m + n + p + q = 3.
M ³ AlR ^c ₄ (B-1b)
(In the general formula (B-1b), M ³ represents Li, Na or K, and R ^c represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms.)
R ^d R ^e M ⁴ (B-1c)
(In the general formula (B-1c), R ^d and R ^e may be the same or different from each other, and represent a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, and M ⁴ represents Mg. , Zn or Cd.)
Examples of the organoaluminum compound represented by the general formula (B-1a) include the following compounds.

R ^a _p Al (OR ^b ) _3-p
(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 p is preferably 1.5 ≦ p ≦ An organoaluminum compound represented by the following formula:
R ^a _p AlY _3-p
(Wherein ^Ra represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, Y represents a halogen atom, and p is preferably a number of 0 <p <3). An organoaluminum compound represented,
R ^a _p AlH _3-p
(Wherein R ^a represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, and p is preferably a number of 2 ≦ p <3),
_{^{R a p Al (OR b)}} q Y s
(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, Y represents a halogen atom, and p represents 0. <P ≦ 3, q is a number of 0 ≦ q <3, s is a number of 0 ≦ s <3, and p + q + s = 3).

More specifically, as an organoaluminum compound belonging to the general formula (B-1a), trimethylaluminum, triethylaluminum, tri-n-butylaluminum, tripropylaluminum, tripentylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum Tri-n-alkylaluminum such as;
Triisopropylaluminum, triisobutylaluminum, trisec-butylaluminum, tritert-butylaluminum, tri-2-methylbutylaluminum, tri-3-methylbutylaluminum, tri-2-methylpentylaluminum, tri-3-methylpentylaluminum, tri-4 A tri-branched alkylaluminum 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;
R ^a _2.5 Al (OR ^b ) Partially alkoxylated alkylaluminum having an average composition represented by _0.5 (wherein R ^a and R ^b may be the same or different from each other; A hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms);
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 in the present invention. Examples of such a compound include an organoaluminum compound in which two or more aluminum compounds are bonded through 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 .

Examples of the compound belonging to the general formula (B-1b) include LiAl (C ₂ H ₅ ) ₄ and LiAl (C ₇ H ₁₅ ) ₄ .

  Examples of the compound belonging to the general formula (B-1c) include dimethyl magnesium, diethyl magnesium, dibutyl magnesium, butyl ethyl magnesium, dimethyl zinc, diethyl zinc, diphenyl zinc, di-n-propyl zinc, diisopropyl zinc, di-n- Examples thereof include butyl zinc, diisobutyl zinc, bis (pentafluorophenyl) zinc, dimethyl cadmium, diethyl cadmium and the like.

  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, butylmagnesium bromide, butylmagnesium chloride and the like can also be used.

  In addition, a compound capable of forming the organoaluminum compound in the polymerization system, for example, a combination of aluminum halide and alkyllithium, or a combination of aluminum halide and alkylmagnesium is used as the (B-1) organometallic compound. It can also be used as

The above (B-1) organometallic compounds are used singly or in combination of two or more.
<(B-2) Organoaluminum oxy compound>
The (B-2) organoaluminum oxy compound used in the present invention may be a conventionally known aluminoxane, or a benzene-insoluble organoaluminum oxy compound as exemplified in JP-A-2-78687. May be. Specific examples of (B-2) organoaluminum oxy compounds include methylaluminoxane, ethylaluminoxane, isobutylaluminoxane, and the like.

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 suspension of the hydrocarbon.
(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 unreacted organoaluminum compound by distillation from the recovered solution of the above aluminoxane, the obtained aluminoxane may be redissolved in a solvent or suspended in a poor aluminoxane solvent.

  Specific examples of the organoaluminum compound used in preparing the aluminoxane include the same organoaluminum compounds as those exemplified as the organoaluminum compound belonging to the general formula (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, it is preferably insoluble or hardly soluble in benzene.

  Examples of the organoaluminum oxy compound (B-2) used in the present invention include an organoaluminum oxy compound containing boron represented by the following general formula (IV).

(In the general formula (IV), R ¹¹ represents a hydrocarbon group having 1 to 10 carbon atoms, and four R ^{12 s} may be the same as or different from each other, and have a hydrogen atom, a halogen atom, or a carbon atom number. 1 to 10 hydrocarbon groups are shown.)
The organoaluminum oxy compound containing boron represented by the general formula (IV) comprises an alkyl boronic acid represented by the following general formula (V) and an organoaluminum compound in an inert solvent under an inert gas atmosphere. It can be produced by reacting at a temperature of -80 ° C to room temperature for 1 minute to 24 hours.

R ¹² -B (OH) ₂ (V)
(In the general formula (V), R ¹² represents the same group as R ¹² in the general formula (IV).)
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-difluoroboronic 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 the general formula (B-1a). As the organoaluminum compound, 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) Compound that reacts with transition metal compound (A) to form an ion pair>
As the compound (B-3) used in the present invention to react with the transition metal compound (A) to form an ion pair (hereinafter also referred to as “(B-3) ionized ionic compound”), JP-A-1-501950, JP-A-1-503636, JP-A-3-179005, JP-A-3-179006, JP-A-3-207703, JP-A-3-207704, US Patent Examples include Lewis acids, ionic compounds, borane compounds, and carborane compounds described in No. 5321106. 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 used. For example, trifluoroboron, triphenylboron, tris (4-fluorophenyl) boron, tris (3,5-difluorophenyl) boron, tris (4-fluoromethylphenyl) boron, tris (pentafluorophenyl) boron, Examples include tris (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 General Formula (VI), R ¹³ is H ⁺ , a carbonium cation, an oxonium cation, an ammonium cation, a phosphonium cation, a cycloheptyltrienyl cation, or a ferrocenium cation having a transition metal, and R ^{14 to} R ^17. May be the same or different from each other and are hydrocarbon groups having 1 to 10 carbon atoms, preferably aryl groups or substituted aryl groups having 6 to 10 carbon atoms.

