Transition metal compound, catalyst for olefin polymerization, and method for producing olefin polymer

Abstract

To provide a new transition metal compound that can be used as a catalyst for olefin polymerization.SOLUTION: The present invention provides a transition metal compound (A) having a specific structure that contains three kinds of atoms selected from the group consisting of boron which is a group 13 element of the periodic table, a group 15 element of the periodic table, and oxygen and sulfur which are each a group 16 element of the periodic table. The transition metal compound (A) is also characterized by that the compound contains one or more anionic ligands. By using such a transition metal compound, polymerization of various olefins becomes possible such as polymerization of ethylene, copolymerization of ethylene and another olefin, copolymerization of ethylene and a cyclic olefin, and the like; and a catalyst for olefin polymerization can be obtained, which is excellent in the balance of performances of activity, increase in molecular weight and copolymerizability.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a novel transition metal compound, and more particularly to a novel transition metal compound that can be used as a catalyst for olefin polymerization, a catalyst for olefin polymerization containing the compound, and a method for producing an olefin polymer using the catalyst. [Background technology]

[0002] Catalysts consisting of a metallocene compound and a co-catalyst such as an organoaluminum oxy compound are known to be used as catalysts for producing olefin polymers such as ethylene-α-olefin copolymers.

[0003] Various types of transition metal compounds, such as metallocene compounds, have been actively developed as catalysts. For example, Patent Document 1 describes a transition metal compound (A) represented by the following general formula:

[0004] [ka] (In the formula, M represents a transition metal of Group 4 of the periodic table such as Ti, L represents a monovalent anionic ligand in which an element of Group 15 of the periodic table acts as the coordinating atom, X represents halogens, etc., m represents an integer from 1 to 3, R 1 ~R 5 (This represents hydrogen, halogens, or alkyl groups with 1 to 20 carbon atoms, etc.)

[0005] The invention also describes a method for producing a cyclic olefin copolymer in which ethylene and / or an α-olefin having 3 to 20 carbon atoms copolymerizes with at least one cyclic olefin compound in the presence of a polymerization catalyst comprising one or more activators (B) selected from organoaluminum oxy compounds and organoboron compounds, and a specific example of the transition metal compound (A) is CpTi(t-Bu2C=N)Cl2, and a comparative example is Cp * Ti(2,6- i Pr2PhO)Cl2 is mentioned. (Cp is a cyclopentadienyl group, Cp * is η 5- Represents a pentamethylcyclopentadienyl group.

[0006] On the other hand, Patent Document 2 discloses an example of the production of ultra-high molecular weight polyethylene using a complex having a Cp*[t-BuPN]Cl2 skeleton.

[0007] The applicant has reported a metal complex with a novel structure and a method for producing olefin polymers using the same. (For example, Patent Document 3) [Prior art documents] [Patent Documents]

[0008] [Patent Document 1] Japanese Patent Publication No. 2007-63409 [Patent Document 2] Special Publication No. 2016-534165 [Patent Document 3] Japanese Patent Publication No. 2021-116302 [Overview of the Initiative] [Problems that the invention aims to solve]

[0009] The market continues to demand polymerization catalysts with excellent polymerization activity, high molecular weight formation capabilities, and copolymerization properties, as well as olefin polymers produced using these catalysts. Therefore, the present invention aims to provide novel transition metal compounds that are useful as catalysts for olefin (co)polymerization.

[0010] Furthermore, the present invention aims to provide an olefin polymerization catalyst suitable for the production of various olefin copolymers (for example, suitable in one or more properties such as polymerization activity, high molecular weight production of polymers, and olefin copolymerizability), and a method for producing olefin polymers using the olefin polymerization catalyst. [Means for solving the problem]

[0011] In view of the above-mentioned problems and objectives, the inventors of the present invention conducted research and found that a compound having a specific complex structure exhibits desirable effects as a component of a catalyst for olefin polymerization, and thus completed the present invention. That is, the present invention has the following configuration.

[0012] [1] A transition metal compound (A) is specified by the following formula (1).

[0013] [ka] [In equation (1), L(l) is an anionic ligand containing hydrogen and an element selected from the group consisting of Group 13, Group 14, and Group 15 elements of the periodic table, where l is a positive integer identical to the valence of the anionic ligand. If l is 2 or more, each of the multiple L(l) is independently the anionic ligand, either bonded to each other to form a ring, or not bonded to each other. M is an atom of a transition metal element in groups 3-11 of the periodic table. n is a positive integer. X represents a hydrogen atom, a halogen atom, or a substituent selected from the group consisting of a hydrocarbon group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a boron-containing group, an aluminum-containing group, a phosphorus-containing group, a halogen-containing group, a heterocyclic compound residue, a silicon-containing group, a germanium-containing group, and a tin-containing group. If n is 2 or more, each of the multiple X values ​​is independently a hydrogen atom, a halogen atom, or one of the substituents, and they are either bonded to each other to form a ring or not bonded to each other. E represents an oxygen atom or a sulfur atom. Z represents a boron atom. The two Qs each independently represent atoms of Group 15 elements in the periodic table. m is a positive integer. If m is 2 or greater, the multiple groups represented by the following formula (1') are either identical or different, bonded to each other to form a ring, or not bonded to each other.

[0014] [ka] The sum of l, m, and n is the same as the valence of M. Each of the multiple Rh and Rp atoms is independently a hydrogen atom, a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, or a halogen atom, or Each of the multiple Rh and Rp groups is independently a hydrocarbon group in which a hydrogen atom, a carbon atom, or both contained in the hydrocarbon are substituted with a structure that includes at least one atom selected from the group consisting of nitrogen, oxygen, phosphorus, halogen, and silicon atoms, or are not substituted with such a structure. Two or more of the Rh and Rp atoms are either bonded to each other to form a monocycle or polycycle, or they are not bonded to each other. If two or more of the Rh and Rp atoms are bonded to each other, adjacent substituents are either directly bonded to each other to form a covalent bond (including multiple bonds), or they are not directly bonded to each other.

[0015] [2] The transition metal compound (A) of [1], wherein M is an atom of a transition metal element in group 4 or 5 of the periodic table.

[0016] [3] The transition metal compound (A) of [2] wherein M is a titanium atom.

[0017] [4] A transition metal compound (A) from any of the above [1] to [3], wherein E is an oxygen atom.

[0018] [5] A transition metal compound (A) from any of the above [1] to [4], which is a transition metal compound (A1) specified by the following formula (2).

[0019] [ka] [In equation (2), L, M, X, E, Z, Q, Rh, l, n, and m are equivalent to L, M, X, E, Z, Q, Rh, l, n, and m in formula (1) above, respectively. Rr represents a substituted or unsubstituted hydrocarbon group with 1 to 20 carbon atoms, or a covalent bond between C and C, or Rr is a hydrocarbon group in which a hydrogen atom, a carbon atom, or both contained in the hydrocarbon are substituted with a structure containing at least one atom selected from the group consisting of nitrogen atoms, oxygen atoms, phosphorus atoms, halogen atoms, and silicon atoms, or are not substituted with such a structure. Each of the multiple Rs is independently a hydrogen atom, a substituted or unsubstituted hydrocarbon group with 1 to 20 carbon atoms, or a halogen atom, or Each of the multiple Rs groups is independently a hydrocarbon group in which a hydrogen atom, a carbon atom, or both contained in the hydrocarbon are substituted with a structure that includes at least one atom selected from the group consisting of nitrogen, oxygen, phosphorus, halogen, and silicon atoms, or are not substituted with such a structure. Two or more of Rr, Rs, and Rh are either bonded to each other to form a monocycle or polycycle, or they are not bonded to each other. If two or more of Rr, Rs, and Rh are bonded to each other, adjacent substituents are either directly bonded to each other to form a covalent bond (including multiple bonds), or they are not directly bonded to each other.

[0020] [6] The transition metal compound (A) in [5] is a transition metal compound (A2) specified by the following formula (3) or formula (4).

[0021] [ka] [In equations (3) and (4), M, X, E, Z, Q, Rh, Rr, Rs, n, and m are equivalent to M, X, E, Z, Q, Rh, Rr, Rs, n, and m in formula (2) above, Each of the multiple Rs is independently a hydrogen atom, a substituted or unsubstituted hydrocarbon group with 1 to 20 carbon atoms, or a halogen atom, or Each of the multiple R groups is independently a hydrocarbon group, wherein the hydrogen atom, carbon atom, or both contained in the hydrocarbon are substituted with a structure containing at least one atom selected from the group consisting of nitrogen, oxygen, phosphorus, halogen, and silicon atoms, or are not substituted with such a structure.

[0022] [7] A transition metal compound (A) from any of the above [1] to [6], (B-1) organometallic compound, (B-2) Organic aluminum oxy compounds, and (B-3) Compounds that react with the transition metal compound to form an ion pair At least one compound (B) selected from the group consisting of and A catalyst for olefin polymerization containing [specific component].

[0023] [8] A method for producing an olefin polymer, comprising polymerizing an olefin in the presence of the olefin polymerization catalyst described in [7] above.

[0024] [9] A method for producing the olefin polymer according to [8], wherein the olefin comprises an α-olefin having 2 to 30 carbon atoms. [Effects of the Invention]

[0025] The transition metal compounds of the present invention are useful as catalysts for olefin (co)polymerization. When used as a catalyst in the polymerization or copolymerization of ethylene or olefins having 3 or more carbon atoms, the transition metal compounds of the present invention exhibit one or more properties of polymerization activity, high molecular weight polymerization, and olefin copolymerizability. For example, they can provide highly active high molecular weight polyolefins, olefin copolymers with low melting points, and cyclic olefin copolymers exhibiting high glass transition temperatures. [Modes for carrying out the invention]

[0026] The transition metal compound according to the present invention is specified by the following structure. Furthermore, when the transition metal compound is used in an olefin polymerization reaction, it is preferable to use it in combination with an organometallic compound containing Group 1, Group 2, or Group 13 elements of the periodic table, such as an organoaluminum compound. Each component will be described below.

[0027] [Transition metal compounds] The transition metal compound of the present invention (hereinafter also referred to as "transition metal compound (A)") is represented by the following formula (1).

[0028] [ka]

[0029] The above L(l) is an anionic ligand containing hydrogen and an element selected from Group 13, Group 14, and Group 15 of the periodic table, where l is a positive integer identical to the valence of the anionic ligand. If l is 2 or greater, the multiple anionic ligands represented by L(l) may be identical or different, and the multiple anionic ligands represented by L(l) may bond to each other to form a ring structure.

[0030] Examples of such L(l) include hydrocarbon-based anionic ligands such as cyclopentadienyl and fluorenyl groups. Furthermore, anionic ligands containing heteroatoms such as halogens, or heteroatom-containing substituents such as alkoxy groups, amino groups, imino groups, phosphino groups, and silyl groups, may also be suitable embodiments. In such substituent-containing hydrocarbon ligands, halogen atoms are preferred as substituents, and fluorine is more preferred.

