JP2014224053A - Transition metal compound, olefin polymerization catalyst and manufacturing method of olefin polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an olefin polymerization catalyst including a transition metal compound, having heat resistance even at high temperature, having high polymerization activity in olefin, and excellent in copolymerization properties at performing copolymerization, and a manufacturing method of olefin polymer under presence of the catalyst.SOLUTION: A transition metal compound is expressed by a general formula (I) below. An olefin polymerization catalyst includes the transition metal compound, and preferably includes at least one type of compound selected from a group consisting of an organometallic compound, an organoaluminum oxy compound, and a compound that reacts with the transition metal compound to form an ion pair.

Description

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

  Conventionally, as a catalyst 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, and a vanadium compound and an organoaluminum compound. Vanadium-based catalysts are 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.

  Moreover, the present applicant has proposed a catalyst for olefin polymerization containing a transition metal compound having a salicylaldoimine ligand (see, for example, Patent Document 1). Although the olefin polymerization catalyst containing the transition metal compound represented by the general formula (I) of Patent Document 1 is known to exhibit high olefin polymerization activity, further improvement in polymerization activity is required. In addition, the olefin polymerization catalyst containing the transition metal compound can copolymerize two or more olefins, but further improvements in polymerization activity and copolymerizability have been demanded.

  Therefore, the present applicant has proposed a transition metal compound represented by the general formula (I) in Patent Document 2. The olefin polymerization catalyst containing the transition metal compound exhibits superior olefin polymerization activity when homopolymerizing the olefin, compared with the one containing the transition metal compound represented by the general formula (I) of Patent Document 1. Moreover, it discovered that the polymerization activity at the time of copolymerizing two or more types of olefins, and a copolymerizability were improved.

Japanese Patent Laid-Open No. 11-315109 JP 2011-016789 A

  As a result of further study of the olefin polymerization catalyst shown in Patent Document 2, the present applicant has not yet been sufficiently heat resistant, and polymerization at a high temperature suitable for commercial production, for example, 60 ° C. The problem that activity became low at the above temperature was discovered.

  Therefore, the problems to be solved by the present invention include heat resistance at high temperatures suitable for commercial production, high olefin polymerization activity, and further, copolymerization when two or more olefins are copolymerized. It is to provide a novel transition metal compound constituting a high olefin polymerization catalyst, an olefin polymerization catalyst containing the transition metal compound, and a method for producing an olefin polymer performed in the presence of the catalyst.

  As a result of intensive studies to solve the above problems, the present inventors have found that the above problems can be solved by a specific transition metal compound and an olefin polymerization catalyst containing the transition metal compound. Was completed.

  That is, in the present invention, the transition metal compound is (A) a transition metal compound represented by the following general formula (I).

(In the above general formula (I), M represents a transition metal atom of Groups 3 to 10 of the periodic table,
Y represents an oxygen atom, a sulfur atom, a nitrogen atom having a bonding group —R ⁸ , or a phosphorus atom having a bonding group —R ⁸ ;
Q represents a carbon atom, a silicon atom, a germanium atom, a tin atom,
R ^{1 to} R ³ may be the same as or different from each other, and are a secondary alkyl group, a tertiary alkyl group, a cycloalkyl group, or an aryl group, and R ¹ and R ² are connected to each other. A ring may be formed, R ² and R ³ may be linked together to form a ring, R ¹ and R ³ may be linked together to form a ring,
R ^{4 to} R ⁸ may be the same or different from each other, and are a hydrogen atom, a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, a sulfur-containing group, phosphorus A containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group, and two or more adjacent groups among them may be linked to each other to form a ring,
n represents 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, a plurality of groups represented by X may be the same or different from each other, and a plurality of groups represented by X may be bonded to each other to form a ring ,
L represents a neutral ligand including elements 13 to 16 of the periodic table;
m is 0 or an integer of 1 to 4,
D represents an optionally substituted hydrocarbon group or heterocyclic compound residue, the shortest number of bonds connecting A and N is 4 to 6, and the number of bonds connecting A and D is two. It may be a heavy bond or a triple bond. )
The shortest bond number connecting A and N of the transition metal compound represented by the general formula (I) is preferably 5 or 6.

  It is preferable that A, N and D of the transition metal compound represented by (A) the general formula (I) form a structure represented by the general formula (II).

(In General Formula (II), Y represents the same atom as that represented by General Formula (I),
R ^{9 to} R ¹² 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 when R ^{9 to} R ¹² are hydrocarbon groups, R ⁹ and R ¹⁰ are connected to each other to form a ring. R ¹¹ and R ¹² may be connected to each other to form a ring. )
It is preferable that M of the transition metal compound represented by the general formula (I) (A) is a transition metal atom of Group 4 of the periodic table and n is 4.

  The catalyst for olefin polymerization of the present invention contains the transition metal compound (A).

  In addition to the transition metal compound (A), the olefin polymerization catalyst of the present invention comprises (B) (B-1) an organometallic compound, (B-2) an organoaluminum oxy compound, and (B-3) a transition metal. It is preferable to include at least one compound selected from compounds that react with the compound (A) to form ion pairs.

  The method for producing an olefin polymer of the present invention is characterized in that an olefin is homopolymerized or copolymerized in the presence of the olefin polymerization catalyst.

  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”.

  Since the transition metal compound of the present invention and the catalyst for olefin polymerization containing the transition metal compound have heat resistance even at a high temperature suitable for commercial production, the olefin polymerization activity is high. When copolymerizing, it shows high copolymerizability.

  Therefore, in particular, when two or more olefins are copolymerized at a high temperature suitable for commercial production in the presence of the olefin polymerization catalyst, an olefin copolymer having a high comonomer content is obtained in a high yield. Can be obtained.

<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 in Groups 3 to 10 of the periodic table (Group 3 includes lanthanoids), preferably a Group 3 to 9 metal atom, more preferably It is a transition metal atom selected from Group 3 to 5, more preferably a transition metal atom selected from Group 4 or Group 5, and particularly preferably a Group 4 transition metal atom. Specifically, titanium atom, zirconium atom, hafnium atom, vanadium atom, niobium atom, tantalum atom, chromium atom, molybdenum atom, tungsten atom, manganese atom, rhenium atom, iron atom, ruthenium atom, cobalt atom, rhodium atom, nickel An atom or a palladium atom, preferably a titanium atom, a zirconium atom or a hafnium atom, particularly preferably a titanium atom.

  In the above general formula (I), a dotted line connecting N and M indicates that N is coordinated to M.

  In the above general formula (I), n is a number satisfying the valence of M, usually an integer of 3 to 7, preferably an integer of 4 to 6, more preferably 4 or 5, particularly preferably 4. is there. When n is 4 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. X will be described later.

In the general formula (I), Y represents an oxygen atom, a sulfur atom, a nitrogen atom having a bonding group —R ⁸ , or a phosphorus atom having a bonding group —R ⁸ , preferably an oxygen atom.

  In the said general formula (I), Q shows a carbon atom, a silicon atom, a germanium atom, and a tin atom, Preferably they are a carbon atom and a silicon atom, More preferably, it is a carbon atom.

In the general formula (I), R ^{1 to} R ³ may be the same or different from each other, and are a secondary alkyl group, a tertiary alkyl group, a cycloalkyl group, or an aryl group, and R ¹ And R ² may be linked together to form a ring, R ² and R ³ may be linked together to form a ring, and R ¹ and R ³ may be linked together to form a ring. It may be.

  Specific examples of the secondary alkyl group include branched alkyl groups having 3 to 30 carbon atoms, preferably 3 to 20 carbon atoms, such as isopropyl, isobutyl, and sec-butyl groups; And cyclic unsaturated hydrocarbon groups having 5 to 30 carbon atoms such as a dienyl group, an indenyl group, and a fluorenyl group.

  Specific examples of the tertiary alkyl group include branched alkyl groups having 4 to 30 carbon atoms, preferably 4 to 20 carbon atoms, such as a tert-butyl group and a tert-pentyl group. It is done.

  Specific examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cyclohexenyl group, an adamantyl group and the like having 3 to 30 carbon atoms, preferably a cyclic group having 3 to 20 carbon atoms. Saturated hydrocarbon group; and the like.

  Specifically, the aryl (Aryl) group has 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. Aryl group; tolyl group, iso-propylphenyl group, tert-butylphenyl group, dimethylphenyl group, di-iso-propylphenyl group, di-tert-butylphenyl group, 2,4,6-trimethylphenyl group, 2, And alkyl-substituted aryl groups such as 4,6-tri-iso-propylphenyl group and 2,4,6-tri-tert-butylphenyl group.

  In the secondary alkyl group, tertiary alkyl group, cycloalkyl group, and aryl group, a hydrogen atom present in the substituent may be substituted with another atom or substituent. For example, 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, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group There may be.