  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 cation, triethylammonium cation, tripropylammonium cation, tributylammonium cation, and tri (n-butyl) ammonium cation; N, N-dimethylanilinium cation; N, N-diethylanilinium cation, N, N-2,4,6-pentamethylanilinium cation and other N, N-dialkylanilinium cation; di (isopropyl) ammonium cation, dicyclohexylammonium cation and other dialkylammonium 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 ¹³⁺ is preferably a carbonium cation or an ammonium cation, particularly preferably a triphenylcarbonium cation, an N, N-dimethylanilinium cation, or an N, N-diethylanilinium cation.

R ^{14 to} R ¹⁷ are each a hydrocarbon group having 1 to 10 carbon atoms, preferably an aryl group or substituted aryl group having 6 to 10 carbon atoms, and specifically includes a phenyl group, a tolyl group, and dimethyl group. Examples thereof include a phenyl group, a trifluoromethylphenyl group, a ditrifluoromethylphenyl group, a pentafluorophenyl group, and a tolylpentafluorophenyl group. Of these, a trifluoromethylphenyl group, a ditrifluoromethylphenyl group, and a pentafluorophenyl group are preferable, and a pentafluorophenyl group is particularly preferable.

  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 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-ditrifluoromethyl) Yl) boron, tri (n- butyl) ammonium tetra (o-tolyl) and boron and the like.

  Specific examples of the N, N-dialkylanilinium salt include N, N-dimethylanilinium tetra (phenyl) boron, N, N-diethylanilinium tetra (phenyl) boron, N, N, 2,4, Examples thereof include 6-pentamethylanilinium tetra (phenyl) boron.

  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 Examples thereof include a cyclopentadienyl complex, an N, N-diethylanilinium pentaphenylcyclopentadienyl complex, and a boron compound represented by the following formula (VII) or (VIII).

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

(In the formula (VIII), Et represents an ethyl group.)
Specifically as a borane compound which is an example of an ionized ionic compound (compound (B-3)), for example, decaborane;
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, bis [tri (n-butyl) ammonium] dodecachlorododecaborate;
Of metal borane anions such as tri (n-butyl) ammonium bis (dodecahydridododecaborate) cobaltate (III), bis [tri (n-butyl) ammonium] bis (dodecahydridododecaborate) nickate (III) Examples include salt.

Specific examples of carborane compounds that are examples of ionized ionic compounds include 4-carbanonaborane, 1,3-dicarbanonaborane, 6,9-dicarbadecarborane, dodecahydride-1-phenyl-1,3- Dicarbanonaborane, dodecahydride-1-methyl-1,3-dicarbanonaborane, undecahydride-1,3-dimethyl-1,3-dicarbanonaborane, 7,8-dicarbaundecaborane, 2 , 7-dicarbaound decaborane, undecahydride-7,8-dimethyl-7,8-dicarbaound decaborane, dodecahydride-11-methyl-2,7-dicarbound decaborane, tri (n-butyl) ammonium 1-carbadecaborate, tri (n-butyl) ammonium 1-carbaundecaborate, tri (n-butyl) L) Ammonium 1-carbadodecaborate, tri (n-butyl) ammonium 1-trimethylsilyl-1-carbadecaborate, tri (n-butyl) ammonium bromo-1-carbadodecaborate, tri (n-butyl) ammonium 6- Carbadecaborate, tri (n-butyl) ammonium 6-carbadecaborate, tri (n-butyl) ammonium 7-carbaundecaborate, tri (n-butyl) ammonium 7,8-dicarbaundecaborate, tri (n -Butyl) ammonium 2,9-dicarbaundecaborate, tri (n-butyl) ammonium dodecahydride-8-methyl-7,9-dicarbaundecaborate, tri (n-butyl) ammonium undecahydride-8-ethyl -7,9-dicarbaounde cabole Tri (n-butyl) ammonium undecahydride-8-butyl-7,9-dicarbaundecaborate, tri (n-butyl) ammonium undecahydride-8-allyl-7,9-dicarbaundecaborate, Anions such as tri (n-butyl) ammonium undecahydride-9-trimethylsilyl-7,8-dicarbaundecaborate, tri (n-butyl) ammonium undecahydride-4,6-dibromo-7-carbaundecaborate Salt of;
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-dicarbaundecaborate) cobaltate (III), tri (n-butyl) ammonium bis (undecahydride-7) , 8-dicarbaundecaborate) nickelate (III), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarboundeborate) cuprate (III), tri (n-butyl) Ammonium bis (undecahydride-7,8-dicarbaundecaborate) aurate (III , Tri (n-butyl) ammonium bis (nonahydride-7,8-dimethyl-7,8-dicarboundecarboxylate) ferrate (III), tri (n-butyl) ammonium bis (nonahydride-7,8 -Dimethyl-7,8-dicarbaundecaborate) chromate (III), tri (n-butyl) ammonium bis (tribromooctahydride-7,8-dicarbaundecaborate) cobaltate (III), tris [Tri (n-butyl) ammonium] bis (undecahydride-7-carbaundecaborate) chromate (III), bis [tri (n-butyl) ammonium] bis (undecahydride-7-carbaundeca Borate) manganate (IV), bis [tri (n-butyl) ammonium] bis (undeca) Metal carborane anions such as idride-7-carbaundecaborate) cobaltate (III), bis [tri (n-butyl) ammonium] bis (undecahydride-7-carbaundecaborate) nickelate (IV) And the like.