[0031] Other examples of ligands include anionic ligands containing elements selected from Group 13, Group 14, and Group 15 of the periodic table, such as phosphine imino, phosphine amino, and phosphine oxy ligands, as well as anionic polydentate ligands such as trispirazolyl borate. These structures are often monovalent anionic ligands, but polyvalent anionic ligands can also be used. Among the above, the (substituted) cyclopentadienyl ligand and the phosphine imino group ligand are preferred structures.

[0032] The above M is an atom of a transition metal element from groups 3 to 11 of the periodic table. Such transition metal elements include lanthanide and actinide elements. Preferably, it is an element selected from the transition metal elements of groups 4 and 5 of the periodic table. Specifically, examples include titanium, zirconium, hafnium, and vanadium. Such elements may, for example, be components that exhibit excellent polymerization activity in olefin polymerization catalysts, as described later. Titanium is particularly preferred. Titanium may, for example, be a component of olefin polymerization catalysts that easily yield high molecular weight products. The above n is a positive integer.

[0033] The above X represents a substituent selected from the group consisting of a hydrogen atom, a halogen atom, or a hydrocarbon group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a boron-containing group, an aluminum-containing group, a phosphorus-containing group, a halogen-containing group, a heterocyclic compound residue, a silicon-containing group, a germanium-containing group, and a tin-containing group. When n is 2 or more, the multiple groups represented by X may be the same or different, and the multiple groups represented by X may be bonded to each other to form a ring. Specifically, halogen atoms or hydrocarbon groups can be given as preferred examples of X. Examples of halogen atoms include fluorine, chlorine, bromine, and iodine, with chlorine and bromine being preferred, and chlorine being particularly preferred. Examples of hydrocarbon groups include hydrocarbon groups having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, and preferred specific examples include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isopropyl group, etc. Furthermore, when multiple X groups are linked to form a ring, examples include butylene group, pentamethylene group, and hexamethylene group.

[0034] The above E represents an oxygen atom or a sulfur atom. Preferably, it is an oxygen atom. The above Z represents a boron atom.

[0035] The above Q represents an atom selected from Group 15 of the periodic table, and the two Qs may be identical or different. Among these, nitrogen is particularly preferred from the viewpoint of availability and performance-cost balance.

[0036] m is a positive integer. When m is 2 or greater, the multiple groups represented by formula (1') below may be identical or different, and the multiple groups shown in formula (1') below may be bonded to each other to form a ring structure.

[0037] [ka]

[0038] The above values ​​of l, m, and n are positive integers, and the sum of l, m, and n is the same as the valence of M. l is preferably 1 to 3, more preferably 1 to 2, and particularly preferably 1. m is preferably 1 to 3, more preferably 1 to 2, and particularly preferably 1. n is preferably 1 to 4, more preferably 1 to 3, and particularly preferably 1 to 2. Furthermore, it is preferable that the sum of l, m, and n is 6 or less.

[0039] Each of the multiple Rh and Rp groups is selected from a hydrogen atom, a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, or a halogen atom, and the hydrogen atom, carbon atom, or both of the Rh and Rp groups may include structures in which at least one atom selected from the group consisting of nitrogen, oxygen, phosphorus, halogen, and silicon atoms is substituted.

[0040] More specific examples of substituents containing nitrogen, oxygen, phosphorus, halogens, and silicon include hydrocarbon groups having substituents containing nitrogen, oxygen, phosphorus, halogens, and silicon. Such substituents can be selected from known structures. More specifically, suitable examples include carboxylic acid ester groups, aldehyde groups, acetyl groups, carbonyl structure-containing groups such as oxycarbonylalkyl groups, alkoxy groups, substituted or unsubstituted alkoxy groups, substituted or unsubstituted alkenyloxy groups, substituted or unsubstituted cycloalkyloxy groups, substituted or unsubstituted cycloalkenyloxy groups, substituted or unsubstituted aryloxy groups, substituted or unsubstituted heteroaryl groups, substituted or unsubstituted heteroaryloxy groups, and siloxy groups. The heteroatoms are preferably nitrogen and oxygen, and more preferably oxygen.

[0041] Among the heteroatom-containing substituents mentioned above, examples include aryl groups containing oxygen-containing substituents, specifically structures in which an oxygen-containing substituent such as an alkoxy group, allyloxy group, alkoxyalkyl group, allyloxyalkyl group, or substituents in which the oxygen of the substituent is replaced with a carboxyl group is bonded to an aromatic skeleton. Among the above, substituents in which an alkoxy group or allyloxy group is bonded to an aromatic skeleton are preferred, and substituents in which an alkoxy group is bonded to an aromatic skeleton are more preferred. The number of carbon atoms in the oxygen-containing substituent is preferably 1 to 10, more preferably 1 to 8, and even more preferably 1 to 6. More specifically, in addition to the methoxyphenyl group mentioned above, ethoxyphenyl group, propyloxyphenyl group, isopropyloxyphenyl group, butoxyphenyl group, phenoxyphenyl group, etc. are preferred examples. In addition, aryl groups containing halogen atoms may also be suitable, with fluorine being a preferred halogen.

[0042] Furthermore, it may be preferable, from the viewpoint of balancing activity, molecular weight, copolymerizability, etc., that at least one substituent of Rh and Rp mentioned above be a substituent other than hydrogen. Specific examples of such substituents will be described later, but in some cases, substituents with bulky structures are preferable. Examples include hydrocarbon groups containing secondary and tertiary carbons, and aromatic substituents containing bulky alkyl groups (so-called hindered structures). Such bulky substituent structures may be preferable from the viewpoint of activity, molecular weight, and copolymerizability, in terms of controlling the electron density and steric effects of the transition metal compound (A). The following are examples of more specific substituents.

[0043] The hydrocarbon group described above is a monovalent hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 10, more preferably 2 to 8, even more preferably 3 to 8, even more preferably 4 to 8, and particularly preferably 4 to 6 carbon atoms. Examples of this hydrocarbon group include aliphatic hydrocarbon groups, alicyclic hydrocarbon groups, and aromatic hydrocarbon groups, such as substituted or unsubstituted aryl groups, substituted or unsubstituted cycloalkenyl groups, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, t-butyl group, hexyl group, heptyl group, octyl group, 2-ethylhexyl group, decyl group, dodecyl group, tetradecyl group, hexadecyl group, octadecyl group, eicosyl group, cyclohexyl group, phenyl group, etc. The alicyclic hydrocarbon group and aromatic hydrocarbon group may contain substituents. Among these, substituted and unsubstituted aryl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, and phenyl groups are preferred.

[0044] The aforementioned Rh and Rp can also be cyclic saturated hydrocarbon groups having 3 to 20 carbon atoms. Specifically, examples include cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, norborneyl group, 1-adamantyl group, 2-adamantyl group, and groups in which the hydrogen atoms of these cyclic saturated hydrocarbon groups are replaced by hydrocarbon groups having 1 to 17 carbon atoms, such as 3-methylcyclopentyl group, 3-methylcyclohexyl group, 4-methylcyclohexyl group, 4-cyclohexylcyclohexyl group, and 4-phenylcyclohexyl group. The number of carbon atoms in the cyclic saturated hydrocarbon group is preferably 5 to 11.

[0045] Examples of chain-like unsaturated hydrocarbon groups having 2 to 20 carbon atoms include alkenyl groups such as the ethenyl group (vinyl group), 1-propenyl group, 2-propenyl group (allyl group), and 1-methylethenyl group (isopropenyl group), and alkynyl groups such as the ethynyl group, 1-propynyl group, and 2-propynyl group (propargyl group). The number of carbon atoms in the chain-like unsaturated hydrocarbon group is preferably 2 to 4.

[0046] Examples of cyclic unsaturated hydrocarbon groups having 3 to 20 carbon atoms include cyclopentadienyl, norbornyl, phenyl, naphthyl, indenyl, azurenyl, phenanthryl, and anthracenyl groups. Other examples include 3-methylphenyl (m-tolyl), 4-methylphenyl (p-tolyl), 4-ethylphenyl, 4-t-butylphenyl, 4-cyclohexylphenyl, biphenylyl, 3,4-dimethylphenyl, 3,5-dimethylphenyl, and 2,4,6-trimethylphenyl (mesityl), which are groups in which the hydrogen atoms of these cyclic unsaturated hydrocarbon groups are replaced by hydrocarbon groups having 1 to 15 carbon atoms. Other examples include benzyl and cumyl groups, which are groups in which the hydrogen atoms of linear or branched saturated hydrocarbon groups are replaced by cyclic saturated or cyclic unsaturated hydrocarbon groups having 3 to 19 carbon atoms. The number of carbon atoms in the cyclic unsaturated hydrocarbon groups is preferably 6 to 10.

[0047] Examples of alkylene groups having 1 to 20 carbon atoms include methylene, ethylene, dimethylmethylene (isopropylidene), ethylmethylene, 1-methylethylene, 2-methylethylene, 1,1-dimethylethylene, 1,2-dimethylethylene, and n-propylene. The alkylene group preferably has 1 to 6 carbon atoms.

[0048] Examples of arylene groups having 6 to 20 carbon atoms include o-phenylene groups, m-phenylene groups, p-phenylene groups, and 4,4'-biphenylene groups. The number of carbon atoms in the arylene group is preferably 6 to 12.

[0049] Examples of aryl groups include those derived from aromatic compounds, such as phenyl, 1-naphthyl, 2-naphthyl, anthracenyl, phenantrenyl, tetracerenyl, chrysenyl, pyrenyl, indenyl, azurenyl, pyrrolyl, pyridyl, furanyl, and thiophenyl groups, although these overlap somewhat with the previously mentioned examples of cyclic unsaturated hydrocarbon groups with 3 to 20 carbon atoms.

[0050] Examples of the aforementioned aromatic compounds include aromatic hydrocarbons and heterocyclic aromatic compounds such as benzene, naphthalene, anthracene, phenanthrene, tetracene, chrysene, pyrene, pyrene, indene, azulene, pyrrole, pyridine, furan, and thiophene.