  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; 2-30 carbon atoms such as vinyl, allyl and isopropenyl groups, preferably 2 20 linear or branched alkenyl groups; linear or branched alkynyl groups having 2 to 30, preferably 2 to 20, more preferably 2 to 10 carbon atoms such as ethynyl and propargyl groups; The number of carbon atoms such as propyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, adamantyl group, etc. is 3-30, preferably 3-20, more preferably 3-1. A cyclic saturated hydrocarbon group of 0; a cyclic unsaturated hydrocarbon group having 5 to 30 carbon atoms such as a cyclopentadienyl group, an indenyl group, a fluorenyl group; a phenyl group, a naphthyl group, a biphenyl group, a terphenyl group, a phenanthryl group, An aryl group having 6-30 carbon atoms, preferably 6-20, more preferably 6-10, such as anthracenyl group; tolyl group, iso-propylphenyl group, t-butylphenyl group, dimethylphenyl group, di-t -An alkyl-substituted aryl group such as a butylphenyl group;

  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 a trimethylsilyl group, a triethylsilyl group, a triphenylsilyl group are particularly preferable. 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, the secondary alkyl group, the tertiary alkyl group, the cycloalkyl group, and the aryl (Aryl) group can be substituted with a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, or a boron-containing group as described above. A group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group or a tin-containing group can also be taken, and examples thereof include those similar to those exemplified in the description of the hydrocarbon group. .

Furthermore, two or more groups of R ^{1 to} R ^{3 in} the general formula (I), specifically, R ¹ and R ² , R ² and R ³ , R ¹ and R ³ are connected 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. Specific examples of the adjacent groups of R ^{1 to} R ³ linked to each other to form a ring include a triptycenyl group.

As R < ¹ > -R < ³ > of the said general formula (I), Preferably, it is an aryl (Aryl) group.

In the general formula (I), R ^{4 to} R ⁸ are hydrogen atom, halogen atom, hydrocarbon group, heterocyclic compound residue, oxygen-containing group, nitrogen-containing group, boron-containing group, sulfur-containing group, phosphorus-containing A group, a silicon-containing group, a germanium-containing group, or a tin-containing group, and two or more of R ^{4 to} R ⁸ may be linked to each other to form a ring.

In R ^{4 to} R ⁸ , 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, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, or the tin-containing groups, secondary alkyl groups as defined in the R ¹ to R ^3, tertiary alkyl group, a cycloalkyl group, a hydrogen atom present on the aryl (aryl) groups may be substituted Of halogen atoms, hydrocarbon groups, heterocyclic compound residues, oxygen-containing groups, nitrogen-containing groups, boron-containing groups, sulfur-containing groups, phosphorus-containing groups, silicon-containing groups, germanium-containing groups, or tin-containing groups. The thing similar to what was illustrated by description is mentioned.

As described above, two or more groups out of R ^{4 to} R ^{8 in} the general formula (I) may be linked to each other to form a ring. More specifically, two or more groups of R ^{4 to} R ⁸ , 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, or the like These rings may further have a substituent.

  In the general formula (I), X is 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, a phosphorus-containing group, or a silicon-containing group. Group, germanium-containing group, or tin-containing group.

In X, 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, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group About, the thing similar to what was illustrated by said R < ⁴ > -R < ⁸ > is mentioned.

  In the said general formula (I), L shows the neutral ligand containing the periodic table group 13-16 element. The group 13 to 16 of the periodic table is preferably boron, carbon, nitrogen, oxygen, aluminum, silicon, phosphorus or sulfur, and more preferably carbon, nitrogen, oxygen, sulfur or phosphorus.

  Examples of the neutral ligand L containing a carbon atom include carbon monoxide, dienes having 4 to 20 carbon atoms; aromatic hydrocarbons having 6 to 20 carbon atoms, and the like.

  Examples of the diene having 4 to 20 carbon atoms include dienes such as cyclopentadiene, cyclooctadiene and norbornadiene. Examples of the aromatic hydrocarbon having 6 to 20 carbon atoms include aromatic hydrocarbons such as benzene, naphthalene, and pyrene.

  Examples of the neutral ligand L containing an oxygen atom include water and ethers having 2 to 20 carbon atoms.

  Examples of the ether having 2 to 20 carbon atoms include aliphatic ethers such as dimethyl ether, dinonyl ether, and ethyl octyl ether, for example, alicyclic ethers such as tetrahydrofuran, 1,4-dioxane, and dicyclohexyl ether, Examples thereof include ethers having an aromatic ring such as dibenzyl ether, and aromatic ethers such as diphenyl ether and naphthylphenyl ether.

  Examples of the neutral ligand L having a nitrogen atom include, for example, nitrogen molecules, ammonia, tertiary amines having 3 to 20 carbon atoms, and 6 to 50 carbon atoms having 2 to 4 tertiary amino groups. Valent amines; aromatic amines having 5 to 30 carbon atoms and the like.

  Examples of the tertiary amine having 3 to 20 carbon atoms include aliphatic tertiary amines such as trimethylamine and diisopropylmethylamine, and alicyclic tertiary amines such as N-methylpiperidine, such as diethylbenzyl. And tertiary amines containing an aromatic ring such as amine. Examples of the polyvalent amine having 6 to 50 carbon atoms having 2 to 4 tertiary amino groups include tetramethylethylenediamine, N, N, N ′, N ″, N ″ -pentamethyldiethylenetriamine, N, N , N ′, N ′, N ″, N ″ -hexamethyltriethylenetetramine, N, N, N ′, N ′, N ″, N ″ -hexakis [(2-n-butoxycarbonyl) ethyl] triethylenetetramine Aliphatic polyamines such as alicyclic polyamines such as 1,2-dipiperidinoethane, for example, tertiary polyamines containing aromatic rings such as 1,4-dibenzylpiperidine And the like. Examples of the aromatic amine having 5 to 30 carbon atoms include pyridine, dipyridine, 2,2′-bipyridine, 2,2 ′-[4,4′-bis (5-nonyl)] bipyridine, quinoline, 1 , 10-phenanthroline and other aromatic amines.

  Examples of the neutral ligand L having a sulfur atom include thioethers having 2 to 20 carbon atoms; aromatic compounds containing a sulfur atom having 3 to 8 carbon atoms, and the like.

  Examples of the thioether having 2 to 20 carbon atoms include aliphatic thioethers such as dimethyl sulfide, alicyclic thioethers such as tetrahydrothiopyran, and thioethers containing an aromatic ring such as dibenzyl sulfide. Can be mentioned. Examples of the aromatic compound containing a sulfur atom having 3 to 8 carbon atoms include aromatic compounds containing a sulfur atom such as thiophene, thiazol, and thiaphthalene.

  Examples of the neutral ligand L having a phosphorus atom include phosphines having 3 to 30 carbon atoms. Examples of the phosphines having 3 to 30 carbon atoms include aliphatic phosphines such as triethylphosphine and tributoxyphosphine, alicyclic phosphines such as 1-ethylphosphinane, and aromatics such as triphenylphosphine. And phosphines containing a ring.

  In the said general formula (I), m represents the number of the neutral ligand L, and is an integer of 0 or 1-8.

  In the above general formula (I), D represents a hydrocarbon group or a heterocyclic compound residue which may have a substituent. The shortest number of bonds connecting Y and N is 4 to 6, preferably 5 or 6. In the formula, the bond connecting Y and N may be a double bond or a triple bond.

  The number of shortest bonds connecting Y and N can be counted as in the following (α) and (β), 5 in the case of (α) and 4 in the case of (β). It is.

  In the general formula (1), D is a group connecting N and Y, and it is preferable that Y, N, and D form a structure represented by the general formula (II).

In the general formula (II), Y is the same atom as that represented by the general formula (I), specifically, an oxygen atom, a sulfur atom, a nitrogen atom having a bonding group -R ⁶ , or It shows a phosphorus atom having a bonding group -R ^6.

In the general formula (II), R ^{9 to} R ¹² 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. -Containing group, sulfur-containing group, phosphorus-containing group, silicon-containing group, germanium-containing group, or tin-containing group, and when R ^{9 to} R ¹² are hydrocarbon groups, R ⁹ and R ¹⁰ are linked to each other May form a ring, and R ¹¹ and R ¹² may be linked to each other to form a ring. Further, when R ⁹ and R ¹⁰ are connected to each other to form a ring, or when R ¹¹ and R ¹² are connected to each other to form a ring, hydrogen bonded to the carbon atom forming the ring The atoms may be substituted with other atoms or substituents. For example, 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, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group There may be. For 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, or tin-containing group, The thing similar to what was illustrated by R < ⁴ > -R < ⁸ > is mentioned.

In R ^{9 to} R ¹² , 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, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, Or about a tin containing group, the thing similar to what was illustrated by said R < ⁴ > -R < ⁸ > is mentioned.

In the general formula (I), the structure of D is more preferably a structure selected from the group represented by the following general formula (III) among the structures represented by the general formula (II). In the structure represented by the general formula (III), the hydrogen atom may be substituted by the substituents represented by R ^{4 to} R ⁸ above. In the structure described in the general formula (III), the wavy line joined to the carbon-carbon double bond means a cis isomer or a trans isomer.

  Among these, the biphenyl structure described in the rightmost among the group represented by the general formula (III) is particularly preferable.

The transition metal compound (A) of the present invention is, as represented by the general formula (I), a monodentate coordination (for one metal) in which three atoms of Y, N, and Q coordinate with a central metal. 1 ligand), a specific structure as D, and ^three relatively bulky substituents as R ^{1 to} R ^{3 with} respect to Q .