  The heteropoly compound that is an example of the ionized ionic compound includes an atom selected from silicon, phosphorus, titanium, germanium, arsenic, and tin, and one or more atoms selected from vanadium, niobium, molybdenum, and tungsten. A compound. 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, germano-tungstovanadic acid, phosphomolybdo-tungstovanadic acid, germano-molybdo-tungstovanadic acid, phosphomolybdotungstic acid , Phosphomolybdoniobic acid, and salts of these acids, but not limited thereto. The salt includes, for example, metals of Group 1 or 2 of the periodic table, specifically lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium and the like. And organic salts such as triphenylethyl salt.

An isopoly compound which is an example of an ionized ionic compound is a compound composed of a metal ion of one kind of atom selected from vanadium, niobium, molybdenum and tungsten, and is regarded as a molecular ionic species of a metal oxide. Can do. Specific examples include vanadic acid, niobic acid, molybdic acid, tungstic acid, and salts of these acids, but are not limited thereto. The salt includes, for example, metals of Group 1 or Group 2 of the periodic table, specifically lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium and the like. Examples thereof include organic salts such as salts and triphenylethyl salts.
The ionized ionic compounds as described above ((B-3) compounds that react with the transition metal compound (A) to form ion pairs) are used singly or in combination of two or more.

  The compounds that react with (B-1) the organometallic compound, (B-2) the organoaluminum oxy compound, and (B-3) the transition metal compound (A), which are detailed above, form ion pairs. It can also be used in combination. In particular, when the transition metal compound (A) in the present invention is used, a combination of (B-1) an organometallic compound and (B-3) a compound that reacts with the transition metal compound (A) to form an ion pair is used. In addition, it was revealed that high polymerization activity and high copolymerization were exhibited. So far, examples of high polymerization activity by using (B-2) organoaluminum oxy compounds such as methylaluminoxane as a promoter component in combination with known transition metal compounds have been reported. (B-2) Organoaluminum oxy compounds are generally expensive, and depending on the amount used, the cost of the resulting olefin polymer has been increased.

  On the other hand, as described above, the transition metal compound (A) in the present invention comprises a compound that reacts with the (B-1) organometallic compound and (B-3) the transition metal compound (A) to form an ion pair as a promoter component. Even when used in combination, it exhibits high polymerization activity and high copolymerizability, and these cocatalyst components can be obtained at a very low cost. There is an advantage that it can be manufactured at a low cost.

The olefin polymerization catalyst according to the present invention comprises the transition metal compound (A), (B-1) an organometallic compound, (B-2) an organoaluminum oxy compound, and (B-3) an ionized ionic compound. Together with at least one compound (B) selected from the group, the following carrier (C) may be included as required.
[Carrier (C)]
The carrier (C) used in the present invention is an inorganic or organic compound and is a granular or particulate solid. By supporting the transition metal compound (A) and the compound (B) on the carrier (C), a polymer having a good morphology can be obtained.

  As the inorganic compound, porous oxides, inorganic halides, clays, clay minerals or ion-exchangeable layered compounds are preferable.

As the porous oxide, specifically, SiO ₂ , Al ₂ O ₃ , MgO, ZrO, TiO ₂ , B ₂ O ₃ , CaO, ZnO, BaO, ThO ₂ or the like, or a composite or mixture containing these is used. can be used, further, for example, natural or synthetic _{zeolites, 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, SiO it can be used, such as ₂ -TiO ₂ -MgO. Among these, as the porous oxide, those containing SiO ₂ and / or Al ₂ O ₃ as main components are preferable.

The porous 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 porous oxide 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. It is desirable that the pore volume be in the range of 50 to 1000 m ² / g, preferably 100 to 700 m ² / g, and the pore volume be in the range of 0.3 to 3.0 cm ³ / g. Such a porous oxide is used after being calcined at 100 to 1000 ° C., preferably 150 to 700 ° C., if necessary.

As the inorganic halide, MgCl ₂ , MgBr ₂ , MnCl ₂ , MnBr ₂ or the like is used. The inorganic halide may be used as it is or after being pulverized by a ball mill or a vibration mill. Further, it is also possible to use a material in which an inorganic halide is dissolved in a solvent such as alcohol and then precipitated into fine particles with a precipitating agent.

  The clay is usually composed mainly of clay minerals. Moreover, the said ion exchange layered compound is a compound which has a crystal structure where the surface comprised by the ionic bond etc. was piled up in parallel with weak mutual binding force, and the ion to contain is exchangeable. 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, examples of the clay, clay mineral, or ion-exchangeable layered compound include ionic crystalline compounds having a layered crystal structure such as a hexagonal close packing type, an antimony type, a CdCl ₂ type, and a CdI ₂ type.