[0051] Examples of substituted aryl groups include those that partially overlap with the examples of cyclic unsaturated hydrocarbon groups having 3 to 20 carbon atoms mentioned above, but also include groups in which one or more hydrogen atoms of the aryl group are substituted by substituents selected from hydrocarbon groups having 1 to 20 carbon atoms, aryl groups, silicon-containing groups, nitrogen-containing groups, oxygen-containing groups, halogen atoms, and halogen-containing groups. Specifically, these include 3-methylphenyl group (m-tolyl group), 4-methylphenyl group (p-tolyl group), 3-ethylphenyl group, 4-ethylphenyl group, 3,4-dimethylphenyl group, 3,5-dimethylphenyl group, biphenylyl group, 4-(trimethylsilyl)phenyl group, and 4-aminophenyl group. Examples of aryl groups include 4-(dimethylamino)phenyl group, 4-(diethylamino)phenyl group, 4-morpholinylphenyl group, 4-methoxyphenyl group, 4-ethoxyphenyl group, 4-phenoxyphenyl group, 3,4-dimethoxyphenyl group, 3,5-dimethoxyphenyl group, 3-methyl-4-methoxyphenyl group, 3,5-dimethyl-4-methoxyphenyl group, 3-(trifluoromethyl)phenyl group, 4-(trifluoromethyl)phenyl group, 3-chlorophenyl group, 4-chlorophenyl group, 3-fluorophenyl group, 4-fluorophenyl group, 5-methylnaphthyl group, and 2-(6-methyl)pyridyl group. Other preferred aryl groups include substituted aryl groups containing so-called higher alkyl groups such as isopropyl group, s-butyl group, and t-butyl group, with hindered aryl groups being particularly preferred due to their bulky structure. Also, "electron-donating group-containing substituted aryl groups," described later, can be mentioned as substituted aryl groups.

[0052] Examples of silicon-containing groups include alkylsilyl groups such as trimethylsilyl, triethylsilyl, t-butyldimethylsilyl, and triisopropylsilyl, which are hydrocarbon groups having 1 to 20 carbon atoms in which carbon atoms are replaced by silicon atoms; arylsilyl groups such as dimethylphenylsilyl, methyldiphenylsilyl, and t-butyldiphenylsilyl; pentamethyldisilanyl; and trimethylsilylmethyl. The number of carbon atoms in alkylsilyl groups is preferably 1 to 10, and the number of carbon atoms in arylsilyl groups is preferably 6 to 18.

[0053] Examples of nitrogen-containing groups include amino groups, nitro groups, N-morpholinyl groups, and, in the above-mentioned hydrocarbon groups having 1 to 20 carbon atoms or silicon-containing groups, groups in which the =CH- structural unit is replaced by a nitrogen atom, groups in which the -CH2- structural unit is replaced by a nitrogen atom to which a hydrocarbon group having 1 to 20 carbon atoms is bonded, or groups in which the -CH3 structural unit is replaced by a nitrogen atom to which a hydrocarbon group having 1 to 20 carbon atoms is bonded or a nitrile group, such as dimethylamino groups, diethylamino groups, dimethylaminomethyl groups, cyano groups, pyrrolidinyl groups, piperidinyl groups, and pyridinyl groups. Dimethylamino groups and N-morpholinyl groups are preferred as nitrogen-containing groups.

[0054] Oxygen-containing groups include hydroxyl groups, the aforementioned hydrocarbon groups with 1 to 20 carbon atoms, silicon-containing groups, or nitrogen-containing groups in which the -CH2- structural unit is replaced by an oxygen atom or a carbonyl group, or in which the -CH3 structural unit is replaced by an oxygen atom to which a hydrocarbon group with 1 to 20 carbon atoms is bonded, such as methoxy groups, ethoxy groups, t-butoxy groups, phenoxy groups, trimethylsiloxy groups, methoxyethoxy groups, hydroxymethyl groups, methoxymethyl groups, ethoxymethyl groups, t-butoxymethyl groups, and 1-hydroxyethyl groups. Examples of oxygen-containing groups include 1-methoxyethyl group, 1-ethoxyethyl group, 2-hydroxyethyl group, 2-methoxyethyl group, 2-ethoxyethyl group, n-2-oxabutylene group, n-2-oxapentylene group, n-3-oxapentylene group, aldehyde group, acetyl group, propionyl group, benzoyl group, trimethylsilylcarbonyl group, carbamoyl group, methylaminocarbonyl group, carboxyl group, methoxycarbonyl group, carboxymethyl group, ethocarboxymethyl group, carbamoylmethyl group, furanyl group, and pyranyl group. Methoxyethyl group is preferred as the oxygen-containing group.

[0055] Examples of halogen atoms include elements from Group 17 such as fluorine, chlorine, bromine, and iodine. Examples of halogen-containing groups include trifluoromethyl, tribromomethyl, pentafluoroethyl, and pentafluorophenyl groups, which are hydrocarbon groups, silicon-containing groups, nitrogen-containing groups, or oxygen-containing groups having 1 to 20 carbon atoms, in which a hydrogen atom is substituted by a halogen atom.

[0056] It is preferable that at least one of the Rh and Rp is a substituent according to the preferred embodiment described above. The Rh and Rp atoms can bond to each other in groups of two or more to form monocyclic or polycyclic rings, and adjacent substituents can form multiple bonds by direct bonding. In the present invention, transition metal compounds in which multiple Rp atoms bond to each other to form a ring structure are preferred. Examples of such compounds include those having the structure of formula (2) shown below.

[0057] [ka]

[0058] The above Rr may include a hydrogen atom, a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, or a structure that simply exhibits a covalent bond in which the hydrogen atom, carbon atom, or both are substituted with at least one atom selected from the group consisting of nitrogen, oxygen, phosphorus, halogen, and silicon atoms.

[0059] Examples of such structures include those corresponding to the divalent substituents of Rh and Rp mentioned above. Furthermore, when Rr is simply a covalent bond, it can be either a single bond or a double bond. A double bond is preferred. In the case of a double bond, the above formula (2) can be represented by the following formula (2'), and this can be considered to correspond to the case where the Rs atoms bonded to the two carbon atoms in the above formula (2) directly bond to each other to form a covalent bond.

[0060] [ka]

[0061] A more preferred embodiment of the double bond formation of Rr is the configuration in which Rs bonded to adjacent carbon atoms further bond to each other to form a cyclic structure. In this case, in addition to the cycloalkene structure, an aryl-type structure is also a preferred embodiment of the cyclic structure. Each of the above Rs groups is selected from a hydrogen atom, a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, or a halogen atom. The hydrogen atom, carbon atom, or both of the Rs group may be substituted with at least one atom selected from the group consisting of nitrogen, oxygen, phosphorus, halogen, and silicon atoms. Specific examples of Rs are the same as those for Rh and Rp.

[0062] The Rr, Rs, and Rh atoms can bond to each other in groups of two or more to form monocyclic or polycyclic rings, and adjacent substituents can also form multiple bonds by directly bonding to each other. More preferred embodiments of the structure of formula (2) above include the structures of formulas (3) and (4) shown below.

[0063] [ka]

[0064] The definition and specific structure of the substituent R in the above formula are the same as those for Rs and Rh described above. With such a structure, properties such as activity, molecular weight, and copolymerizability tend to be easily adjusted by changing the structure of various substituents. Specific examples of transition metal compounds (A) that satisfy the above requirements include compounds with the following structures.

[0065] [ka]

[0066] [ka]

[0067] [ka] (Adm represents either a 1-adamantyl group or a 2-adamantyl group.)

[0068] In the present invention, the above-mentioned transition metal compound (A) may be a single compound or a combination of two or more compounds. The transition metal compound (A) can be produced by referring to the "Synthesis Experiment Examples" described later. More specifically, for example, a method can be given in which the anion at the site represented by formula (1') is reacted with a transition metal halide corresponding to the other sites.

[0069] While some of the latter transition metal halides are commercially available, they can also be produced by well-known methods of reacting the anion corresponding to L(l) with the transition metal halide. Furthermore, when X in formula (1) is a hydrocarbon group, they can be synthesized by well-known methods of reacting the aforementioned halide with the corresponding Grignard reagent or organometallic compound such as alkyllithium.

[0070] Another method involves, for example, when X is an alkyl group, generating a compound by alkylating a transition metal halide corresponding to the other part, and reacting it with a hydroxyl compound corresponding to the part represented by formula (1'). An example of a synthesis reaction equation corresponding to the above method can be represented by the following formula. (This is an example of a synthesis method for a transition metal compound different from Synthesis Example 9 described later.) [ka]

[0071] Furthermore, the transition metal compounds of the present invention can also be synthesized using known reactions. The compound corresponding to the site represented by the former formula (1') can be produced by a known method of reacting a compound corresponding to the structural site containing Q and Rp, specifically an anion of a group 15 element-containing compound such as an amine compound or an aniline compound, with a boron halide compound.

[0072] As described above, the transition metal compound (A) of the present invention can be synthesized by synthesizing each of the above-mentioned parts using known synthesis methods and then bonding them together using known methods. Of course, the method for producing the transition metal compound (A) of the present invention is not limited to the method described above.

[0073] [Catalyst for olefin polymerization] The olefin polymerization catalyst of the present invention comprises the transition metal compound (A) described above and the compound (B) described below.

[0074] (Component (B) used in combination with transition metal compound (A)) Examples of the above component (B) of the present invention include the following components (B-1) to (B-3).

[0075] ((B-1) Organometallic compound) Specific examples of the organometallic compound (B-1) used in the present invention include compounds containing at least one element selected from Groups 1, 2, 12, and 13 of the periodic table, represented by the following general formulas (B-1a) to (B-1c): R a p Al(ОR 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 represent a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms. Y represents a halogen atom, p is a number where 0 < p ≦ 3, q is a number where 0 ≦ q < 3, r is a number where 0 ≦ r < 3, s is a number where 0 ≦ s < 3, and m + n + p + q = 3.) An organoaluminum compound represented by; 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.) A complex alkyl compound of an alkali metal of Group 1 of the periodic table and aluminum; R d R<00​​​​​​​​​​​​​​Examples of the organoaluminum compound belonging to the general formula (B-1a) include the following compounds. R a p Al(ОR b ) 3-p ···(B-1a-1) (In the formula (B-1a-1), R a and R b may be the same as or different from each other, and represent a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, and p is preferably a number of 1.5 ≦ p ≦ 3.) An organoaluminum compound represented by R a p AlY 3-p ···(B-1a-2) (In the formula (B-1a-2), R a 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 by R a p AlH 3-p ···(B-1a-3) (In the formula (B-1a-3), 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.) An organoaluminum compound represented by R a p Al(ОR b ) q Y s ···(B-1a-4) (In the formula (B-1a-4), R a and R b may be the same as or different from each other, and represent a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, Y represents a halogen atom, p is a number of 0 < p ≦ 3, q is a number of 0 ≦ q < 3, s is a number of 0 ≦ s < 3, and p + q + s = 3.) An organoaluminum compound represented by