As described above, the catalyst for olefin polymerization containing the transition metal compound (A) has heat resistance at high temperatures and high olefin polymerization activity. Further, when copolymerizing two or more olefins, copolymerization is performed. High nature. Although the reason for having such excellent properties is not clear, the present inventors assume the following matters.
(I) Since the transition metal compound (A) represented by the general formula (I) is a monodentate structure as described above and has a specific structure consisting of D, it is described in Patent Document 1. Compared with transition metal compounds having a salicylaldoimine ligand of bidentate coordination type (two ligands for one metal), a wide polymerization reaction field can be secured around the central metal Therefore, the copolymerization reaction is likely to proceed.
(Ii) Since a relatively bulky substituent composed of R ^{1 to} R ³ is arranged around the central metal, side reactions with the alkylaluminum compound during the polymerization reaction can be suppressed. Improves.

In addition, in producing the effect of the above-described invention in the present invention, the essential part is the structure of the monodentate coordination (one ligand per metal) in the general formula (I) as described above. Yes, D has a specific structure, and Q has ^three relatively bulky substituents as R ^{1 to} R ³ . On the other hand, the types of substituents of R ^{4 to} R ^{8 in} the general formula (I) and the types of X and Z are high or low in catalytic activity and copolymerizable when two or more olefins are copolymerized. Although it has some influence on the height, it is not an essential part. Therefore, as for R ^{4 to} R ⁸ , X, and Z, the effect of the present invention can be exhibited regardless of the substituents bonded to each other as long as they are atoms or substituents described above.

<Method for producing transition metal compound (A)>
The transition metal compound (A) represented by the general formula (I) can be produced by a known method. Specifically, it can be obtained by reacting a corresponding ligand compound and a transition metal-containing compound.

  The ligand compound can be obtained by reacting a salicylaldehyde compound having a desired substituent with a primary amine compound having a desired structure and substituent. The reaction proceeds in the solvent. As the solvent, a common one can be used, and among them, an alcohol solvent such as methanol and ethanol, or a hydrocarbon solvent such as toluene is preferable. Next, when the mixture is stirred at room temperature to reflux conditions for about 1 to 48 hours, the corresponding ligand is obtained in good yield. When synthesizing the ligand compound, an acid catalyst such as formic acid, acetic acid, and paratoluenesulfonic acid may be used as a catalyst. Further, when molecular sieves, anhydrous magnesium sulfate or anhydrous sodium sulfate is used as a dehydrating agent, or while dehydrating with Dean Stark, the reaction proceeds effectively.

  Next, by reacting the obtained ligand with a transition metal-containing compound, a corresponding transition metal compound can be synthesized. Specifically, the above ligand is dissolved in a solvent and, if necessary, contacted with a base to prepare a phenoxide salt, and then mixed with a metal halide, metal alkylate, etc. at low temperature as a transition metal-containing compound. The mixture is stirred for about 1 to 48 hours at -78 ° C to room temperature or under reflux conditions. As the solvent, those commonly used for such a reaction can be used, and among them, polar solvents such as ether and tetrahydrofuran (THF), hydrocarbon solvents such as toluene and the like are preferably used. Examples of the base used in preparing the phenoxide salt include lithium salts such as n-butyllithium, metal salts such as sodium salts such as sodium hydride, triethylamine, and pyridine. This is not the case. In addition, the solvent used for reaction of a ligand and a transition metal containing compound may become the neutral ligand L by liganding to the transition metal atom M at the time of transition metal compound (A) manufacture.

<Olefin polymerization catalyst>
The catalyst for olefin polymerization of the present invention contains the transition metal compound (A) represented by the general formula (I), and further includes (B) an organometallic compound (B-1) and an organoaluminum oxy compound (B-2). And at least one compound selected from the group consisting of a compound (B-3) that reacts with the transition metal compound (A) to form an ion pair. In the present specification, the olefin refers to a hydrocarbon having one carbon / carbon double bond in the molecule.

  As the transition metal compound (A) contained in the olefin polymerization catalyst of the present invention, the above-described transition metal compound (A) is used.

  Hereinafter, the compound (B) will be described in detail.

[Compound (B)]
The catalyst for olefin polymerization of the present invention comprises (B) an organometallic compound (B-1), an organoaluminum oxy compound (B-2), and a transition metal compound (A) in addition to the transition metal compound (A). It is preferable from the point of polymerization activity to further contain at least one compound selected from compounds (B-3) that react to form ion pairs. Hereinafter, the compounds (B-1), (B-2), and (B-3) will be described.

((B-1) Organometallic compound)
As the organometallic compound (B-1) 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 1 metal and aluminum, and a complex alkylated product of a group 1 metal and aluminum of the periodic table represented by formula (B-1c).

^{_{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, and examples of such a compound include an organoaluminum compound in which two or more aluminum compounds are bonded via a nitrogen atom. Specific examples of such a compound include (C ₂ H ₅ ) ₂ AlN (C ₂ H ₅ ) Al (C ₂ H ₅ ) ₂ .

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, examples of the organometallic compound (B-1) 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, such as a combination of an aluminum halide and an alkyl lithium, or a combination of an aluminum halide and an alkyl magnesium, is used as the organometallic compound (B-1). It can also be used as

  The organometallic compound (B-1) as described above is used singly or in combination of two or more.

((B-2) Organoaluminum oxy compound)
The organoaluminum oxy compound (B-2) 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 the organoaluminum oxy compound (B-2) include methylaluminoxane, ethylaluminoxane, and isobutylaluminoxane.

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 or different from each other, and have a hydrogen atom, a halogen atom, or a carbon atom number. 1-10 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. In particular, 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 above organoaluminum oxy compounds (B-2) 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) (hereinafter referred to as “ionized ionic compound”) that reacts with the transition metal compound (A) to form an ion pair, used in the present invention, JP-A-1-501950, Lewis described in JP-A-1-502036, JP-A-3-179005, JP-A-3-179006, JP-A-3-207703, JP-A-3-207704, USP-5321106, etc. Examples thereof include acids, ionic compounds, borane compounds and carborane compounds. 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 the 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 as or different from each other and are an organic group, preferably an aryl group or a substituted aryl group.

  Specific examples of the carbonium cation include trisubstituted carbonium cations such as triphenylcarbonium cation, tri (methylphenyl) carbonium cation, and tri (dimethylphenyl) carbonium cation.

  Specific examples of the ammonium cation include trialkylammonium 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, and particularly preferably a triphenylcarbonium cation, an N, N-dimethylanilinium cation, or an N, N-diethylanilinium cation.

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

  Specific examples of the trialkyl-substituted ammonium salt include 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, bis [tri (n-butyl) ammonium] decachlorodecaborate, bis [tri (n- Butyl) ammonium] dodecachlorododecaborate, and the like; tri (n-butyl) ammonium bis (dodecahydridododecaborate) cobaltate (III), bis [tri (n-butyl) ammonium] bis (dodecahydridododeca) Borate) Metals such as nickelate (III) Such as the salt of the run-anion, and the like.

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 above ionized ionic compounds (compound (B-3) which reacts with the transition metal compound (A) to form an ion pair) are used singly or in combination of two or more.

  In addition to the transition metal compound (A), when an organoaluminum oxy compound (B-2) such as methylaluminoxane as a co-catalyst component is used in combination, the olefin compound exhibits a very high polymerization activity.

  Moreover, the catalyst for olefin polymerization according to the present invention includes the transition metal compound (A), the organometallic compound (B-1), the organoaluminum oxy compound (B-2), and the ionized ionic compound (B-3). The following carrier (C) may be included as necessary together with at least one compound (B) selected from the group consisting of:

[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, Halloysite, etc.
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 , γ-Ti ( Examples thereof include crystalline acidic salts of polyvalent metals such as 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. Further, 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 contains the transition metal compound (A), preferably the compound (B), and optionally a carrier (C). 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 ² 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. As described above, in the present specification, olefin refers to a hydrocarbon having one carbon / carbon double bond in the molecule.

  In the olefin polymer production method of the present invention, olefin homopolymerization or olefin copolymerization is carried out in the presence of the olefin polymerization catalyst. 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 for using each component constituting the catalyst of the present invention in polymerization and the order of addition to the polymerization vessel 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. It may be polymerized, and a catalyst component may be further supported on the prepolymerized solid catalyst component.

  In the present invention, the polymerization can be carried out by either a liquid phase polymerization method such as solution polymerization or suspension polymerization or a gas phase polymerization method. Specific examples of the inert hydrocarbon medium used in the liquid phase polymerization method include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; cyclopentane, cyclohexane, and methylcyclopentane. Alicyclic hydrocarbons such as: 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.

  The organometallic compound (B-1) usually has a molar ratio [(B-1) / M] of the organometallic compound (B-1) 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. The organoaluminum oxy compound (B-2) is a molar ratio of the aluminum atom in the organoaluminum oxy compound (B-2) to 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. The compound that reacts with the transition metal compound (A) to form an ion pair (ionized ionic compound) (B-3) includes the ionized ionic compound (B-3) and the 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 an organometallic compound (B-1), 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 organoaluminum oxy compound (B-2), 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 an ionized ionic compound (B-3), 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., and more preferably 45 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 allowing hydrogen to be present in the polymerization system or 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 such an 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, For example, 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-eicosene;
Cyclic olefins having 3 to 30, preferably 3 to 20 carbon atoms, such as cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene, 2-methyl 1,4,5,8-dimethano- 1,2,3,4,4a, 5,8,8a-octahydronaphthalene and the like.