In addition, as clay and clay minerals, kaolin, bentonite, kibushi clay, gyrome clay, allophane, hysingelite, pyrophyllite, unmo group, montmorillonite group, vermiculite, ryokdeite group, palygorskite, kaolinite, nacrite, dickite, Examples of the ion exchange layered compound include 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 , crystalline acid salts of polyvalent metals such as γ-Ti (NH ₄ PO ₄ ) ₂ .H ₂ O.

  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 to 5 cc / g as measured by mercury porosimetry. It is particularly preferred. Here, the pore volume is measured in a range of pore radius of 20 to 30000 mm 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⁺ , and [Fe ₃ O (OCOCH ₃ ) ₆ ] ⁺ Can be mentioned. These compounds are used alone or in combination of two or more. Further, when intercalating these compounds, metal alkoxides such as Si (OR) ₄ , Al (OR) ₃ , Ge (OR) ₄ (R represents a hydrocarbon group, etc.) are hydrolyzed. The obtained polymer, a colloidal inorganic compound such as SiO _2, etc. can also 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.

  Of these, preferred are clays or clay minerals, and particularly preferred are montmorillonite, vermiculite, pectolite, teniolite and synthetic mica.

  As described above, the carrier (C) is an inorganic or organic compound, and examples of the organic compound include a granular or fine particle solid having a particle size in the range of 10 to 300 μm. Specifically, a (co) polymer produced mainly from an α-olefin having 2 to 14 carbon atoms such as ethylene, propylene, 1-butene, 4-methyl-1-pentene, vinylcyclohexane, styrene (Co) polymers produced by the main component, and their modified products.

The catalyst for olefin polymerization according to the present invention includes the transition metal compound (A), preferably the compound (B), and a carrier (C) as necessary. An organic compound component (D) can also be included.
[Organic compound component (D)]
In the present invention, the organic compound component (D) improves the polymerization performance (for example, catalytic activity) of the olefin polymerization catalyst of the present invention and the physical properties of the generated polymer (for example, increase the molecular weight of the generated polymer) as necessary. Used for purposes. Examples of such organic compounds include, but are not limited to, alcohols, phenolic compounds, carboxylic acids, phosphorus compounds, and sulfonates.

As the alcohols and the phenolic compounds, those represented by R ¹⁸ —OH are usually used, wherein R ¹⁸ is a hydrocarbon group having 1 to 50 carbon atoms (in the case of phenols, carbon atoms). The number is 6 to 50) or a halogenated hydrocarbon group having 1 to 50 carbon atoms (6 to 50 carbon atoms in the case of phenols).

As the alcohol, R ¹⁸ is preferably a halogenated hydrocarbon group. Moreover, as a phenolic compound, what substituted the (alpha) and (alpha) '-position of the hydroxyl group with the C1-C20 hydrocarbon is preferable.

As said carboxylic acid, what is normally represented by R < ¹⁹ > -COOH is used. R ¹⁹ 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 acids having a P—O—H bond, P—OR, phosphate having a P═O bond, and a phosphine oxide compound are preferably used.

  Examples of the sulfonate include those represented by the following general formula (IX).

(In General Formula (IX), M ⁵ is an element of Groups 1 to 14 of the periodic table, and R ²⁰ is hydrogen, a hydrocarbon group having 1 to 20 carbon atoms, or a halogenated carbonization having 1 to 20 carbon atoms. A hydrogen group, Z 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, and t is an integer of 1 to 7 , U is an integer satisfying 1 ≦ u ≦ 7, and t−u is an integer satisfying t−u ≧ 1.
<Olefin polymer production method>
In the method for producing an olefin polymer according to the present invention, an olefin polymer is obtained by homopolymerizing or copolymerizing an olefin in the presence of the olefin polymerization catalyst as described above. In addition, in this specification, an olefin shows the hydrocarbon which has one carbon-carbon double bond in a molecule | numerator.

  In the present invention, the olefin copolymerization means that at least one monomer may be an olefin, and two or more olefins may be copolymerized, or a monomer other than an olefin may be copolymerized with an olefin. .