[0077] More specifically, organoaluminum compounds belonging to general formula (B-1a) include trimethylaluminum, triethylaluminum, tri-n-butylaluminum, tripropylaluminum, tripentylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum, and other tri-n-alkylaluminum compounds; Tri-branched alkylaluminum compounds such as triisopropylaluminum, triisobutylaluminum, trisec-butylaluminum, tritert-butylaluminum, tri-2-methylbutylaluminum, tri-3-methylbutylaluminum, tri-2-methylpentylaluminum, tri-3-methylpentylaluminum, tri-4-methylpentylaluminum, tri-2-methylhexylaluminum, tri-3-methylhexylaluminum, and tri-2-ethylhexylaluminum; Tricycloalkylaluminum such as tricyclohexylaluminum and tricyclooctylaluminum; Triarylaluminum, such as triphenylaluminum and tritrilaluminum; Dialkylaluminum hydrides such as diisobutylaluminum hydride; (i-C4H9) x Al y (C5H 10 ) z Trialkenyl aluminum, such as triisoprenyl aluminum, represented by the formula (where x, y, and z are positive numbers and z ≥ 2x); Alkylaluminum alkoxides such as isobutylaluminum methoxide, isobutylaluminum ethoxide, and isobutylaluminum isopropoxide; Dialkylaluminum alkoxides such as dimethylaluminum methoxide, diethylaluminum ethoxide, and dibutylaluminum butoxide; Alkylaluminum sesquialkoxides such as ethylaluminum sesquiethoxide and butylaluminum sesquibutoxide; R a 2.5 Al(OR) b )0.5 Partially alkoxylated alkylaluminum having an average composition represented by the formula (wherein R a and R b These may be identical or different from each other, and represent hydrocarbon groups having 1 to 15, preferably 1 to 4, carbon atoms. Dialkylaluminum allyloxides such as diethylaluminum phenoxide, diethylaluminum (2,6-di-t-butyl-4-methylphenoxide), ethylaluminum bis(2,6-di-t-butyl-4-methylphenoxide), diisobutylaluminum (2,6-di-t-butyl-4-methylphenoxide), and isobutylaluminum bis(2,6-di-t-butyl-4-methylphenoxide); Dialkylaluminum halides such as dimethylaluminum chloride, diethylaluminum chloride, dibutylaluminum chloride, diethylaluminum bromide, and diisobutylaluminum chloride; Alkylaluminum sesquihalides such as ethylaluminum sesquichloride, butylaluminum sesquichloride, and ethylaluminum sesquibromide; Partially halogenated alkylaluminums such as alkylaluminum dihalides, ethylaluminum dichloride, propylaluminum dichloride, and butylaluminum dibromide; Dialkylaluminum hydrides such as diethylaluminum hydride and dibutylaluminum hydride; Other partially hydrogenated alkylaluminum dihydrides such as ethylaluminum dihydride and propylaluminum dihydride; Examples include partially alkoxylated and halogenated alkylaluminums such as ethylaluminum ethoxycyclolide, butylaluminum butoxycyclolide, and ethylaluminum ethoxybromide.

[0078] Compounds similar to (B-1a) can also be used in the present invention, and examples of such compounds include organoaluminum compounds in which two or more aluminum compounds are bonded via a nitrogen atom. Specifically, examples of such compounds include (C2H5)2AlN(C2H5)Al(C2H5)2.

[0079] Compounds belonging to the general formula (B-1b) include LiAl(C2H5)4 and LiAl(C7H 15 Examples include 4. Examples of compounds belonging to the general formula (B-1c) include dimethylmagnesium, diethylmagnesium, dibutylmagnesium, butylethylmagnesium, dimethylzinc, diethylzinc, diphenylzinc, di-n-propylzinc, diisopropylzinc, di-n-butylzinc, diisobutylzinc, bis(pentafluorophenyl)zinc, dimethylcadmium, and diethylcadmium.

[0080] In addition, other organometallic compounds (B-1) that can be used include methyllithium, ethyllithium, propyllithium, butyllithium, methylmagnesium bromide, methylmagnesium chloride, ethylmagnesium bromide, ethylmagnesium chloride, propylmagnesium bromide, propylmagnesium chloride, butylmagnesium bromide, and butylmagnesium chloride.

[0081] Furthermore, compounds such as a combination of aluminum halide and alkyllithium, or a combination of aluminum halide and alkylmagnesium, which form the above-mentioned organoaluminum compound within the polymerization system, can also be used as the organometallic compound (B-1).

[0082] Among organometallic compounds (B-1), organoaluminum compounds are preferred from the viewpoint of catalytic activity. The organometallic compounds (B-1) described above can be used individually or in combination of two or more.

[0083] ((B-2) Organoaluminum oxy compounds) The organoaluminum oxy compound (B-2) used in the present invention may be a conventionally known aluminoxane, or it may be a benzene-insoluble organoaluminum oxy compound as exemplified in Japanese Patent Application Publication No. 2-78687.

[0084] Conventionally known aluminoxanes can be produced by methods such as those described below, and are usually obtained as solutions in a hydrocarbon solvent.

[0085] (1) A method of reacting the adsorbed water or crystal water with the organoaluminum compound by adding an organoaluminum compound such as trialkylaluminum to a suspension of a hydrocarbon medium containing a compound or salt containing crystal water, such as magnesium chloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate, or cerium chloride hydrate.

[0086] (2) A method of reacting an organoaluminum compound such as trialkylaluminum directly with water, ice, or water vapor in a medium such as benzene, toluene, ethyl ether, or tetrahydrofuran.

[0087] (3) A method of reacting organoaluminum compounds such as trialkylaluminum with organotin oxides such as dimethyltin oxide and dibutyltin oxide in a medium such as decane, benzene, or toluene.

[0088] The aluminoxane may contain a small amount of organometallic components. Alternatively, after removing the solvent or unreacted organoaluminum compounds from the recovered aluminoxane solution by distillation, the obtained aluminoxane may be redissolved in a solvent or suspended in a poor solvent for aluminoxane.

[0089] Specific examples of organoaluminum compounds used in the preparation of aluminoxanes include those similar to those exemplified as organoaluminum compounds belonging to the general formula (B-1a) above.

[0090] Of these, trialkylaluminum and tricycloalkylaluminum are preferred, and trimethylaluminum is particularly preferred. The organoaluminum compounds described above can be used individually or in combination of two or more.

[0091] Solvents used in the preparation of aluminoxanes include aromatic hydrocarbons such as benzene, toluene, xylene, cumene, and cymene; aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, hexadecane, and octadecane; alicyclic hydrocarbons such as cyclopentane, cyclohexane, cyclooctane, and methylcyclopentane; petroleum fractions such as gasoline, kerosene, and diesel fuel; or halogenated compounds of the above aromatic hydrocarbons, aliphatic hydrocarbons, and alicyclic hydrocarbons, particularly chlorinated and brominated hydrocarbon solvents. Furthermore, ethers such as ethyl ether and tetrahydrofuran can also be used. Of these solvents, aromatic hydrocarbons or aliphatic hydrocarbons are particularly preferred. These solvents can be used individually or in combination.

[0092] The organoaluminum oxy compound (B-2) used in the present invention includes aluminoxanes selected from at least one of aluminoxanes having a structure represented by the following general formula (B-2a) or (B-2b), and aluminoxanes having a repeating unit represented by the following general formula (B-2c) and a repeating unit represented by the following general formula (B-2d) as part of their structure.

[0093] [ka] (In the general formula, R cEach of these is independently a hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms, and specific examples of hydrocarbon groups include methyl group, ethyl group, propyl group, isopropyl group, isopropenyl group, n-butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, octyl group, decyl group, dodecyl group, tridecyl group, tetradecyl group, hexadecyl group, octadecyl group, eicosyl group, cyclohexyl group, cyclooctyl group, phenyl group, tolyl group, and ethylphenyl group. Among these examples, methyl group, ethyl group, and isobutyl group are preferred, and methyl group is particularly preferred, and in the general formulas (B-2a), (B-2b), and (B-2c), R c A portion of it may be substituted with halogen atoms such as chlorine or bromine, and the halogen content may be 40% by weight or less.

[0094] In the general formulas (B-2a) and (B-2b) above, r represents an integer between 2 and 500, preferably between 6 and 300, and particularly preferably between 10 and 100. In the above general formulas (B-2c) and (B-2d), s and t each represent an integer of 1 or greater.

[0095] The aluminoxane having the repeating unit represented by the general formula (B-2c) and the repeating unit represented by the general formula (B-2d) is preferably such that its molecular weight, measured by the freezing point depression method of benzene, is in the range of 200 to 2000.

[0096] Furthermore, the benzene-insoluble organoaluminum oxy compounds used in this invention are preferably those in which the Al component that dissolves in benzene at 60°C is typically 10% or less, preferably 5% or less, and particularly preferably 2% or less in terms of Al atoms; in other words, they are preferably insoluble or sparingly soluble in benzene.

[0097] In the present invention, the organoaluminum oxy compound (B-2) can also be an organoaluminum oxy compound containing boron represented by the following general formula (B-2e).

[0098] [ka] (In general formula (B-2e), R 15 This indicates a hydrocarbon group with 1 to 10 carbon atoms, and four R 16 These may be identical or different from each other, and each independently represents a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 10 carbon atoms.

[0099] The boron-containing organoaluminum oxy compound represented by the general formula (B-2e) can be produced by reacting an alkylboronic acid represented by the general formula (B-2f) with an organoaluminum compound in an inert solvent under an inert gas atmosphere at a temperature of -80°C to room temperature for 1 minute to 24 hours.

[0100] R 15 -B(OH)2···(B-2f) (In general formula (B-2f), R 15 R in the above general formula (B-2e) is 15 (It shows the same base.)

[0101] Specific examples of alkylboronic acids represented by the general formula (B-2f) include methylboronic acid, ethylboronic acid, isopropylboronic acid, n-propylboronic acid, n-butylboronic acid, isobutylboronic acid, n-hexylboronic acid, cyclohexylboronic acid, phenylboronic acid, 3,5-difluoroboronic acid, pentafluorophenylboronic acid, and 3,5-bis(trifluoromethyl)phenylboronic acid. Among these, methylboronic acid, n-butylboronic acid, isobutylboronic acid, 3,5-difluorophenylboronic acid, and pentafluorophenylboronic acid are preferred. These can be used individually or in combination of two or more.

[0102] Specific examples of organoaluminum compounds that react with such alkylboronic acids include organoaluminum compounds similar to those exemplified as organoaluminum compounds belonging to the general formula (B-1a) above.

[0103] The organoaluminum compounds mentioned above are preferably trialkylaluminum and tricycloalkylaluminum, and particularly preferably trimethylaluminum, triethylaluminum, and triisobutylaluminum. These can be used individually or in combination of two or more.

[0104] When an organoaluminum oxy compound (B-2), such as methylaluminoxane, is used in combination with a transition metal compound (A) as a co-catalyst component, it exhibits very high polymerization activity towards olefin compounds. The organoaluminum oxy compounds (B-2) described above can be used individually or in combination of two or more.

[0105] ((B-3) Compounds that react with transition metal compounds (A) to form ion pairs) Examples of compounds (B-3) used in the present invention that react with a transition metal compound (A) to form an ion pair (hereinafter referred to as "ionized ionic compound") include Lewis acids, ionic compounds, borane compounds, and carborane compounds described in Japanese Patent Publication No. 1-501950, Japanese Patent Publication No. 1-502036, Japanese Patent Application Publication No. 3-179005, Japanese Patent Application Publication No. 3-179006, Japanese Patent Application Publication No. 3-207703, Japanese Patent Application Publication No. 3-207704, US-5321106, etc. Furthermore, heteropoly compounds and isopoly compounds can also be mentioned.