  The olefin polymerization catalyst of the present invention can also copolymerize olefins and other monomers. 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 tilamide (in the case where the unsaturated carboxylic acid is a dicarboxylic acid, it may be a monoamide or a diamide); maleic anhydride, itaconic anhydride, allyl succinic anhydride, Butenyl succinic anhydride, (2,7-octadien-1-yl) succinic anhydride, tetrahydrophthalic anhydride, bicyclo [2.2.1] -5-heptene-2,3-dicarboxylic anhydride Unsaturated carboxylic acid anhydrides such as vinyl acetate, vinyl propionate, vinyl caproate, vinyl caprate, vinyl laurate, vinyl stearate, vinyl trifluoroacetate, etc .; vinyl chloride, vinyl fluoride, Halogenated olefins such as vinyl bromide, vinyl iodide, allyl bromide, allyl chloride, allyl fluoride, allyl bromide Kind;
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; allyl alcohol, 3-butenol, 4 -Unsaturated alcohol compounds such as pentenol, 5-hexenol, 6-hebutenol, 7-octenol, 8-nonenol, 9-decenol, 10-undecenol, 11-dodecenol, 12-tridecenol, and their acetates, benzoates Unsaturated esters such as acid ester, propionic acid ester, caproic acid ester, capric acid ester, lauric acid ester and stearic acid ester; substituted phenols such as vinylphenol and allylphenol; methyl vinyl ether, ethyl vinyl ether, allyl methyl ether, Allyl Unsaturated ethers such as propyl ether, allyl butyl ether, allyl methallyl ether, methoxy styrene, ethoxy styrene, and allyl anisole; butadiene monoxide, 1,2-epoxy-7-octene, 3-vinyl-7-oxabicyclo [4.1 0.0] unsaturated epoxides such as heptane; unsaturated aldehydes such as acrolein and undecenal, and unsaturated acetals such as dimethyl acetal and diethyl acetal; methyl vinyl ketone, ethyl vinyl ketone, allyl methyl ketone, allyl ethyl Unsaturated ketones such as ketone, allyl propyl ketone, allyl butyl ketone and allyl benzyl ketone, and unsaturated acetals such as dimethyl acetal and diethyl acetal; allyl methyl sulfide, acetal Unsaturated thioethers such as ruphenyl 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; And unsaturated phosphine oxides such as allyl diphenylphosphine 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, ethylidenenorbornene, vinylnorbornene, dicyclopentadiene, divinylbenzene; 7-methyl-1,6- Examples include 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.

  As described above, the olefin polymerization catalyst of the present invention has a higher polymerization activity and a higher comonomer content than a transition metal compound having a salicylaldoimine ligand, which is suitable for commercial production at 60 ° C. or higher. A polymer can be produced.

  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, 270 MHz ¹ H NMR (JEOL GSH-270), was determined using the FD- Mass spectrometry (JEOL SX-102A) and the like.

  In this example, the intrinsic viscosity ([η]) was measured at 135 ° C. in decalin.

  Further, the comonomer content of the copolymer obtained in the examples was measured by IR (JASCO FT / IR-4200).

IR uses the film obtained by melt-stretching the copolymer obtained in the example with a hot press heated to 180 ° C. and then cooling under pressure at room temperature as a measurement sample, and the light source wavelength is 5000 cm ^−1. Measured between ˜400 cm ⁻¹ . The propylene content is C-CH3 skeletal vibration (1150 cm ⁻¹ ) based on propylene, with the key band absorbance (D1150) and internal standard band (4320 cm ⁻¹ : C—H stretching vibration and methylene / methyl bending vibration). ) And the absorbance (D4320) [D1150 / D4320]. The hexene content is determined by using C-CH ₃ skeletal vibration (1378 cm ⁻¹ ) based on hexene as a key band, absorbance of the key band (D1378) and internal standard band (4320 cm ⁻¹ : C—H stretching vibration, methylene and methyl deformation angle. It was determined by the ratio [D1378 / D4320] of the combined vibration sound) to the absorbance (D4320).
(1) Synthesis of ligand [Synthesis Example 1]
Charge a fully dry, nitrogen-substituted 300 mL reactor with 20.6 g (100 mmol) of 2,4-di-tert-butylphenol and 0.06 g (0.25 mmol) of pyridinium p-toluenesulfonate and add 100 mL of dichloromethane. Then, 14.0 mL (154 mmol) of 3,4-dihydro-2H-pyran was added. After stirring at room temperature for 5 hours, a saturated aqueous sodium hydrogen carbonate solution was added to quench the reaction. The organic phase was separated, and the obtained fraction was dried over anhydrous magnesium sulfate. After filtering the magnesium sulfate, the filtrate was distilled off to obtain the target product represented by the following formula (1) (hereinafter referred to as compound (1)) almost quantitatively.
¹ H NMR (270 MHz, CDCl ₃ ) d 7.33 (1H, d, J = 2.3 Hz, Ar—H), 7.19-7.07 (2H, m, Ar—H), 5.46 (1H , t, J = 2.9Hz, -OCHO -), 3.91 (1H, dt, J = 11.1and3.1Hz, -OCH 2 CH 2 -), 3.70-3.59 (1H, m, _{-OCH 2 CH 2 -), 2.16-1.58} (6H, m, -CH 2 (CH 2) 3 CH -), 1.43 (9H, s, Ar-C (CH 3) 3), _{1.30 (9H, s, Ar-} C (CH 3) 3) ppm

[Synthesis Example 2]
In a fully dry, nitrogen-substituted 500 mL reactor, 29.0 g (100 mmol) of the compound (1) obtained in Synthesis Example 1 and 200 mL of tetrahydrofuran were charged, and 76.0 mL of n-butyllithium solution (hexane solution, 1. 57M, 119 mmol) was added. After stirring at room temperature for 2 hours, the mixture was cooled to −78 ° C., and 17.0 mL (153 mmol) of trimethoxyborane was added dropwise over 10 minutes. After stirring overnight while raising the temperature to room temperature, 13.8 g (80.0 mmol) of 2-bromoaniline, 0.19 g (0.83 mmol) of palladium acetate, 42.6 g of tripotassium phosphate (K ₃ PO ₄ ) ( 200 mmol), 2-dicyclohexylphosphino-2 ′, 6′-dimethoxybiphenyl 0.52 g (1.25 mmol) and distilled water 40 mL were charged, and the mixture was heated to reflux for 7 hours in an oil bath. Furthermore, 0.85 g (1.25 mmol) of [1,3-bis (2,6-diisopropylphenyl) imidazol-2-ylidene] (3-chloropyridyl) palladium (II) dichloride was added, and the mixture was placed in an oil bath for 7 hours. Heated to reflux. After cooling the reaction solution to room temperature, the soluble component was extracted with ethyl acetate, and the obtained fraction was washed with saturated brine and dried over anhydrous magnesium sulfate. After filtering the magnesium sulfate, the residue obtained by distilling off the filtrate was purified by silica gel column chromatography. As a result, 25.9 g of the desired product represented by the following formula (2) (hereinafter referred to as compound (2)) was obtained. Yield 85%).
¹ H NMR (270 MHz, CDCl ₃ ) d 7.37 (1H, t, J = 0.7 Hz, Ar—H), 7.26-7.00 (3H, m, Ar—H), 6.87-6 .67 (2H, m, Ar- H), 4.56-4.40 (1H, m, -OCHO -), 3.86-3.66 (3H, br-m, -NH 2 and-OCH 2 _{CH 2 -), 3.15-2.95 (1H} , m, -OCH 2 CH 2 -), 1.73-1.00 (6H, m, -CH 2 (CH 2) 3 CH -), 1 .48 (9H, d, J = 0.4 Hz, −C (CH ₃ ) ₃ ), 1.30 (9H, d, J = 0.2 Hz, Ar—C (CH ₃ ) ₃ ) ppm

[Synthesis Example 3]
Into a 500 mL reactor thoroughly dried and purged with nitrogen, charge 25.9 g (68.0 mmol) of the compound (2) obtained in Synthesis Example 2, 40 mL of dichloromethane and 40 mL of methanol, and add 70 mL of dilute hydrochloric acid (3M, 210 mmol). It was. After stirring at room temperature for 3 hours, a saturated aqueous sodium hydrogen carbonate solution was added to quench the reaction. The soluble component was extracted with dichloromethane, and the obtained fraction was dried over anhydrous magnesium sulfate. After filtering the magnesium sulfate, the residue obtained by distilling off the filtrate was purified by silica gel column chromatography, whereby the desired product (hereinafter referred to as compound (3)) represented by the following formula (3) was obtained. 0.9 g (yield 95%) was obtained.
¹ H NMR (270 MHz, CDCl ₃ ) d 7.36 (1H, d, J = 2.7 Hz, Ar—H), 7.19-7.25 (2H, m, Ar—H), 7.13 (1H , D, J = 2.7 Hz, Ar-H), 6.82-6.96 (2H, m, Ar-H), 6.52 (1H, s, Ar-OH), 3.75 (2H, _{s, Ar-NH 2),} 1.46 (9H, s, -C (CH 3) 3), 1.32 (9H, s, -C (CH 3) 3) ppm