The method of using each component constituting the catalyst of the present invention and the order of addition to the polymerization vessel in the polymerization reaction are arbitrarily selected, and the following methods are exemplified.
(1) A method of adding the transition metal compound (A) alone to the polymerization vessel.
(2) A method of adding the transition metal compound (A) and the compound (B) to the polymerization vessel in an arbitrary order.
(3) A method in which the catalyst component having the transition metal compound (A) supported on the carrier (C) and the compound (B) are added to the polymerization vessel in any order.
(4) A method in which the catalyst component having the compound (B) supported on the carrier (C) and the transition metal compound (A) are added to the polymerization vessel in any order.
(5) A method in which a catalyst component in which a transition metal compound (A) and a compound (B) are supported on a carrier (C) is added to a polymerization vessel.
(6) A method in which the catalyst component having the transition metal compound (A) and the compound (B) supported on the carrier (C) and the compound (B) are added to the polymerization vessel in any order. In this case, the compounds (B) may be the same or different.
(7) A method in which the catalyst component having the compound (B) supported on the carrier (C) and the transition metal compound (A) are added to the polymerization vessel in any order.
(8) A method in which the catalyst component having the compound (B) supported on the carrier (C), the transition metal compound (A), and the compound (B) are added to the polymerization vessel in an arbitrary order. In this case, the compounds (B) may be the same or different.
(9) A method in which a component carrying the transition metal compound (A) on the carrier (C) and a component carrying the compound (B) on the carrier (C) are added to the polymerization vessel in any order.
(10) A method in which a component in which the transition metal compound (A) is supported on the carrier (C), a component in which the compound (B) is supported on the carrier (C), and the compound (B) are added to an arbitrary sequential polymerization vessel. In this case, the compounds (B) may be the same or different.
(11) A method in which the transition metal compound (A), the compound (B), and the organic compound component (D) are added to the polymerization vessel in an arbitrary order.
(12) A method in which the component (B) and the organic compound component (D) previously contacted and the transition metal compound (A) are added to the polymerization vessel in an arbitrary order.
(13) A method in which the component (B) and the organic compound component (D) supported on the carrier (C) and the transition metal compound (A) are added to the polymerization vessel in any order.
(14) A method in which the catalyst component obtained by previously contacting the transition metal compound (A) and the compound (B) and the organic compound component (D) are added to the polymerization vessel in an arbitrary order.
(15) A method in which the transition metal compound (A) and the compound (B) are contacted in advance, and the compound (B) and the organic compound component (D) are added to the polymerization vessel in any order. In this case, the compounds (B) may be the same or different.
(16) A catalyst component in which the transition metal compound (A) and the compound (B) are contacted in advance, and a component in which the compound (B) and the organic compound component (D) are contacted in advance are added to the polymerization vessel in any order. Method. In this case, the compounds (B) may be the same or different.
(17) A method in which a component in which a transition metal compound (A) is supported on a carrier (C), a compound (B), and an organic compound component (D) are added to the polymerization vessel in an arbitrary order.
(18) A method in which a component in which the transition metal compound (A) is supported on the carrier (C) and a component in which the compound (B) and the organic compound 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 a transition metal compound (A), a compound (B) and an organic compound component (D) into contact in advance in an arbitrary order is added to a polymerization vessel.
(20) A method in which a transition metal compound (A), a compound (B) and an organic compound component (D) are contacted in advance in any order, and the compound (B) is added to the polymerization vessel in any order. In this case, the compounds (B) may be the same or different.
(21) A method in which a catalyst in which a transition metal compound (A), a compound (B), and an organic compound component (D) are supported on a carrier (C) is added to a polymerization vessel.
(22) A method in which the transition metal compound (A), the compound (B), the catalyst component having the organic compound component (D) supported on the carrier (C), and the compound (B) are added to the polymerization vessel in any order. In this case, the compounds (B) may be the same or different.

  The solid catalyst component in which the transition metal compound (A) is supported on the carrier (C) and the solid catalyst component in which the transition metal compound (A) and the compound (B) are supported on the carrier (C) are preliminarily provided with olefin. The transition metal compound (A) or the compound (B) may be further supported on the prepolymerized solid catalyst component.

  The prepolymerization is preferably carried out by substantially homopolymerization of 95 mol% or more of olefin. The olefin used for the prepolymerization is preferably the same as that used for the main polymerization. Specifically, ethylene, propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 4,4-dimethyl-1-pentene, 1-heptene 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 3-ethyl-1-hexene, 4-ethyl-1-hexene, 1-octene, 1-decene, cyclopentene, vinylcyclohexane, Particularly preferred are ethylene, propylene, 1-butene, 1-heptene, 3-methyl-1-butene, 1-hexene and 4-methyl-1-pentene.

  The amount of olefin polymerization in the prepolymerization is in the range of 0.1 to 1000 g, preferably 1 to 50 g, per 1 g of the solid catalyst component.

  In general, slurry polymerization is preferably applied to the prepolymerization, and a saturated aliphatic hydrocarbon or aromatic hydrocarbon such as hexane, heptane, cyclohexane, benzene, and toluene is used alone, or a mixed solvent thereof is used. Can do.

The prepolymerization temperature is preferably −50 to + 100 ° C., particularly preferably −20 to + 80 ° C., more preferably 0 to + 40 ° C. The prepolymerization time may be appropriately determined according to the prepolymerization temperature and the polymerization amount in the prepolymerization, and the pressure in the prepolymerization is not limited, but in the case of slurry polymerization, generally from normal pressure to 50 kg / cm ^2. Degree. Each preliminary polymerization may be carried out by any of batch, semi-batch and continuous methods. Further, after completion of each prepolymerization, it is preferable to wash saturated aliphatic hydrocarbons or aromatic hydrocarbons such as hexane, heptane, cyclohexane, benzene, and toluene alone or with a mixed solvent thereof. In this case, 5 to 6 times are preferable.

  In the present invention, olefin polymerization can be carried out by any of liquid phase polymerization methods such as solution polymerization and suspension polymerization, or gas phase polymerization methods. 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: aromatic hydrocarbons such as benzene, toluene, xylene; halogenated hydrocarbons such as ethylene chloride, chlorobenzene, dichloromethane or mixtures thereof, and (co) polymerization The olefin (monomer) to be provided can also be used as a solvent.

When the olefin polymerization is performed using the olefin polymerization catalyst as described above, the transition metal compound (A) is usually 10 ⁻¹² to 10 ⁻² mol, preferably 10 ⁻¹⁰ to 10 ⁻¹⁰ per liter of reaction volume. It is used in such an amount that it becomes ^-3 mol.