[0106] Specifically, examples of the Lewis acid include compounds represented by BR3 (where R is a phenyl group or fluorine which may have substituents such as fluorine, a methyl group, or a trifluoromethyl group), such as trifluoroborone, triphenylborone, tris(4-fluorophenyl)borone, tris(3,5-difluorophenyl)borone, tris(4-fluoromethylphenyl)borone, tris(pentafluorophenyl)borone, tris(p-tolyl)borone, tris(o-tolyl)borone, and tris(3,5-dimethylphenyl)borone.

[0107] Examples of the aforementioned ionic compounds include those represented by the following general formula (B-3a).

[0108] [ka] (In general formula (B-3a), R 17 is H + R is a carbonium cation, oxonium cation, ammonium cation, phosphonium cation, cycloheptyltrienyl cation, or ferrocenium cation having a transition metal. 18 ~R 21 These may be the same or different groups, and are organic groups, preferably aryl groups or substituted aryl groups.

[0109] Specific examples of the carbonium cation include trisubstituted carbonium cations such as triphenylcarbonium cation, tri(methylphenyl)carbonium cation, and tri(dimethylphenyl)carbonium cation.

[0110] Examples of the aforementioned ammonium cations include trialkylammonium cations such as trimethylammonium cation, triethylammonium cation, tripropylammonium cation, tributylammonium cation, and tri(n-butyl)ammonium cation; N,N-dialkylanilinium cations such as N,N-dimethylanilinium cation, N,N-diethylanilinium cation, and N,N-2,4,6-pentamethylanilinium cation; and dialkylammonium cations such as di(isopropyl)ammonium cation and dicyclohexylammonium cation.

[0111] Examples of the phosphonium cation include triarylphosphonium cations such as triphenylphosphonium cation, tri(methylphenyl)phosphonium cation, and tri(dimethylphenyl)phosphonium cation.

[0112] R17 As such, carbonium cations and ammonium cations are preferred, and triphenylcarbonium cations, N,N-dimethylanilinium cations, and N,N-diethylanilinium cations are particularly preferred.

[0113] Other examples of ionic compounds include trialkylsubstituted ammonium salts, N,N-dialkylanilinium salts, dialkylammonium salts, and triarylphosphonium salts.

[0114] Specific examples of the aforementioned trialkyl-substituted ammonium salts include triethylammonium tetra(phenyl)boron, tripropylammonium tetra(phenyl)boron, tri(n-butyl)ammonium tetra(phenyl)boron, trimethylammonium tetra(p-tolyl)boron, trimethylammonium tetra(o-tolyl)boron, tri(n-butyl)ammonium tetra(pentafluorophenyl)boron, tripropylammonium tetra(o,p-dimethylphenyl)boron, tri(n-butyl)ammonium tetra(m,m-dimethylphenyl)boron, tri(n-butyl)ammonium tetra(p-trifluoromethylphenyl)boron, tri(n-butyl)ammonium tetra(3,5-ditrifluoromethylphenyl)boron, and tri(n-butyl)ammonium tetra(o-tolyl)boron.

[0115] Specific examples of the aforementioned N,N-dialkylanilinium salts include, for example, N,N-dimethylanilinium tetra(phenyl)boron, N,N-diethylanilinium tetra(phenyl)boron, and N,N,2,4,6-pentamethylanilinium tetra(phenyl)boron.

[0116] Examples of the aforementioned dialkylammonium salts include di(1-propyl)ammonium tetra(pentafluorophenyl)boron and dicyclohexylammonium tetra(phenyl)boron.

[0117] Furthermore, as ionic compounds, we can also mention triphenylcarbenium tetrakis(pentafluorophenyl)borate, N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, ferrocenium tetra(pentafluorophenyl)borate, triphenylcarbenium pentaphenylcyclopentadienyl complex, N,N-diethylanilinium pentaphenylcyclopentadienyl complex, and boron compounds represented by the following formulas (B-3b) or (B-3c).

[0118] [ka] (In formula (B-3b), Et represents an ethyl group.)

[0119] [ka] (In formula (B-3c), Et represents an ethyl group.)

[0120] Examples of ionized ionic compounds (compound (B-3)) specifically include borane compounds such as decaborane; Salts of anions such as 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, and bis[tri(n-butyl)ammonium]dodecachlorododecaborate; Examples include salts of metal borane anions such as tri(n-butyl)ammonium bis(dodecahydridedodecaborate)cobaltate(III) and bis[tri(n-butyl)ammonium]bis(dodecahydridedodecaborate)nickelate(III).

[0121] Examples of ionized ionic compounds include, specifically, carborane compounds such as 4-carbanonaborane, 1,3-dicarbanonaborane, 6,9-dicarbadecaborane, dodecahydride-1-phenyl-1,3-dicarbanonaborane, dodecahydride-1-methyl-1,3-dicarbanonaborane, undecahydride-1,3-dimethyl-1,3-dicarbanonaborane, 7,8-dicarbowndecaborane, 2,7-dicarbowndecaborane, and undecahydride-7,8-dimethyl Tyl-7,8-dicarboundecaporane, dodecahydride-11-methyl-2,7-dicarboundecaporane, tri(n-butyl)ammonium 1-carbadecaborate, tri(n-butyl)ammonium 1-carbadodecaborate, tri(n-butyl)ammonium 1-carbadodecaborate, tri(n-butyl)ammonium 1-trimethylsilyl-1-carbadecaborate, tri(n-butyl)ammonium bromo-1-carbadodecaborate, tri(n-butyl)ammonium 6-carbadecaborate, tri(n-butyl)ammonium 6-carbadecaborate, tri(n-butyl)ammonium 7-carbound decaborate, tri(n-butyl)ammonium 7,8-dicalbound decaborate, tri(n-butyl)ammonium 2,9-dicalbound decaborate, tri(n-butyl)ammonium dodecahydride-8-methyl-7,9-dicalbound decaborate, tri(n-butyl)ammonium undecahydride-8-ethyl-7,9-dical Salts of anions such as bounce decaborate, tri(n-butyl)ammonium undecahydride-8-butyl-7,9-dic bounce decaborate, tri(n-butyl)ammonium undecahydride-8-allyl-7,9-dic bounce decaborate, tri(n-butyl)ammonium undecahydride-9-trimethylsilyl-7,8-dic bounce decaborate, and tri(n-butyl)ammonium undecahydride-4,6-dibromo-7-carb bounce decaborate; Tri(n-butyl)ammonium bis(nonahydride-1,3-dicarbanonaborate)cobaltate (III), tri(n-butyl)ammonium bis(undekahydride-7,8-dicarbowndecaborate)ferrate (III), tri(n-butyl)ammonium bis(undekahydride-7,8-dicarbowndecaborate)cobaltate (III), tri(n-butyl)ammonium bis(undekahydride-7,8-dicarbowndecaborate)niclate (III), tri(n-butyl)ammonium bis(undekahydride-7,8-dicarbowndecaborate)copperate (III), tri(n-butyl)ammonium bis(undekahydride-7,8-dicarbowndecaborate)goldate (III), tri(n-butyl)ammonium bis(nonahydride-7,8-dimethyl-7,8-dicarbowndecaborate)ferric acid Examples include salts of metal carborane anions such as salt (III), tri(n-butyl)ammonium bis(nonahydride-7,8-dimethyl-7,8-dicarboundecaborate)chromate (III), tri(n-butyl)ammonium bis(tribromooctahydride-7,8-dicarboundecaborate)cobaltate (III), tris[tri(n-butyl)ammonium]bis(undekahydride-7-carboundecaborate)chromate (III), bis[tri(n-butyl)ammonium]bis(undekahydride-7-carboundecaborate)manganate (IV), bis[tri(n-butyl)ammonium]bis(undekahydride-7-carboundecaborate)cobaltate (III), and bis[tri(n-butyl)ammonium]bis(undekahydride-7-carboundecaborate)nickelate (IV).

[0122] Heteropoly compounds, which are examples of ionized ionic compounds, are compounds containing an atom selected from silicon, phosphorus, titanium, germanium, arsenic, and tin, and one or more atoms selected from vanadium, niobium, molybdenum, and tungsten. Specifically, these include, but are not limited to, phosphovanadic acid, germanovanadic acid, arsenic vanadic acid, phosphoniobic acid, germanoniobic acid, siliconomolybdic acid, phosphomolybdic acid, titaniummolybdic acid, germanomolybdic acid, arsenic molybdic acid, tinmolybdic acid, phosphotungstic acid, germanotungstic acid, tintungstic acid, phosphomolybdovanadic acid, phosphotungstovanadic acid, germanotungstovanadic acid, phosphomolybdotungstovanadic acid, germanomolybdotungstovanadic acid, phosphomolybdotungstovanadic acid, phosphomolybdoniobic acid, and salts of these acids. Furthermore, examples of the salts include salts of the acid with alkali metals from Group 1 or alkaline earth metals from Group 2 of the periodic table, specifically lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium, etc., and organic salts such as triphenylethyl salts.

[0123] Isopoly compounds, which are examples of ionized ionic compounds, are compounds composed of a metal ion of one atom selected from vanadium, niobium, molybdenum, and tungsten, and can be considered as molecular ionic species of metal oxides. Specifically, examples include, but are not limited to, vanadic acid, niobic acid, molybdic acid, tungstic acid, and salts of these acids. Furthermore, examples of the salts include salts of the acids with metals from Group 1 or 2 of the periodic table, specifically lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium, etc., and organic salts such as triphenylethyl salts.

[0124] The ionized ionic compounds described above (compounds (B-3) that react with transition metal compounds (A) to form ion pairs) are used individually or in combination of two or more types. Furthermore, the catalyst for olefin polymerization according to the present invention may also optionally include the following support (C) along with the above-mentioned transition metal compound (A) (hereinafter sometimes abbreviated as "component (A)") and at least one compound (B) selected from the group consisting of organometallic compounds (B-1), organoaluminum oxy compounds (B-2), and ionized ionic compounds (B-3).

[0125] ((C) Carrier) The carrier (C) used in the present invention is an inorganic or organic compound, and is in the form of a granular or fine particle solid. By supporting the above-mentioned transition metal compound (A) and compound (B) on the carrier (C), a polymer with good morphology can be obtained.

[0126] The inorganic compound is preferably a porous oxide, a solid aluminoxane compound, an inorganic halide, clay, a clay mineral, or an ion-exchangeable layered compound. Specifically, the porous oxide can be SiO2, Al2O3, MgO, ZrO, TiO2, B2O3, CaO, ZnO, BaO, ThO2, or composites or mixtures containing these. Furthermore, natural or synthetic zeolites, SiO2-MgO, SiO2-Al2O3, SiO2-TiO2, SiO2-V2O5, SiO2-Cr2O3, SiO2-TiO2-MgO, etc., can be used. Among these, porous oxides mainly composed of SiO2 and / or Al2O3 are preferred.