[Synthesis Example 4]
A 300 mL reactor thoroughly dried and purged with nitrogen was charged with 1.80 g (60 wt%, 45.0 mmol) of sodium hydride (oil), 20 mL of diethyl ether was added, and m-cresol 15. 0 mL (144 mmol) was added dropwise with a syringe. After dropwise addition, diethyl ether was distilled off under reduced pressure, 8.37 g (30.0 mmol) of triphenylchloromethane was added, and the mixture was heated at 150 ° C. for 3 hours. After the reaction solution was cooled to room temperature, it was diluted with 100 mL of diethyl ether, and 100 mL (1.00 M, 0.10 mmol) of aqueous sodium hydroxide solution was added to quench the reaction. The soluble component was extracted with diethyl ether, and the obtained fraction was dried over anhydrous magnesium sulfate. After filtering the magnesium sulfate, the residue obtained by distilling off the filtrate was purified by silica gel column chromatography, whereby the desired product (hereinafter referred to as compound (4)) represented by the following formula (4) was converted to 4 .05 g (yield 38%) was obtained.
¹ H NMR (270 MHz, CDCl ₃ ) d 7.32-7.15 (16H, m, Ar—H), 6.93 (1H, dd, J = 6.3 and 2.3 Hz, Ar—H), 6.66 (1H, d, J = 6.7Hz , Ar-H), 4.43 (1H, s, -OH), 2.29 (3H, s, -CH 3) ppm

[Synthesis Example 5]
Into a 200 mL reactor sufficiently dried and purged with nitrogen, 3.96 g (11.3 mmol) of the compound (4) obtained in Synthesis Example 4 and 25 mL of tetrahydrofuran were charged and stirred under ice cooling. 4.15 mL of ethyl magnesium bromide (diethyl ether solution, 3M, 12.5 mmol) was added dropwise over 30 minutes. After stirring at room temperature for 2 hours, 0.86 g (28.8 mmol) of paraformaldehyde and 2.40 mL (17.2 mmol) of triethylamine were added, and the mixture was heated to reflux at 80 ° C. for 2 hours. After cooling the reaction solution to room temperature, the reaction solution was neutralized with 150 mL of 18% hydrochloric acid. The organic phase was separated, washed with saturated brine, and dried over anhydrous magnesium sulfate. After filtering the magnesium sulfate, the residue obtained by distilling off the filtrate was purified by silica gel column chromatography. As a result, 4.20 g of the desired product represented by the following formula (5) (hereinafter referred to as compound (5)) was obtained. (Yield 98%) was obtained.
¹ H NMR (270 MHz, CDCl ₃ ) d12.24 (1H, s, —OH), 10.23 (1H, s, —CHO), 7.37 (1H, d, J = 8.0 Hz, Ar—H) ), 7.26-7.13 (15H, m, Ar-H), 6.64 (1H, dd, J = 7.9 and 0.8 Hz, Ar-H), 2.56 (3H, s, -CH) ₃ ) ppm

[Synthesis Example 6]
In a 100 mL reactor thoroughly dried and purged with nitrogen, 0.94 g (3.16 mmol) of the compound (3) obtained in Synthesis Example 3 and 1.13 g of the compound (12) obtained in Synthesis Example 12 (2. 99 mmol), a small amount of p-toluenesulfonic acid and 15 mL of toluene were charged, and the mixture was stirred for 2 hours under reflux with heating. When the residue obtained by distilling off the solvent was purified by silica gel column chromatography, 1.62 g (yield 82%) of the desired product represented by the following formula (6) (hereinafter referred to as compound (6)) was obtained. It was.
¹ H NMR (270 MHz, CDCl ₃ ) d 13.4 (1H, s, —OH), 8.44 (1H, s, —CH═N—), 7.42-7.07 (21H, m, Ar— H), 6.99 (1H, d, J = 2.4 Hz, Ar-H), 6.47 (1H, d, J = 8.1 Hz, Ar-H), 4.81 (1H, s,- _{OH), 1.98 (3H, s} , -CH 3), 1.24 (18H, s, -C (CH 3) 3) ppm

[Synthesis Example 7]
In a 100 mL reactor thoroughly dried and purged with nitrogen, 0.76 g (2.56 mmol) of compound (3) obtained in Synthesis Example 3, 0.48 g (2.58 mmol) of 3-t-butylsalicylaldehyde, a small amount P-toluenesulfonic acid and toluene (20 mL) were added, and the mixture was stirred for 13 hours under reflux with heating. The reaction solution was washed with a saturated aqueous sodium hydrogen carbonate solution and then dried over anhydrous magnesium sulfate. By filtering the desiccant and distilling off the filtrate, 0.97 g (yield 83%) of the desired product represented by the following formula (7) (hereinafter referred to as compound (7)) was obtained.
¹ H NMR (270 MHz, CDCl ₃ ): 11.8 (1H, s, —OH), 8.69 (1H, s, —C═NH—), 7.71-6.80 (9H, m, Ar) -H), 5.02 (1H, s , -OH), 1.47 (9H, s, -C (CH 3) 3), 1.41 (9H, s, -C (CH 3) 3), _{1.27 (9H, s, -C (} CH 3) 3) ppm
FD-mass spectrometry (M ⁺ ): 457

[Synthesis Example 8]
In a 50 mL reactor sufficiently dried and purged with nitrogen, 1.15 g (3.87 mmol) of the compound (3) obtained in Synthesis Example 3 and 0.70 g (3.87 mmol) of 3-cumyl-5-methylsalicylaldehyde were obtained. A small amount of p-toluenesulfonic acid and 20 mL of toluene were charged, and the mixture was stirred for 3 hours under reflux with heating. The reaction solution was cooled to room temperature, neutralized with a saturated aqueous sodium hydrogen carbonate solution, and dried over anhydrous magnesium sulfate. After filtering the magnesium sulfate, the filtrate was distilled off to obtain 1.94 g (yield 94%) of the desired product (hereinafter referred to as compound (8)) represented by the following formula (8).
¹ H NMR (270 MHz, CDCl ₃ ): 11.8 (1H, s, —OH), 8.30 (1H, s, —C═NH—), 7.43-7.10 (11H, m, Ar -H), 6.92 (2H, d , J = 2.7Hz, Ar-H), 5.00 (1H, s, -OH), 2.29 (3H, s, Ar-CH 3), 1 .65 (6H, s, C—CH ₃ ), 1.33 (9 H, s, —C (CH ₃ ) ₃ ), 1.23 (9H, s, —C (CH ₃ ) ₃ ) ppm
FD-mass spectrometry (M ⁺ ): 533

[Synthesis Example 9]
In a 50 mL reactor sufficiently dried and purged with nitrogen, 0.50 g (1.68 mmol) of the compound (3) obtained in Synthesis Example 3 and 0.51 g (1) of 3- (1,1-diphenylethyl) salicylaldehyde were obtained. .68 mmol), a small amount of p-toluenesulfonic acid and 10 mL of toluene were added, and the mixture was stirred for 4 hours under reflux with heating. The reaction solution was cooled to room temperature, neutralized with a saturated aqueous sodium hydrogen carbonate solution, and dried over anhydrous magnesium sulfate. After filtering the magnesium sulfate, the filtrate was distilled off to obtain 0.89 g (yield 91%) of the desired product represented by the following formula (9) (hereinafter referred to as compound (9)).
¹ H NMR (270 MHz, CDCl ₃ ): 12.6 (1H, s, —OH), 8.37 (1H, s, —C═NH—), 7.47-7.04 (16H, m, Ar) -H), 6.94 (1H, d, J = 2.7 Hz, Ar-H), 6.68-6.62 (2H, m, Ar-H), 4.89 (1H, s, -OH) _{), 2.25 (3H, s,} C-CH 3), 1.29 (9H, s, -C (CH 3) 3), 1.21 (9H, s, -C (CH 3) 3) ppm

(2) Synthesis of transition metal compound [Example 1]
In a 100 mL reactor sufficiently dried and purged with argon, 0.33 g (0.50 mmol) of the compound (6) obtained in Synthesis Example 6 and 15 mL of a toluene solution were charged and stirred. This solution was cooled to −78 ° C., and 0.50 mL (1.00 M, 0.50 mmol) of a toluene solution of titanium tetrachloride was added dropwise. After completion of the dropwise addition, stirring was continued for 22 hours while slowly returning to room temperature. After the solvent of the reaction solution was distilled off, 30 mL of n-hexane was added to the obtained solid, and ultrasonic waves were applied to adjust the suspension. Insoluble matter was filtered off with a glass filter, and the residue was dried under reduced pressure to obtain 0.35 g (yield 89%) of a brown powder compound represented by the following formula (A) (hereinafter referred to as titanium compound (A)). .
¹ H NMR (270 MHz, CDCl ₃ ) d 8.65 (1H, s, —CH═N—), 7.58 (1H, d, J = 8.0 Hz, Ar—H), 7.49-7.42 (2H, m, Ar-H), 7.38-7.07 (18H, m, Ar-H), 699-6.89 (2H, m, Ar-H), 2.51 (3H, _{s, -CH 3), 1.29 (} 9H, s, -C (CH 3) 3), 1.25 (9H, s, -C (CH 3) 3) ppm
FD-mass spectrometry (M ⁺ ): 773