  (B-1) The organometallic compound usually has a molar ratio [(B-1) / M] of (B-1) the organometallic compound and all transition metal atoms (M) in the transition metal compound (A). It is used in an amount of 0.01 to 100,000, preferably 0.05 to 50,000. (B-2) The organoaluminum oxy compound is a molar ratio of the aluminum atom in the (B-2) organoaluminum oxy compound and the total transition metal (M) in the transition metal compound (A) [(B-2). / M] is usually used in an amount of 10 to 500,000, preferably 20 to 100,000. (B-3) A compound (ionized ionic compound) that reacts with the transition metal compound (A) to form an ion pair includes (B-3) an ionized ionic compound and a transition metal in the transition metal compound (A). The molar ratio [(B-3) / M] with the atom (M) is usually 1 to 10, preferably 1 to 5.

  When the compound (B) is the (B-1) organometallic compound, the organic compound component (D) has a molar ratio [(D) / (B-1)] of usually 0.01 to 10, preferably 0. Used in such an amount that it becomes 1-5. When the compound (B) is an (B-2) organoaluminum oxy compound, the molar ratio [(D) / (B-2)] is usually 0.01 to 2, preferably 0.005 to 1. Used in various amounts. When the compound (B) is a (B-3) ionized ionic compound, the molar ratio [(D) / (B-3)] is usually 0.01 to 10, preferably 0.1 to 5. Used in quantity.

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 -G, preferably from normal pressure to 50 kg / cm ² -G, and the polymerization reaction is carried out in any of batch, semi-continuous and continuous methods. Can also be done. Furthermore, the polymerization can be performed 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 with the quantity of the compound (B) to be used.

The olefin that can be polymerized by the olefin polymerization catalyst of the present invention is not particularly limited, but a linear or branched α-olefin having 2 to 30 carbon atoms, preferably 2 to 20 carbon atoms, such as ethylene, Propylene, 1-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-eicocene;
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 and the like.

  The catalyst for olefin polymerization of the present invention can also copolymerize an olefin and another monomer having a polymerizable carbon-carbon double bond in the molecule. The other monomer may be any monomer other than olefin and is not particularly limited. For example, a polar group (for example, a carbonyl group, a hydroxyl group, an ether bond group, etc.) and a polymerizable carbon-carbon double bond are included in the molecule. Monomer (hereinafter also referred to as polar group-containing monomer).

Specific examples of the polar group-containing monomer include acrylic acid, 3-butenoic acid, 4-pentenoic acid, 5-hexenoic acid, 6-heptenoic acid, 7-octenoic acid, 8-nonenoic acid, and 9-decenoic acid. 10-undecenoic acid, 11-dodecenoic acid, 12-tridecenoic acid, 13-tetradecenoic acid, 14-pentadecenoic acid, 15-hexadecenoic acid, 16-heptadecenoic acid, 17-octadecenoic acid, 18-nonadecenoic acid, 19-eicosenoic acid 20-Henicosenoic acid, 21-docosenoic acid, 22-tricosenoic acid, methacrylic acid, 2-methylpentenoic acid, 2,2-dimethyl-3-butenoic acid, 2,2-dimethyl-4-pentenoic acid, 3-vinyl Benzoic acid, 4-vinylbenzoic acid, 2,6-heptadienoic acid, 2- (4-isopropylbenzylidene) -4-pentenoic acid, allylmalonic acid, -(10-undecenyl) malonic acid, fumaric acid, itaconic acid, bicyclo [2.2.1] -5-heptene-2-carboxylic acid, bicyclo [2.2.1] -5-heptene-2,3- Unsaturated carboxylic acids such as dicarboxylic acids, and metal salts such as sodium salts, potassium salts, lithium salts, zinc salts, magnesium salts, and calcium salts, and methyl esters, ethyl esters, and n-propyls of these unsaturated carboxylic acids Unsaturated carboxylic acid esters such as ester, isopropyl ester, n-butyl ester, isobutyl ester, (5-norbornen-2-yl) ester (in the case where the unsaturated carboxylic acid is a dicarboxylic acid, Can also be diesters), and amides of these unsaturated carboxylic acids, N, N-di- Unsaturated carboxylic acid amides such as Chiruamido (may be a diamide be a monoamide when unsaturated carboxylic acid is a dicarboxylic acid);
Maleic anhydride, itaconic anhydride, allyl succinic anhydride, isobutenyl succinic anhydride, (2,7-octadien-1-yl) succinic anhydride, tetrahydrophthalic anhydride, bicyclo [2.2.1 ] Unsaturated carboxylic acid anhydrides such as -5-heptene-2,3-dicarboxylic acid anhydride;
Vinyl esters such as vinyl acetate, vinyl propionate, vinyl caproate, vinyl caprate, vinyl laurate, vinyl stearate, vinyl trifluoroacetate;
Halogenated olefins such as vinyl chloride, vinyl fluoride, vinyl bromide, vinyl iodide, allyl bromide, allyl chloride, allyl fluoride, allyl bromide;
Silylated olefins such as allyltrimethylsilane, diallyldimethylsilane, 3-butenyltrimethylsilane, allyltriisopropylsilane, allyltriphenylsilane;
Unsaturated nitriles such as acrylonitrile, 2-cyanobicyclo [2.2.1] -5-heptene, 2,3-dicyanobicyclo [2.2.1] -5-heptene;
Unsaturated alcohol compounds such as allyl alcohol, 3-butenol, 4-pentenol, 5-hexenol, 6-hebutenol, 7-octenol, 8-nonenol, 9-decenol, 10-undecenol, 11-dodecenol, 12-tridecenol And unsaturated esters thereof such as acetates, benzoates, propionates, caproates, caprates, laurates, stearates;
Substituted phenols such as vinylphenol and allylphenol;
Unsaturated ethers such as methyl vinyl ether, ethyl vinyl ether, allyl methyl ether, allyl propyl ether, allyl butyl ether, allyl methallyl ether, methoxy styrene, ethoxy styrene, allyl anisole;
Unsaturated epoxides such as butadiene monoxide, 1,2-epoxy-7-octene, 3-vinyl-7-oxabicyclo [4.1.0] heptane;
Unsaturated aldehydes such as acrolein and undecenal, and unsaturated acetals such as dimethyl acetal and diethyl acetal;
Unsaturated ketones such as methyl vinyl ketone, ethyl vinyl ketone, allyl methyl ketone, allyl ethyl ketone, allyl propyl ketone, allyl butyl ketone, and allyl benzyl ketone, and unsaturated acetals such as dimethyl acetal and diethyl acetal;
Unsaturated thioethers such as allyl methyl sulfide, allyl phenyl sulfide, allyl isopropyl sulfide, allyl n-propyl sulfide, 4-pentenyl phenyl sulfide;
Unsaturated sulfoxides such as allyl phenyl sulfoxide;
Unsaturated sulfones such as allyl phenyl sulfone;
Unsaturated phosphines such as allyldiphenylphosphine;
And unsaturated phosphine oxides such as allyldiphenylphosphine oxide.