[0127] Furthermore, the porous oxide may contain small amounts of carbonates, sulfates, nitrates, and oxide components such as Na2CO3, K2CO3, CaCO3, MgCO3, Na2SO4, Al2(SO4)3, BaSO4, KNO3, Mg(NO3)2, Al(NO3)3, Na2O, K2O, and Li2O.

[0128] Such porous oxides have different properties depending on the type and manufacturing method, but the porous oxides preferably used in the present invention have a particle size of 10 to 300 μm, preferably 20 to 200 μm, and a specific surface area of ​​50 to 1000 m². 2 / g, preferably 100-700m 2 It is in the range of / g, and the pore volume is 0.3-3.0 cm³. 3 It is desirable that the value be within the range of / g. Such porous oxides are used after being calcined at 100-1000°C, preferably 150-700°C, as needed.

[0129] The solid aluminoxane compound mentioned above can be an aluminoxane selected from at least one of the aluminoxanes shown in (B-2a) to (B-2d). The solid aluminoxane used in this invention differs from conventionally known olefin polymerization catalyst supports in that it does not contain inorganic solid components such as silica or alumina, or organic polymer components such as polyethylene or polystyrene, and is solidified with alkylaluminum compounds as the main component. In this invention, "solid" means that the aluminoxane maintains a substantially solid state under the reaction environment in which it is used. More specifically, for example, when preparing a solid catalyst component for olefin polymerization by contacting component (A) and component (B) as described later, it means that component (B) is in a solid state in an inert hydrocarbon solvent such as hexane or toluene used in the reaction, under a specific temperature and pressure environment. Furthermore, for example, when performing suspension polymerization using a solid catalyst component for olefin polymerization prepared using component (B) as described later, it is also a necessary requirement that component (B) contained in the catalyst component is in a solid state in a hydrocarbon solvent such as hexane, heptane, or toluene, under a specific temperature and pressure environment. The same applies to bulk polymerization, where polymerization is carried out in liquefied monomer instead of a solvent, and gas-phase polymerization, where polymerization is carried out in monomer gas.

[0130] Under the above-described environment, visual inspection is the simplest way to determine whether component (B) is in a solid state; however, visual inspection is often difficult, for example, during polymerization. In such cases, it is possible to determine this from, for example, the properties of the polymer powder obtained after polymerization or its adhesion to the reactor. Conversely, if the polymer powder has good properties and minimal adhesion to the reactor, even if some of component (B) dissolves under polymerization conditions, the present invention will not deviate from its purpose. Indicators for determining the properties of the polymer powder include bulk density, particle shape, surface shape, and the degree of presence of amorphous polymers; however, polymer bulk density is preferred from the viewpoint of quantitative accuracy. In the present invention, the bulk density is usually 0.01 to 0.9, preferably 0.05 to 0.6, and more preferably 0.1 to 0.5.

[0131] The solid aluminoxane used in this invention dissolves in n-hexane held at a temperature of 25°C in a range of typically 0 to 40 mol%, preferably 0 to 20 mol%, and particularly preferably 0 to 10 mol%.

[0132] The dissolution ratio of the solid aluminoxane used in this invention in n-hexane was determined by adding 2 g of solid aluminoxane support to 50 ml of n-hexane maintained at 25°C, stirring for 2 hours, then separating the solution using a G-4 glass filter, and measuring the aluminum concentration in the filtrate. Therefore, the dissolution ratio is determined as the ratio of aluminum atoms present in the filtrate to the amount of aluminum atoms corresponding to 2 g of aluminoxane used.

[0133] As the solid aluminoxane, any known solid aluminoxane can be used without limit. Examples of known manufacturing methods include Japanese Patent Publication No. 7-42301, Japanese Patent Publication No. 6-220126, Japanese Patent Publication No. 6-220128, Japanese Patent Publication No. 11-140113, Japanese Patent Publication No. 11-310607, Japanese Patent Publication No. 2000-38410, Japanese Patent Publication No. 2000-95810, and WO2010 / 55652.

[0134] The average particle size of the solid aluminoxane is generally in the range of 0.01 to 50,000 μm, preferably 1 to 1,000 μm, and particularly preferably 1 to 200 μm. The average particle size of solid aluminoxane is determined by observing the particles with a scanning electron microscope, measuring the particle sizes of 100 or more particles, and weight-averaging them. The particle size of solid aluminoxane was measured from the particle image using the Pythagorean method to determine the maximum length. That is, the length of the particle image enclosed by two parallel lines was measured in both the horizontal and vertical directions, and the particle size was calculated using the following formula. Particle size = ((horizontal length)) 2 + (vertical length) 2 ) 0.5

[0135] The weight-average particle size of solid aluminoxane can be calculated using the particle size obtained above, according to the following formula. Average particle size=Σnd 4 / Σnd 3 (where n is the number of particles and d is the particle size)

[0136] The solid aluminoxane preferably used in the present invention has a specific surface area of ​​50 to 1000 m². 2 / g, preferably 100-800m 2 The density is / g, and the pore volume is 0.1-2.5 cm³. 3 It is preferable that the value be / g.

[0137] Examples of inorganic halides include MgCl2, MgBr2, MnCl2, and MnBr2. The inorganic halides may be used as is, or they may be used after being ground using a ball mill or vibration mill. Alternatively, the inorganic halides may be dissolved in a solvent such as alcohol, and then precipitated into fine particles using a precipitating agent.

[0138] The aforementioned clay is usually composed mainly of clay minerals. The ion-exchangeable layered compound is a compound having a crystalline structure in which planes formed by ionic bonds are stacked parallel to each other with weak bonding forces, and the ions it contains are exchangeable. Most clay minerals are ion-exchangeable layered compounds. Furthermore, these clays, clay minerals, and ion-exchangeable layered compounds are not limited to natural sources; artificially synthesized materials can also be used.

[0139] Furthermore, examples of clay, clay minerals, or ion-exchangeable layered compounds include ionic crystalline compounds having layered crystalline structures such as hexagonal close-packing type, antimony type, CdCl2 type, and CdI2 type.

[0140] Furthermore, clays and clay minerals include kaolin, bentonite, kibushi clay, gylome clay, allophane, hisingerite, pyrophyllite, ummo group, montmorillonite group, vermiculite, lyokdiite group, palygorskite, kaolinite, nacrite, dickite, and halloysite. Examples of ion-exchangeable layered compounds include crystalline acidic salts of polyvalent metals such as α-Zr(HAsO4)2·H2O, α-Zr(HPO4)2, α-Zr(KPO4)2·3H2O, α-Ti(HPO4)2, α-Ti(HAsO4)2·H2O, α-Sn(HPO4)2·H2O, γ-Zr(HPO4)2, γ-Ti(HPO4)2, and γ-Ti(NH4PO4)2·H2O.

[0141] Such clays, clay minerals, or ion-exchangeable layered compounds preferably have a pore volume of 0.1 cc / g or more, and particularly preferably 0.3 to 5 cc / g, as measured by the mercury intrusion method for pores with a radius of 20 Å or more. Here, the pore volume is measured in the range of pore radii from 20 to 30,000 Å by the mercury intrusion method using a mercury porosimeter. When using a support material with a pore volume of less than 0.1 cc / g and a radius of 20 Å or more, it tends to be difficult to obtain high polymerization activity.

[0142] It is also preferable to subject the clay and clay minerals used in this invention to chemical treatment. Chemical treatments can include surface treatments to remove impurities adhering to the surface, and treatments that affect the crystalline structure of the clay. Specific examples of chemical treatments include acid treatment, alkali treatment, salt treatment, and organic treatment. Acid treatment removes surface impurities and increases the surface area by dissolving cations such as Al, Fe, and Mg in the crystalline structure. Alkali treatment destroys the crystalline structure of the clay, leading to a change in its structure. Salt treatment and organic treatment can form ionic complexes, molecular complexes, and organic derivatives, thereby altering the surface area and interlayer distance.

[0143] The ion-exchangeable layered compound used in this invention may be a layered compound in which the interlayers are expanded by utilizing ion exchange properties and exchanging the exchangeable ions between layers with other large, bulky ions. Such bulky ions play a supporting role in the layered structure and are usually called pillars. The introduction of another substance between the layers of a layered compound in this way is called intercalation. Possible guest compounds for intercalation include cationic inorganic compounds such as TiCl4 and ZrCl4, metal alkoxides such as Ti(OR)4, Zr(OR)4, PO(OR)3, and B(OR)3 (where R is a hydrocarbon group, etc.), and [Al 13 O4(OH) 24 ] 7+ [Zr4(OH) 14 ] 2+ [Fe3O(OCOCH3)6] + Examples include metal hydroxide ions. These compounds can be used individually or in combination of two or more. Furthermore, when intercalating these compounds, polymers obtained by hydrolyzing metal alkoxides (where R represents a hydrocarbon group, etc.) such as Si(OR)4, Al(OR)3, and Ge(OR)4, or colloidal inorganic compounds such as SiO2 can also be present. In addition, as pillars, oxides produced by heating and dehydrating after intercalating the above-mentioned metal hydroxide ions between layers can also be used.

[0144] The clay, clay minerals, and ion-exchangeable layered compounds used in this invention may be used as is, or after being subjected to treatments such as ball milling or sieving. They may also be used after being newly treated with water adsorption or heat dehydration. Furthermore, they may be used individually or in combination of two or more. Of these, clay or clay minerals are preferred, with montmorillonite, vermiculite, pectolite, teniolite, and synthetic mica being particularly preferred.

[0145] As mentioned above, the support (C) is an inorganic or organic compound, but examples of organic compounds include granular or particulate solids with a particle size in the range of 10 to 300 μm. Specifically, examples include (co)polymers produced mainly from α-olefins with 2 to 14 carbon atoms, such as ethylene, propylene, 1-butene, and 4-methyl-1-pentene, or (co)polymers produced mainly from vinylcyclohexane and styrene, and modified versions thereof.

[0146] The olefin polymerization catalyst according to the present invention may also optionally contain the following specific organic compound component (D) along with the above-mentioned transition metal compound (A), the above-mentioned compound (B), and optionally a support (C).

[0147] ((D) Organic compound component) In the present invention, the organic compound component (D) is used, if necessary, to improve the polymerization performance of the olefin polymerization catalyst of the present invention and the physical properties of the resulting polymer (for example, the molecular weight of the resulting polymer) (in the case of molecular weight, to increase the molecular weight). Examples of such organic compounds include, but are not limited to, alcohols, phenolic compounds, carboxylic acids, phosphorus compounds, and sulfonates.