[Example 2]
In a 100 mL reactor sufficiently dried and purged with nitrogen, 0.33 g (0.50 mmol) of the compound (6) obtained in Synthesis Example 6 and 10 mL of tetrahydrofuran were charged. The solution was cooled to −78 ° C. and 0.63 mL of n-butyllithium solution (hexane solution, 1.59 M, 1.00 mmol) was added. After stirring at room temperature for 2 hours, the mixture was cooled to −78 ° C., 0.19 g (0.51 mmol) of tetrachlorobis (tetrahydrofuran) zirconium was added, and stirring was continued for 17 hours while slowly returning to room temperature. After distilling off the solvent of the reaction solution, 5 mL of dichloromethane was added to the obtained solid, and the suspension was adjusted by irradiating ultrasonic waves, and insoluble matters were removed with Celite on a glass filter. After distilling off the solvent of the obtained solution, 10 mL of n-hexane was added to the obtained solid, and the suspension was adjusted by irradiating with ultrasonic waves, and the insoluble matter was separated by filtration with a glass filter. Was dried under reduced pressure to obtain 0.31 g (yield 69%) of a yellow powder compound represented by the following formula (B) (hereinafter referred to as zirconium compound (B)).
¹ H NMR (270 MHz, CDCl ₃ ): 8.42 (1H, s, —CH═N—), 7.52 to 7.07 (21H, m, Ar—H), 7.03 (1H, d, J = 2.5 Hz, Ar—H), 6.69 (1H, d, J = 8.1 Hz, Ar—H), 3.75 (4H, brs, THF), 2.38 (3H, s, − _{CH 3), 1.57 (4H,} brs, THF), 1.27 (9H, s, -C (CH 3) 3), 1.12 (9H, s, -C (CH 3) 3) ppm
FD-mass spectrometry (M-THF ⁺ ): 817

Example 3
In a 100 mL reactor sufficiently dried and purged with nitrogen, 0.33 g (0.50 mmol) of the compound (6) obtained in Synthesis Example 6 and 10 mL of tetrahydrofuran were charged. The solution was cooled to −78 ° C. and 0.63 mL of n-butyllithium solution (hexane solution, 1.59 M, 1.00 mmol) was added. After stirring at room temperature for 2 hours, the mixture was cooled to −78 ° C., 0.17 g (0.52 mmol) of tetrachlorohanium was added, and stirring was continued for 14 hours while slowly returning to room temperature. After distilling off the solvent of the reaction solution, 5 mL of dichloromethane was added to the obtained solid, and the suspension was adjusted by irradiating ultrasonic waves, and insoluble matters were removed with Celite on a glass filter. After distilling off the solvent of the obtained solution, 10 mL of n-hexane was added to the obtained solid, and the suspension was adjusted by irradiating with ultrasonic waves, and the insoluble matter was separated by filtration with a glass filter. Was dried under reduced pressure to obtain 0.38 g (yield 74%) of a yellow powdered compound represented by the following formula (C) (hereinafter referred to as hafnium compound (C)).
¹ H NMR (270 MHz, CDCl ₃ ): 8.47 (1H, s, —CH═N—), 7.49 (1H, d, J = 8.0 Hz, Ar—H), 7.46-7. 35 (3H, m, Ar-H), 7.35-7.16 (17H, m, Ar-H), 7.16-7.06 (3H, m, Ar-H), 7.03 (1H , D, J = 2.6 Hz, Ar—H), 6.66 (1H, d, J = 8.4 Hz, Ar—H), 3.77 (4H, brs, THF), 2.37 (3H, _{s, -CH 3), 1.58 (} 4H, brs, THF), 1.27 (9H, s, -C (CH 3) 3), 1.11 (9H, s, -C (CH 3) 3 ) Ppm
FD-mass spectrometry (M-THF ⁺ ): 905

[Comparative Example 1]
In a 100 mL reactor sufficiently dried and purged with nitrogen, 1.21 g (2.13 mmol) of the compound (7) obtained in Synthesis Example 7 and 25 mL of a toluene solution were charged and stirred. This solution was added dropwise to 25 mL of a toluene solution containing 1.21 mL (1.00 M, 1.21 mmol) of a titanium tetrachloride toluene solution cooled to −78 ° C. After completion of dropping, stirring was continued for 15 hours while slowly returning to room temperature.

  After distilling off the solvent of the reaction solution, 20 mL of n-hexane was added to the obtained solid to prepare a suspension. Insoluble matter was filtered off with a glass filter, and the residue was dried under reduced pressure to obtain 0.78 g (yield: 64%) of an orange powder compound represented by the following formula (D) (hereinafter referred to as titanium compound (D)). .

¹ H NMR (270 MHz, CDCl ₃ ): 8.39 (1H, s, —C═NH—), 7.66 (1H, dd, J = 7.6 and 1.7 Hz, Ar—H), 7.54- 7.37 (4H, m, Ar-H), 7.31-7.25 (1H, m, Ar-H), 7.17-7.03 (3H, Ar-H), 1.41 (9H _{, s, -C (CH 3)} 3), 1.30 (9H, s, -C (CH 3) 3) ppm
FD-mass spectrometry (M ⁺ ): 574

[Comparative Example 2]
In a 50 mL reactor sufficiently dried and purged with nitrogen, 0.47 g (0.87 mmol) of the compound (8) obtained in Synthesis Example 8 and 7.5 mL of a toluene solution were charged and stirred. This solution was added dropwise to 7.5 mL of a toluene solution containing 0.89 mL (1.00 M, 0.89 mmol) of a titanium tetrachloride toluene solution cooled to −78 ° C. After completion of dropping, stirring was continued for 18 hours while slowly returning to room temperature.

After distilling off the solvent of the reaction solution, the obtained solid was washed with hexane, and the residue was dried under reduced pressure to obtain an orange powder compound (hereinafter referred to as titanium compound (E)) represented by the following formula (E). Obtained .42 g (74% yield).
¹ H NMR (270 MHz, CDCl ₃ ): 8.26 (1H, s, —C═NH—), 7.47-7.19 (11H, m, Ar—H), 7.11 (1H, d, J = 2.7Hz, Ar-H) , 6.99-6.96 (1H, m, Ar-H), 2.36 (3H, s, Ar-CH 3), 1.83 (3H, s, _{C-CH 3), 1.81 (} 3H, s, C-CH 3) 1.34 (9H, s, -C (CH 3) 3), 1.29 (9H, s, -C (CH 3) ₃ ) ppm
FD-mass spectrometry (M ⁺ ): 649

[Comparative Example 3]
In a 50 mL reactor sufficiently dried and purged with nitrogen, 0.42 g (0.73 mmol) of the compound (9) obtained in Synthesis Example 9 and 7.5 mL of a toluene solution were charged and stirred. This solution was added dropwise to 7.5 mL of a toluene solution containing 0.76 mL (1.00 M, 0.76 mmol) of a titanium tetrachloride toluene solution cooled to −78 ° C. After completion of dropping, stirring was continued for 16 hours while slowly returning to room temperature.

After distilling off the solvent of the reaction solution, the obtained solid was washed with hexane, and the residue was dried under reduced pressure to obtain an orange powder compound (hereinafter referred to as titanium compound (F)) represented by the following formula (F). Obtained .41 g (yield 81%).
¹ H NMR (270 MHz, CDCl ₃ ): 8.38 (1H, s, —C═NH—), 7.48-6.98 (19H, m, Ar—H), 2.48 (3H, s, _{C-CH 3), 1.35 (} 9H, s, -C (CH 3) 3), 1.30 (9H, s, -C (CH 3) 3) ppm
FD-mass spectrometry (M ⁺ ): 697

[Comparative Example 4]
In a 30 mL reactor sufficiently dried and purged with nitrogen, 0.20 g (0.67 mmol) of the compound (3) obtained in Synthesis Example 3 and 0.18 g of 3-adamantyl-2-hydroxy-5-methylbenzaldehyde bi ( 0.67 mmol), a small amount of p-toluenesulfonic acid, and 5 mL of toluene were added, and the mixture was stirred for 2 hours while heating under reflux. The reaction solution was washed with a saturated aqueous sodium hydrogen carbonate solution and then dried over anhydrous magnesium sulfate. The desiccant was filtered and the filtrate was distilled off to obtain 0.31 g of a yellow solid (a). (A) 0.13 g was dissolved in 5 mL of toluene and added dropwise to 5 mL of a toluene solution containing 0.24 mL (1.00 M, 0.24 mmol) of titanium tetrachloride toluene solution cooled to −78 ° C. After dropping, stirring was continued for 15 hours while slowly returning to room temperature. After distilling off the solvent of the reaction solution, the obtained solid was washed with hexane, and the residue was dried under reduced pressure to obtain an orange powder compound (hereinafter referred to as titanium compound (G)) represented by the following formula (G). .14 g (yield 86% based on titanium tetrachloride) was obtained.
¹ H NMR (270 MHz, CDCl ₃ ): 8.32 (1H, s, —C═NH—), 7.51 to 7.38 (4H, m, Ar—H), 7.28 (1H, d, J = 2.7 Hz, Ar-H), 7.16 (1H, brs, Ar-H), 7.13 (1H, d, J = 2.7 Hz, Ar-H), 7.07-7.04 _{(1H, m, Ar-H} ), 2.35 (3H, s, -CH 3), 2.16-1.77 (15H, m, Ad) 1.44 (9H, s, -C (CH 3 _{) 3), 1.30 (9H,} s, -C (CH 3) 3) ppm