  Furthermore, examples of the polar group-containing monomer include vinyl benzyl acetate, hydroxystyrene, methyl 4- (3-butenyloxy) benzoate, methoxystyrene, ethoxystyrene, allyl trifluoroacetate, o-chlorostyrene, and p-chlorostyrene. Glycidyl acrylate, allyl glycidyl ether, (2H-perfluoropropyl) -2-propenyl ether, linalool oxide, 3-allyloxy-1,2-propanediol, 2- (allyloxy) ethanol, N-allylmorpholine, allyl glycine, N-vinylpyrrolidone, allyltrichlorosilane, acryltrimethylsilane, allyldimethyl (diisopropylamino) silane, 7-octenyltrimethoxysilane, allyloxytrimethylsilane, allyloxytrifluoro Rushiran etc. also mentioned, it is possible to olefin copolymerized with the olefin polymerization catalyst of the present invention.

  Moreover, as a monomer other than the polar group-containing monomer, vinylcyclohexane, diene, polyene, or the like can be used. In the presence of the olefin polymerization catalyst of the present invention, these monomers can also be copolymerized with the olefin.

Examples of the diene or polyene include cyclic or chain compounds having 4 to 30 carbon atoms, preferably 4 to 20 carbon atoms, and having two or more carbon / carbon double bonds. 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, divinylbenzene;
Examples include 7-methyl-1,6-octadiene, 4-ethylidene-8-methyl-1,7-nonadiene, and 5,9-dimethyl-1,4,8-decatriene.

Furthermore, an aromatic vinyl compound can be used as another monomer. Specifically, mono- or polyalkyl styrene 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;
Functional group-containing styrene derivatives such as methoxystyrene, ethoxystyrene, vinyl benzoic acid, methyl vinyl benzoate, vinyl benzyl acetate, hydroxystyrene, o-chlorostyrene, p-chlorostyrene;
And 3-phenylpropylene, 4-phenylpropylene, α-methylstyrene and the like.

  Among these, when the olefin polymerization catalyst according to the present invention is used, compared with the conventional olefin polymerization catalyst using a transition metal compound having a pyrrolimine ligand represented by the general formula (PI), ethylene In the copolymerization reaction between olefin and α-olefin, an olefin copolymer having a particularly high polymerization activity and a high comonomer content can be produced.

  As the α-olefin, α-olefins listed in the description of the olefin can be used without limitation. In the polymerization reaction using the olefin polymerization catalyst according to the present invention, the viewpoints of polymerization activity and copolymerization are used. To Preferable are propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene and 3-methyl-1-pentene. Of these, propylene, 1-butene, 1-hexene and 4-methyl-1-pentene are more preferable, and propylene is more preferable.

  EXAMPLES Hereinafter, although this invention is demonstrated further more concretely based on an Example, this invention is not limited to these.

The structures of the compounds obtained in Synthesis Examples and Examples was determined using 270MHz ¹ H-NMR (JEOL EX-270) or the like. Further, the comonomer content of the copolymer obtained in the examples was measured by IR (JASCO FT / IR-410 type).