[0148] The alcohols and phenolic compounds are typically R 22 -The one represented by OH is used, where R 22represents a hydrocarbon group having 1 to 50 carbon atoms (in the case of phenols, the number of carbon atoms is 6 to 50) or a halogenated hydrocarbon group having 1 to 50 carbon atoms (in the case of phenols, the number of carbon atoms is 6 to 50).

[0149] As alcohols, those in which R 22 is a halogenated hydrocarbon group are preferred. As phenolic compounds, those in which the α,α'-positions of the hydroxyl groups are substituted with hydrocarbons having 1 to 20 carbon atoms are preferred.

[0150] As the above carboxylic acid, usually, those represented by R 23 -COOH are used. R 23 represents a hydrocarbon group having 1 to 50 carbon atoms or a halogenated hydrocarbon group having 1 to 50 carbon atoms, and particularly, a halogenated hydrocarbon group having 1 to 50 carbon atoms is preferred.

[0151] As the above phosphorus compound, phosphoric acids having a P-О-H bond, phosphates having a P-ОR, P=О bond, and phosphine oxide compounds are preferably used. As the above sulfonate, those represented by the following general formula (D-a) can be mentioned.

[0152]

Chemical formula

[0153] [Method for producing olefin polymers] The method for producing an olefin polymer according to the present invention includes a step of polymerizing or copolymerizing an olefin in the presence of an olefin polymerization catalyst as described above, thereby obtaining an olefin polymer. As stated above, in this specification, olefin refers to any compound having a polymerizable double bond.

[0154] The method of using each component constituting the catalyst of the present invention in polymerization, and the order of addition to the polymerizer, can be arbitrarily selected, but the following methods are examples. (1) A method of adding a transition metal compound (A) alone to a polymerizer. (2) A method of adding transition metal compound (A) and compound (B) to a polymerizer in any order. (3) A method of adding a catalyst component in which a transition metal compound (A) is supported on a support (C) and a compound (B) to a polymerizer in any order. (4) A method of adding a catalyst component in which compound (B) is supported on a support (C) and a transition metal compound (A) to a polymerizer in any order. (5) A method of adding a catalyst component, in which a transition metal compound (A) and a compound (B) are supported on a support (C), to a polymerizer. (6) A method of adding a catalyst component comprising a transition metal compound (A) and a compound (B) supported on a support (C), and compound (B) to a polymerizer in any order. In this case, the compound (B) supported on the support (C) and the compound (B) added alone may be the same or different. (7) A method of adding a catalyst component in which compound (B) is supported on a support (C), and a transition metal compound (A) to a polymerizer in any order. (8) A method of adding a catalyst component in which compound (B) is supported on a support (C), a transition metal compound (A), and compound (B) to a polymerizer in any order. In this case, compound (B) supported on the support (C) and compound (B) added alone may be the same or different. (9) A method of adding a component in which a transition metal compound (A) is supported on a support (C), and a component in which compound (B) is supported on a support (C), to a polymerizer in any order. (10) A method of adding a component in which a transition metal compound (A) is supported on a support (C), a component in which compound (B) is supported on a support (C), and compound (B) to a polymerizer in any sequence. In this case, compound (B) supported on support (C) and compound (B) added alone may be the same or different. (11) A method for adding a transition metal compound (A), a compound (B), and an organic compound component (D) to a polymerizer in any order. (12) A method of adding a component in which compound (B) and an organic compound component (D) have been brought into contact beforehand, and a transition metal compound (A), to a polymerizer in any order. (13) A method of adding a component in which compound (B) and an organic compound component (D) are supported on a carrier (C), and a transition metal compound (A) to a polymerizer in any order. (14) A method of adding a catalyst component, which consists of a transition metal compound (A) and a compound (B) in prior contact, and an organic compound component (D) to a polymerizer in any order. (15) A method of adding a catalyst component in which a transition metal compound (A) and a compound (B) have been brought into contact beforehand, and compound (B) and an organic compound component (D) to a polymerizer in any order. (16) A method of adding a catalyst component in which a transition metal compound (A) and a compound (B) have been brought into contact beforehand, and a component in which a compound (B) and an organic compound component (D) have been brought into contact beforehand, to a polymerizer in any order. In this case, the compound (B) that is brought into contact with the transition metal compound (A) and the compound (B) that is brought into contact with the organic compound component (D) may be the same or different. (17) A method of adding a component in which a transition metal compound (A) is supported on a carrier (C), a compound (B), and an organic compound component (D) to a polymerizer in any order. (18) A method of adding a component in which a transition metal compound (A) is supported on a carrier (C), and a component in which a compound (B) and an organic compound component (D) have been brought into contact in any order to a polymerizer. (19) A method of adding a catalyst component to a polymerizer, in which a transition metal compound (A), a compound (B), and an organic compound component (D) have been brought into contact in any order beforehand. (20) A method of adding to a polymerization reactor a catalyst component obtained by previously contacting a transition metal compound (A), a compound (B), and an organic compound component (D), and the compound (B) in any order. In this case, the compound (B) contacted with the transition metal compound (A) and the organic compound component (D) and the compound (B) added alone may be the same or different. (21) A method of adding to a polymerization reactor a catalyst in which a transition metal compound (A), a compound (B), and an organic compound component (D) are supported on a carrier (C). (22) A method of adding to a polymerization reactor a catalyst component in which a transition metal compound (A), a compound (B), and an organic compound component (D) are supported on a carrier (C), and the component (B) in any order. In this case, the compound (B) supported on the carrier (C) and the compound (B) added alone may be the same or different.

[0155] In the above 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), olefin may be prepolymerized, and a catalyst component may be further supported on the prepolymerized solid catalyst component.

[0156] In the present invention, the (co)polymerization can be carried out in any of liquid phase polymerization methods such as solution polymerization and suspension polymerization or gas phase polymerization methods. Specific examples of the inert hydrocarbon medium used in the liquid phase polymerization method include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; alicyclic hydrocarbons such as cyclopentane, cyclohexane, and methylcyclopentane; aromatic hydrocarbons such as benzene, toluene, and xylene; halogenated hydrocarbons such as ethylene chloride, chlorobenzene, and dichloromethane, or mixtures thereof, and the olefin itself to be subjected to (co)polymerization can also be used as a solvent.

[0157] When carrying out the polymerization of an olefin using the olefin polymerization catalyst as described above, the transition metal compound (A) is usually 1×10 -12 ~1×10 -2 mol per liter of the reaction volume, preferably 1×10-10 ~1×10 -3 is used in an amount such that it becomes ~1×10 moles.

[0158] The organometallic compound (B-1) is used in an amount such that the molar ratio [(B-1) / M] of the organometallic compound (B-1) to all transition metal atoms (M) in the transition metal compound (A) is usually 0.01 to 100,000, preferably 0.05 to 50,000. The organoaluminum oxy compound (B-2) is used in an amount such that the molar ratio [(B-2) / M] of the aluminum atom in the organoaluminum oxy compound (B-2) to all transition metals (M) in the transition metal compound (A) is usually 10 to 500,000, preferably 20 to 100,000. The compound (ionized ionic compound) (B-3) that reacts with the transition metal compound (A) to form an ion pair is used in an amount such that the molar ratio [(B-3) / M] of the ionized ionic compound (B-3) to the transition metal atom (M) in the transition metal compound (A) is usually 1 to 10, preferably 1 to 5.

[0159] The organic compound component (D) is used in an amount such that the molar ratio [(D) / (B-1)] to the organometallic compound (B-1) is usually 0.01 to 10, preferably 0.1 to 5. The organic compound component (D) is used in an amount such that the molar ratio [(D) / (B-2)] to the organoaluminum oxy compound (B-2) is usually 0.001 to 2, preferably 0.005 to 1. The organic compound component (D) is used in an amount such that the molar ratio [(D) / (B-3)] to the ionized ionic compound (B-3) is usually 0.01 to 10, preferably 0.1 to 5.

[0160] Also, the polymerization temperature of the olefin using such a catalyst for olefin polymerization is usually in the range of -50 to +200 °C, preferably 0 to 170 °C. The polymerization pressure is usually normal pressure to 100 kg / cm 2 -G, preferably normal pressure to 50 kg / cm 2 -G, and the polymerization reaction can be carried out by any of the batch, semi-continuous, and continuous methods. Further, the polymerization can also be carried out in two or more steps with different reaction conditions.

[0161] The molecular weight of the resulting olefin polymer can be adjusted by introducing hydrogen into the polymerization system or by changing the polymerization temperature. Furthermore, it can also be adjusted by the amount of compound (B) used.

[0162] The olefins that can be polymerized by the olefin polymerization catalyst of the present invention are not particularly limited as long as they have polymerizable double bonds, but include linear or branched α-olefins having 2 to 30 carbon atoms, preferably 2 to 20, more preferably 2 to 10, such as ethylene, propylene, 1-butene, 2-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene; Examples of cyclic olefins having 3 to 30 carbon atoms, preferably 3 to 20, and more preferably 3 to 10, include cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene, and 2-methyl-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene.

[0163] The olefin polymerization catalyst of the present invention is more preferably used for the homopolymerization of ethylene, or for the copolymerization of ethylene with an olefin having 3 to 20 carbon atoms, preferably a linear or branched α-olefin having 3 to 10 carbon atoms. The α-olefin may be used alone or in combination of two or more types.

[0164] In the copolymerization of ethylene with an α-olefin having 3 to 20 carbon atoms, preferably 3 to 10 carbon atoms, the α-olefin (hereinafter also referred to as olefin A) is not particularly limited as long as it achieves the effects of the present invention, but for example, propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-octene, and 1-decene are preferred. These α-olefins may be used individually or in combination of two or more. Among these, it is more preferable that at least one selected from 1-butene, 1-hexene, 4-methyl-1-pentene, and 1-octene is used.

[0165] When ethylene is used as the α-olefin and the above-mentioned olefin A is used, the ratio of ethylene to the above-mentioned olefin A used is typically 1:10 to 5000:1, preferably 1:5 to 1000:1, in terms of ethylene:the above-mentioned olefin A (molar ratio).

[0166] The olefin polymerization catalyst of the present invention may (co)polymerize known chain-like unsaturated hydrocarbons having polar groups (for example, carbonyl groups, hydroxyl groups, ether-bonding groups, etc.). Furthermore, the olefin polymerization catalyst of the present invention may be used to (co)polymerize vinylcyclohexane, diene, or polyene, etc.