[Comparative Example 5]
A 100 mL reactor that had been thoroughly dried and purged with nitrogen was charged with 23 mg (60 wt%, 0.58 mmol) of sodium hydride and 2 mL of diethyl ether. Under ice cooling, a solution prepared by dissolving 0.23 g (0.50 mmol) of the compound (7) obtained in Synthesis Example 7 in 3 mL of diethyl ether was added with a syringe, and the mixture was stirred at room temperature for 30 minutes. This solution was added dropwise to 5 mL of a diethyl ether solution containing 0.18 g (0.48 mmol) of tetrachlorobis (tetrahydrofuran) zirconium cooled to -78 ° C. After dropping, stirring was continued for 16 hours while slowly returning to room temperature. After distilling off the solvent of the reaction solution, 5 mL of dichloromethane was added to the obtained solid, and the suspension was adjusted by irradiating ultrasonic waves, and insoluble matters were removed with Celite on a glass filter. After the solvent of the obtained solution was distilled off, 7 mL of n-hexane was added to the obtained solid, and the suspension was adjusted by irradiating with ultrasonic waves. Insoluble matter was filtered off with a glass filter, and the residue was dried under reduced pressure to obtain 0.24 g (yield 71%) of a yellow powder compound represented by the following formula (H) (hereinafter referred to as zirconium compound (H)). .
¹ H NMR (270 MHz, CDCl ₃ ) d 8.08 (1H, s, —C═NH—), 7.54 (1 H, dd, J = 7.7 and 1.7 Hz, Ar—H), 7.49-7 .42 (3H, m, Ar-H), 7.32-7.23 (2H, m, Ar-H), 7.19 (1H, dd, J = 7.7 and 1.7 Hz, Ar-H), 7.08 (1H, d, J = 2.6 Hz, Ar-H), 6.87 (1H, t, J = 7.7 Hz, Ar-H), 4.01 (2H, brs, THF), 3 .94 (2H, brs, THF) , 1.63 (4H, brs, THF), 1.49 (9H, s, -C (CH 3) 3), 1.43 (9H, s, -C (CH _{3) 3), 1.30 (9H} , s, -C (CH 3) 3) ppm
FD-mass spectrometry (M-THF ⁺ ): 617

[Comparative Example 6]
A 30 mL reactor that had been thoroughly dried and purged with nitrogen was charged with 35 mg (60 wt%, 0.88 mmol) of sodium hydride and 3 mL of diethyl ether and cooled to 0 ° C. Under ice cooling, a solution prepared by dissolving 0.19 g (0.35 mmol) of the compound (8) obtained in Synthesis Example 8 in 3 mL of diethyl ether was added with a syringe, and the mixture was stirred at room temperature for 1 hour. This solution was added dropwise to 3 mL of a diethyl ether solution containing 131 mg (0.35 mmol) of tetrachlorobis (tetrahydrofuran) zirconium cooled to -78 ° C. After dropping, stirring was continued for 15 hours while slowly returning to room temperature. After the solvent of the reaction solution was distilled off, n-hexane was added to the obtained solid and stirred, and after standing, the supernatant solution was removed. Celite filtration was performed using toluene, and the resulting solution was dried under reduced pressure to obtain 0.14 g (yield) of a pale yellow powder compound represented by the following formula (I) (hereinafter referred to as zirconium compound (I)). 54%).

¹ H NMR (270 MHz, CDCl ₃ ): 7.96 (1H, s, —C═NH—), 7.40 (2H, m, Ar—H), 7.30-7.16 (9H, m, Ar-H), 7.05 (1H, d, J = 2.7 Hz, Ar-H), 6.98 (1H, s, Ar-H), 3.85 (brs, 4H, THF), 2. _{26 (3H, s, -CH 3} ), 1.84 (3H, s, -CH 3), 1.76 (3H, s, -CH 3), 1.56 (4H, brs, THF), 1. _{35 (9H, s, -C (} CH 3) 3), 1.29 (9H, s, -C (CH 3) 3) ppm
FD-mass spectrometry (M ⁺ ): 691

[Comparative Example 7]
A 30 mL reactor that had been thoroughly dried and purged with nitrogen was charged with 35 mg (60 wt%, 0.88 mmol) of sodium hydride and 5 mL of diethyl ether and cooled to 0 ° C. Under ice-cooling, a solution prepared by dissolving 0.19 g of the compound (a) obtained in Comparative Example 4 in 5 mL of diethyl ether was added with a syringe and stirred at room temperature for 1 hour. This solution was added dropwise to 5 mL of a diethyl ether solution containing 133 mg (0.35 mmol) of tetrachlorobis (tetrahydrofuran) zirconium cooled to -78 ° C. After dropping, stirring was continued for 15 hours while slowly returning to room temperature. After the solvent of the reaction solution was distilled off, n-hexane was added to the obtained solid and stirred, and after standing, the supernatant solution was removed. Celite filtration was performed using toluene, and the resulting solution was dried under reduced pressure, whereby 0.062 g (yield) of a pale yellow powder compound represented by the following formula (J) (hereinafter referred to as zirconium compound (J)). 22%).

¹ H NMR (270 MHz, CDCl ₃ ): 8.03 (1H, s, —C═NH—), 7.45 (3H, m, Ar—H), 7.28 (2H, t, J = 2. 7 Hz, Ar-H), 7.24 (1H, br, Ar-H), 7.07 (1H, d, J = 2.7 Hz, Ar-H), 6.96 (1H, br, Ar-H) _{), 3.96 (4H, br,} THF), 2.26 (3H, s, -CH 3), 2.18 (4H, br, THF), 2.11-1.62 (15H, brm, Ad _{) 1.44 (9H, s, -C} (CH 3) 3), 1.29 (9H, s, -C (CH 3) 3) ppm
FD-mass spectrometry (M ⁺ ): 707

[Comparative Example 8]
A 100 mL reactor thoroughly dried and purged with nitrogen was charged with 26 mg (60 wt%, 0.64 mmol) of sodium hydride and 2 mL of tetrahydrofuran. Under ice cooling, a solution prepared by dissolving 0.23 g (0.50 mmol) of the compound (7) obtained in Synthesis Example 7 in 3 mL of tetrahydrofuran was added with a syringe, and the mixture was stirred at room temperature for 3 hours. This solution was added dropwise to 5 mL of a tetrahydrofuran solution containing 0.16 g (0.50 mmol) of tetrachlorohanium cooled to -78 ° C. After the dropping, stirring was continued for 19 hours while slowly returning to room temperature. After distilling off the solvent of the reaction solution, 5 mL of dichloromethane was added to the obtained solid, and the suspension was adjusted by irradiating ultrasonic waves, and insoluble matters were removed with Celite on a glass filter. After the solvent of the obtained solution was distilled off, 10 mL of n-hexane was added to the obtained solid, and the suspension was adjusted by irradiating with ultrasonic waves. Insoluble matter was filtered off with a glass filter, and the residue was dried under reduced pressure to obtain 0.29 g (yield 75%) of an amber powder compound represented by the following formula (K) (hereinafter referred to as hafnium compound (K)). It was.
¹ H NMR (270 MHz, CDCl ₃ ) d 8.12 (1H, s, —C═NH—), 7.56 (1 H, dd, J = 7.7 and 1.6 Hz, Ar—H), 7.50-7 .40 (4H, m, Ar-H), 7.33 (1H, d, J = 2.6 Hz, Ar-H), 7.18 (1H, dd, J = 7.7 and 1.6 Hz, Ar-H) ), 7.08 (1H, d, J = 2.6 Hz, Ar-H), 6.84 (1H, t, J = 7.6 Hz, Ar-H), 4.05 (2H, brs, THF) , 3.93 (2H, brs, THF ), 1.62 (2H, brs, THF), 1.48 (9H, s, -C (CH 3) 3), 1.44 (9H, s, -C _{(CH 3) 3), 1.32} (2H, brs, THF), 1.30 (9H, s, -C (CH 3) 3) ppm
FD-mass spectrometry (M-THF ⁺ ): 705

(3) Production method of olefin polymer [Example 4]
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 100 liter / hr of ethylene. Thereafter, 0.20 mmol of methylaluminoxane (MAO) in terms of aluminum atom was added, and then 0.005 mmol of the titanium compound (A) obtained in Example 1 was added to initiate polymerization.

  Ethylene was continuously supplied at 100 liters / hr, polymerization was performed at 75 ° C. for 5 minutes under normal pressure, and then 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 0.12 g of polyethylene. The polymerization activity was 3450 g / mmol-Ti · hr, and the intrinsic viscosity [η] of the obtained polyethylene was 5.74 dL / g.

Example 5
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 100 liter / hr of ethylene. Thereafter, triisobutylaluminum (TIBA) was 0.125 mmol, followed by 0.001 mmol of the titanium compound (A) obtained in Example 1, and 0.001 mmol of triphenylcarbenium tetrakis (pentafluorophenyl) borate (TrB). In addition, polymerization was started.

  Ethylene was continuously supplied at 100 liters / hr, polymerization was performed at 25 ° C. for 5 minutes under normal pressure, and then 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 0.47 g of polyethylene. The polymerization activity was 13980 g / mmol-Ti · hr, and the intrinsic viscosity [η] of the obtained polyethylene was 7.21 dL / g.