IR measurement uses the film obtained by melt-stretching the obtained copolymer with a hot press heated to 180 ° C. and then pressure-cooling at room temperature as a measurement sample, and a light source wavelength of 5000 cm ^{−1 to} 400 cm. Between ^-1 . When the α-olefin copolymerized with ethylene is propylene, the propylene content is determined by measuring the IR spectrum of a sample having a known propylene content by ¹³ C-NMR spectrum measurement, and then determining the propylene-based C—CH ₃ skeletal vibration (1150 cm ^{− 1} ) as a key band, and the ratio between the absorbance of the key band (D1150) and the absorbance (D4320) of the internal standard band (4320 cm ⁻¹ : the combined sound of C—H stretching vibration and methylene and methyl bending vibration) [D1150 / D4320] was calculated. Next, [D1150 / D4320] and the propylene content were plotted to create a calibration curve. [D1150 / D4320] of the measurement sample was applied to the calibration curve to determine the propylene content. Even when other α-olefin is used as a comonomer, the comonomer content can be measured by the same method.
[Synthesis Example 1]
A 30 mL reactor that has been thoroughly dried and purged with nitrogen is charged with 0.18 g (0.34 mmol) of tetrabenzylhafnium and 3 mL of toluene, and 0.20 g (0. 0.3 g) of 3,5-diphenyl-2- (2-pyridyl) pyrrole. 68 mmol) in 3 mL of toluene was added with a pipette and stirred at room temperature for 90 minutes. By removing the solvent under reduced pressure, 0.14 g (yield 42%) of an orange powder compound represented by the following formula (A) (hereinafter referred to as transition metal compound (A)) was obtained.
¹ H-NMR (270 MHz, CDCl ₃ ): 8.18 (2H, brd, J = 5.4 Hz, Ar—H), 6.38-7.40 (36H, m, Ar—H), 6.01 (2H, s, Ar—H), 2.26 (4H, brd, J = 16.2 Hz, —CH ₂ —C ₆ H ₅ ) ppm

[Example 1]
To a glass reactor having an internal volume of 500 ml sufficiently purged with nitrogen, 250 ml of toluene was charged, and the liquid phase and the gas phase were saturated with ethylene 50 liter / hr and propylene 150 liter / hr.

  Thereafter, 0.125 mmol of triisobutylaluminum (TIBA), 0.0025 mmol of the transition metal compound (A) obtained in Example 1, and 0.005 mmol of triphenylcarbenium tetrakis (pentafluorophenyl) borate (TrB) were obtained. Polymerization was started by adding 003 mmol.

  After continuously supplying ethylene at 50 liter / hr and propylene at 150 liter / hr and performing polymerization at 50 ° C. for 10 minutes under normal pressure, the polymerization was stopped by adding a small amount of isobutanol.

After completion of the polymerization, the reaction product was added to 1 liter of methanol containing a small amount of hydrochloric acid to precipitate a polymer. After washing with methanol, it was dried under reduced pressure at 80 ° C. for 10 hours to obtain 1.21 g of an ethylene / propylene copolymer (EPR). The polymerization activity was 2906 g / mmol-Hf · hr. By measuring the IR spectrum of the obtained EPR, the absorbance of the key band (D1150) and the ratio of the absorbance (D4320) of the internal standard band (4320 cm ⁻¹ : the combined sound of C—H stretching vibration and methylene and methyl bending vibration) [D1150 / D4320] was calculated, and the propylene content calculated using the calibration curve was 58.3 mol%.
[Comparative Example 1]
To a glass reactor having an internal volume of 500 ml sufficiently purged with nitrogen, 250 ml of toluene was charged, and the liquid phase and the gas phase were saturated with ethylene 50 liter / hr and propylene 150 liter / hr.

  Thereafter, 0.250 mmol of triisobutylaluminum (TIBA), 0.0050 mmol of titanium compound represented by the following formula (T), and 0.006 mmol of triphenylcarbenium tetrakis (pentafluorophenyl) borate (TrB) were added for polymerization. Started.

  After continuously supplying ethylene at 50 liters / hr and propylene at 150 liters / hr and performing polymerization at 50 ° C. for 30 minutes under normal pressure, the polymerization was stopped by adding a small amount of isobutanol.

After completion of the polymerization, the reaction product was added to 1 liter of methanol containing a small amount of hydrochloric acid to precipitate a polymer. After washing with methanol, it was dried under reduced pressure at 80 ° C. for 10 hours to obtain 0.20 g of an ethylene / propylene copolymer (EPR). The polymerization activity was 80 g / mmol-Ti · hr. By measuring the IR spectrum of the obtained EPR, the absorbance of the key band (D1150) and the ratio of the absorbance (D4320) of the internal standard band (4320 cm ⁻¹ : the combined sound of C—H stretching vibration and methylene and methyl bending vibration) [D1150 / D4320] was calculated, and the propylene content calculated using the calibration curve was 8.4 mol%.

  If the catalyst for olefin polymerization containing the transition metal compound according to the present invention is used, an olefin polymer having a high comonomer content can be obtained with high activity. Since the olefin polymer is excellent in impact resistance, flexibility, high elasticity, lightness, transparency, high heat resistance, weather resistance, chemical resistance, etc., the present invention has extremely high industrial value. .

Claims (4)

A transition metal compound (A) represented by the following general formula ( A ),
(B) (B-1) an organometallic compound, (B-2) an organoaluminum oxy compound, and (B-3) at least one selected from compounds that react with the transition metal compound (A) to form an ion pair. A compound of
An olefin polymerization catalyst comprising:
Further comprises a carrier (C), a catalyst for olefin polymerization according to claim 1. The presence of an olefin polymerization catalyst according to claim 1 or 2, process for producing an olefin polymer which olefin (co) polymer. The method for producing an olefin polymer according to claim 3 , wherein the olefin is ethylene and α-olefin.