[Examples 6 to 13]
Using the compounds shown in Tables 1 to 3, ethylene polymerization was carried out in the same manner as in Example 5 except that the polymerization conditions were changed as shown in Tables 1 to 3. The results are shown in Tables 1 to 3.

[Comparative Example 9]
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 100 liter / hr of ethylene. Thereafter, 1.25 mmol of methylaluminoxane (MAO) in terms of aluminum atom was added, and subsequently 0.005 mmol of the titanium compound (D) obtained in Comparative Example 1 was added to initiate polymerization.

  Ethylene was continuously supplied at 100 liters / hr, polymerization was performed at 25 ° C. under normal pressure for 10 minutes, and then 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 0.12 g of polyethylene. The polymerization activity was 140 g / mmol-Ti · hr, and the intrinsic viscosity [η] of the obtained polyethylene was 3.14 dL / g.

[Comparative Examples 10-14]
Using the compounds shown in Table 1, ethylene polymerization was carried out in the same manner as in Comparative Example 9 except that the polymerization conditions were changed as shown in Table 1. The results are shown in Table 1.

[Comparative Example 15]
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 100 liter / hr of ethylene. Thereafter, triisobutylaluminum (TIBA) was 0.125 mmol, subsequently, the titanium compound (D) obtained in Comparative Example 1 was 0.0025 mmol, and triphenylcarbenium tetrakis (pentafluorophenyl) borate (TrB) was 0.003 mmol. In addition, polymerization was started.

  Ethylene was continuously supplied at 100 liters / hr, polymerization was performed at 25 ° C. for 5 minutes under normal pressure, and then 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 0.56 g of polyethylene. The polymerization activity was 2670 g / mmol-Ti · hr, and the intrinsic viscosity [η] of the obtained polyethylene was 1.22 dL / g.

[Comparative Examples 16 to 38]
Using the compounds shown in Tables 1 to 3, ethylene polymerization was carried out in the same manner as in Comparative Example 15 except that the polymerization conditions were changed as shown in Tables 1 to 3. The results are shown in Tables 1 to 3.

Example 14
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 a mixed gas of ethylene 100 liter / hr and propylene 100 liter / hr. Thereafter, 0.125 mmol of triisobutylaluminum, 0.0004 mmol of the titanium compound (A) obtained in Example 1 and 0.0024 mmol of triphenylcarbenium tetrakis (pentafluorophenyl) borate were added to initiate copolymerization. . After copolymerization at 50 ° C. for 10 minutes, the polymerization was stopped by adding a small amount of isobutanol.

  To the obtained polymer suspension, 100 mL of water containing a small amount of hydrochloric acid was added, shaken vigorously, allowed to stand, and then the aqueous layer was removed. After repeating this operation three times in total, the solvent was distilled off under reduced pressure and further dried under reduced pressure at 130 ° C. for 10 hours.

  The obtained ethylene / propylene copolymer (EPR) was 0.27 g. The polymerization activity was 4101 g / mmol-Ti · hr, and the propylene content measured by IR was 24.9 mol%.

[Examples 15 to 19]
Using the compounds shown in Table 4, ethylene / propylene copolymerization was carried out in the same manner as in Example 14 except that the polymerization conditions were changed as shown in Table 4. The results are shown in Table 4.

[Comparative Example 39]
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 a mixed gas of ethylene 100 liter / hr and propylene 100 liter / hr. Thereafter, 0.125 mmol of triisobutylaluminum, 0.0025 mmol of the titanium compound (D) obtained in Comparative Example 1 and 0.003 mmol of triphenylcarbenium tetrakis (pentafluorophenyl) borate were added to initiate copolymerization. . After copolymerization at 50 ° C. for 10 minutes, the polymerization was stopped by adding a small amount of isobutanol.

  To the obtained polymer suspension, 100 mL of water containing a small amount of hydrochloric acid was added, shaken vigorously, allowed to stand, and then the aqueous layer was removed. After repeating this operation three times in total, the solvent was distilled off under reduced pressure and further dried under reduced pressure at 130 ° C. for 10 hours.

  The obtained ethylene / propylene copolymer (EPR) was 2.82 g. The polymerization activity was 6770 g / mmol-Ti · hr, and the propylene content measured by IR was 57.0 mol%.

[Comparative Examples 40 to 44]
Using the compounds shown in Table 4, ethylene / propylene copolymerization was carried out in the same manner as in Comparative Example 39, except that the polymerization conditions were changed as shown in Table 4. The results are shown in Table 4.

[Comparative Example 45]
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 gas phase were saturated with a mixed gas of ethylene 100 liter / hr and propylene 100 liter / hr. Thereafter, 1.25 mmol of methylaluminoxane (MAO) in terms of aluminum atom was added, and then 0.005 mmol of the following titanium compound (L) was added to initiate polymerization.

  After copolymerization at 50 ° C. for 15 minutes, the polymerization was stopped by adding a small amount of isobutanol.

  To the obtained polymer suspension, 100 mL of water containing a small amount of hydrochloric acid was added, shaken vigorously, allowed to stand, and then the aqueous layer was removed. After repeating this operation three times in total, the solvent was distilled off under reduced pressure and further dried under reduced pressure at 130 ° C. for 10 hours.

  The obtained ethylene / propylene copolymer (EPR) was 2.32 g. The polymerization activity was 1860 g / mmol-Ti · hr, and the propylene content measured by IR was 1.6 mol%.

[Comparative Example 46]
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 a mixed gas of ethylene 100 liter / hr and propylene 100 liter / hr. Thereafter, 0.20 mmol of triisobutylaluminum, 0.005 mmol of titanium compound (L) and 0.01 mmol of triphenylcarbenium tetrakis (pentafluorophenyl) borate were added to initiate polymerization. After copolymerization at 50 ° C. for 5 minutes, the polymerization was stopped by adding a small amount of isobutanol.

  To the obtained polymer suspension, 100 mL of water containing a small amount of hydrochloric acid was added, shaken vigorously, allowed to stand, and then the aqueous layer was removed. After repeating this operation three times in total, the solvent was distilled off under reduced pressure and further dried under reduced pressure at 130 ° C. for 10 hours.

  The obtained ethylene / propylene copolymer (EPR) was 0.14 g. The polymerization activity was 320 g / mmol-Ti · hr, and the propylene content measured by IR was 36.9 mol%.

  If the novel transition metal compound according to the present invention and an olefin polymerization catalyst containing the transition metal compound are used, since there is heat resistance in polymerization at a high temperature suitable for commercial production, the polymerization activity of olefin is high, Furthermore, since it has high copolymerizability when two or more types of olefins are copolymerized, the present invention is industrially extremely valuable.

Claims (7)

(A) A transition metal compound represented by the following general formula (I).

(In the above general formula (I), M represents a transition metal atom of Groups 3 to 10 of the periodic table,
A represents an oxygen atom, a sulfur atom, a nitrogen atom having a bonding group —R ⁸ , or a phosphorus atom having a bonding group —R ⁸ ;
Q represents a carbon atom, a silicon atom, a germanium atom, a tin atom,
R ^{1 to} R ³ may be the same as or different from each other, and are a secondary alkyl group, a tertiary alkyl group, a cycloalkyl group, or an aryl group, and R ¹ and R ² are connected to each other. A ring may be formed, R ² and R ³ may be linked together to form a ring, R ¹ and R ³ may be linked together to form a ring,
R ^{4 to} R ⁸ may be the same or different from each other, and are a hydrogen atom, a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, a sulfur-containing group, phosphorus A containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group, and two or more adjacent groups among them may be linked to each other to form a ring,
n represents 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, a plurality of groups represented by X may be the same or different from each other, and a plurality of groups represented by X may be bonded to each other to form a ring ,
L represents a neutral ligand including elements 13 to 16 of the periodic table;
m is 0 or an integer of 1 to 4,
D represents an optionally substituted hydrocarbon group or heterocyclic compound residue, the shortest number of bonds connecting A and N is 4 to 6, and the number of bonds connecting A and D is two. It may be a heavy bond or a triple bond. ) The transition metal compound according to claim 1, wherein the shortest bond number connecting A and N in the general formula (I) is 5 or 6. The transition metal compound according to claim 1, wherein A, N and D in the general formula (I) form a structure represented by the general formula (II).

(In General Formula (II), Y represents the same atom as that represented by General Formula (I),
R ^{9 to} R ¹² 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 when R ^{9 to} R ¹² are hydrocarbon groups, R ⁹ and R ¹⁰ are connected to each other to form a ring. R ¹¹ and R ¹² may be connected to each other to form a ring. ) The transition metal compound according to any one of claims 1 to 3, wherein M in the general formula (I) is a transition metal atom of Group 4 of the periodic table and n is 4. The catalyst for olefin polymerization containing the (A) transition metal compound of any one of Claim 1 to 4. In addition to (A) the transition metal compound according to any one of claims 1 to 4,
(B) (B-1) an organometallic compound,
(B-2) an organoaluminum oxy compound, and (B-3) a compound that reacts with the transition metal compound (A) to form an ion pair,
An olefin polymerization catalyst further comprising at least one compound selected from the group consisting of: A method for producing an olefin polymer, wherein the olefin is homopolymerized or copolymerized in the presence of the olefin polymerization catalyst according to claim 5 or 6.