[0167] Examples of the diene or polyene include cyclic or chain-like compounds having 4 to 30 carbon atoms, preferably 4 to 20, and possessing two or more double bonds. Specifically, these include butadiene, isoprene, 4-methyl-1,3-pentadiene, 1,3-pentadiene, 1,4-pentadiene, 1,5-hexadiene, 1,4-hexadiene, 1,3-hexadiene, 1,3-octadiene, 1,4-octadiene, 1,5-octadiene, 1,6-octadiene, 1,7-octadiene, ethylidene norbornene, vinyl norbornene, and dicyclopentadiene. 7-methyl-1,6-octadiene, 4-ethylidene-8-methyl-1,7-nonadien, 5,9-dimethyl-1,4,8-decatriene; Furthermore, aromatic vinyl compounds, such as mono- or polyalkylstyrenes including styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, o,p-dimethylstyrene, o-ethylstyrene, m-ethylstyrene, and p-ethylstyrene; Functional group-containing styrene derivatives such as methoxystyrene, ethoxystyrene, vinylbenzoic acid, methyl vinylbenzoate, vinylbenzyl acetate, hydroxystyrene, o-chlorostyrene, p-chlorostyrene, and divinylbenzene; Other examples include 3-phenylpropylene, 4-phenylpropylene, and α-methylstyrene.

[0168] In addition, vinylidene-type reactive double-bond-containing compounds such as isobutene, 2-methyl-1-butene, 2-methyl-1-pentene, 2-methyl-1-hexene, and 2-ethyl-1-pentene can also be used. Other examples include at least one cyclic olefin (Z) selected from the group consisting of compounds represented by the following general formulas [ZI], [Z-II], [Z-III], [Z-IV], or [ZV].

[0169] [ka] [In equation [ZI], u is either 0 or 1, v is 0 or a positive integer, w is either 0 or 1. R 61 ~R 78 Furthermore, R a1 and R b1 Each is independently selected from a hydrogen atom, a halogen atom, and a hydrocarbon group, R 75 ~R 78 These may be bonded to each other to form a monocycle or polycycle, and the monocycle or polycycle may have a double bond, and R 75 and R 76 And, or R 77 and R 78 They may form alkylidene groups.

[0170]

Chem.

[0171]

Chem.

[0172]

Chem.

Chem.

[0173] Specific examples of such cyclic olefins include, for example, the compounds disclosed in Japanese Patent Publication No. 2020-164719. Among these, the most preferred specific example is tetracyclo[4.4.0.1 2,5 .1 7,10 It is ]-3-dodecene.

[0174] The transition metal compound (A) of the present invention is characterized in that it has a structure in which elements from different groups of the periodic table, E, Z, and Q, as shown in formula (1), are bonded in a specific positional relationship. The inventors believe that such a structure can be used to exhibit catalytic performance for olefin polymerization with an excellent balance of polymerization activity, high molecular weight, and copolymerizability. Furthermore, by selecting substituents (Rh, Rp in formula (1), and Rr, Rh, Rs in formula (2)), the electron density, electron distribution, and steric hindrance of the transition metal compound can be controlled, so it is thought that the balance of performance such as polymerization activity, high molecular weight, and copolymerizability can be adjusted according to the application and purpose.

[0175] When the transition metal compound (A) of the present invention is used as a catalyst for olefin polymerization, in particular, in copolymerization of cyclic olefin compounds such as tetracyclododecene and cyclic diene compounds such as 5-ethylidene-2-norbornene with olefins, these cyclic compounds tend to react relatively easily, and olefin copolymers with a relatively high content of structural units derived from these cyclic compounds are easily obtained. The reason for this tendency is not yet clear, but the inventors speculate as follows.

[0176] It is generally known that olefin polymerization using transition metal compound catalysts involves a step in which the olefin coordinates to the catalyst. As described above, the transition metal compound (A) of the present invention is particularly characterized by having a structure in which elements from different groups of the periodic table, E, Z, and Q, as shown in formula (1), are directly bonded. Since these so-called heteroatom-unevenly distributed sites are likely to have a unique polarity, olefins and cyclic olefins are likely to coordinate easily. Furthermore, it can be expected that the rate of coordination will be less affected by the stereostructure of the compounds having these olefin double bonds (hereinafter sometimes referred to as olefin compounds) due to the high polarity of the heteroatom-unevenly distributed sites.

[0177] On the other hand, it is known that transition metal compounds with highly polar sites may exhibit strong coordination with olefins, making polymerization of olefins difficult and potentially resulting in low polymerization activity. However, the transition metal compound (A) of the present invention has a structure in which elements from different groups of the periodic table are in a specific positional relationship. It is thought that the difference in their electron density and electronegativity acts as a driving force, pushing the coordinated olefin compound towards the transition metal side of M, which is considered the main active site, thereby promoting the reaction. Furthermore, it is considered preferable that the substituent bonded to Q has a propeller-like structure that rotates easily, such as an aromatic group or a substituted aromatic group. This is because the rotation of the substituent is expected to potentially promote the pushing of the olefin.

[0178] Since the transition metal compound (A) is expected to possess the characteristics described above, it can be considered that it will have the aforementioned excellent balance of performance not only in the polymerization of ethylene but also in copolymerization using olefins with different structures. In particular, characteristic polymerization reactions (e.g., excellent copolymerizability) tend to occur in copolymerization of cyclic olefins or polyene compounds with olefins. (e.g., excellent copolymerizability.) Furthermore, it can be expected that even more characteristic performance will be exhibited depending on the combination with ligand L(l).

[0179] [Olefin polymer] According to the present invention, olefin polymers can be efficiently produced by polymerizing an olefin selected from one or more α-olefins having 2 to 30 carbon atoms in the presence of an olefin polymerization catalyst containing a useful and novel transition metal compound (A) having the specific structure described above; preferably, by homopolymerization of ethylene, or by copolymerization of ethylene with at least one olefin A selected from olefins having 3 to 20 carbon atoms.

[0180] One embodiment of the olefin polymer is an ethylene-based polymer containing ethylene-derived structural units in a range of preferably 50 to 100 mol%, more preferably 70 to 100 mol%, and even more preferably 90 to 100 mol%. The ethylene-based polymer contains olefin A-derived structural units in a range of preferably 0 to 50 mol%, more preferably 0 to 30 mol%, and even more preferably 0 to 10 mol% in total. However, the sum of the content of ethylene-derived structural units and the content of olefin A-derived structural units is 100 mol%. The ethylene-based polymer in which the olefin A-derived structural units are within the above range exhibits excellent moldability. In addition, other structural units may be included without departing from the spirit of the present invention. These contents can be measured by nuclear magnetic resonance spectroscopy, or by infrared spectroscopy if a reference substance is available.

[0181] Among these polymers, ethylene homopolymer, ethylene-propylene copolymer, ethylene-1-butene copolymer, ethylene-propylene-1-butene copolymer, ethylene-1-octene polymer, ethylene-1-hexene polymer, ethylene-4-methyl-1-pentene polymer, ethylene-propylene-1-octene polymer, ethylene-propylene-1-hexene polymer, and ethylene-propylene-4-methyl-1-pentene polymer are particularly preferred. The above copolymers are usually random copolymers, but they may also be so-called block copolymers (impact copolymers) obtained by mixing or continuously producing two or more polymers selected from these polymers.

[0182] Among the polymers having the constituent units described above, α-olefin polymers consisting substantially only of constituent units derived from α-olefins having 2 to 20 carbon atoms are preferred. "Substantially" means that the proportion of constituent units derived from α-olefins having 2 to 20 carbon atoms is 95% by weight or more of the total constituent units.

[0183] In the olefin polymer, the weight-average molecular weight measured by gel permeation chromatography (GPC) is not particularly limited, but is preferably 10,000 to 5,000,000, more preferably 10,000 to 2,000,000, and especially preferably 20,000 to 1,000,000. The molecular weight distribution (Mw / Mn), which is the ratio of the weight-average molecular weight (Mw) to the number-average molecular weight (Mn), is not particularly limited, but is preferably 1 to 10, more preferably 1 to 7, and especially preferably 1 to 5.

[0184] In the olefin polymer, the density is not particularly limited, but is 875 kg / m³. 3 More than 975kg / m 3 The following is preferable: In the olefin polymer, the intrinsic viscosity [η] in decalin at 135°C is not particularly limited, but is preferably 0.1 to 40 dl / g, more preferably 0.5 to 15 dl / g, and most preferably 1 to 10 dl / g.

[0185] In the olefin polymer, the melt mass flow rate (MFR; in units of g / 10 min) measured under conditions of 190°C and a 2.16 kg load in accordance with ASTM D1238-89 is not particularly limited, but is preferably 0.001 g / 10 min or more and 300 g / 10 min or less, and more preferably 0.001 g / 10 min or more and 200 g / 10 min or less.

[0186] Furthermore, it is preferable that the value obtained by dividing the MFR value measured under conditions of 190°C and a 10kg load in accordance with ASTM D1238-89 by the MFR value measured under the conditions of 190°C and a 2.16kg load (I10 / I2) is 5.0 or more and less than 300. The details of the measurement conditions for the above physical properties are as described in the examples. [Examples]

[0187] The present invention will be described in more detail below based on examples, but the present invention is not limited to these examples.

[0188] [Measurement method] Transition metal compounds are 1 The specimen was identified by measuring 1H-NMR spectra (270 MHz, JEOL GSH-270) and FD-mass (FD-MS) spectra (JEOL SX-102A), among others.

[0189] The physical properties of ethylene / 1-octene copolymer and ethylene / propylene / 5-ethylidene-2-norbornene copolymer were measured by the following method. [Comonomer content] The comonomer content of ethylene / 1-octene copolymers and ethylene / propylene / 5-ethylidene-2-norbornene copolymers is determined by FT-IR (Japan Spectroscopic Engineering FT-IR410 infrared spectrophotometer) or 1 The measurement was performed by 1H-NMR.

[0190] (FT-IR measurement method) For FT-IR, the polymer obtained in the examples was heated to 135°C, dissolved and stretched using a hot press, and then cooled under pressure at room temperature. The resulting film was used as the measurement sample, and the 1-octene structural unit content, propylene structural unit content, and 5-ethylidene-2-norbornene structural unit content were measured using a calibration curve. The ethylene / 1-octene copolymer and ethylene / propylene / 5-ethylidene-2-norbornene copolymer samples used for calibration curve preparation were prepared under the same conditions as described above. 13 The comonomer content was determined by 13C-NMR measurement. ( 1 H-NMR measurement) Using o-dichlorobenzene d4 as the measurement solvent, or under measurement conditions of 120°C temperature, 250 ppm spectral width, 7.0 seconds pulse repetition time, and 5.0 μs pulse width (45° pulse) (500 MHz, Bruker BioSpin AVANCE III CRYO-500) 1 1H-NMR measurements were performed. Various signals, such as methyl groups and ethylidene groups, were assigned using conventional methods, and the comonomer content was quantified based on the cumulative signal intensity. The physical properties of the ethylene / TD copolymer were measured using the following method.

[0191] [Tg of the polymer] The translucency (Tg) of the polymer was determined by DSC measurement under the following conditions. Equipment: SII Nanotechnology Co., Ltd. DSC6220 Measurement conditions: A sample held at 300°C for 5 minutes was rapidly cooled to 0°C, and then the Tg was determined during the heating process at a rate of 20°C / min to 250°C.

[0192] [TD content rate] The TD content was calculated using the relationship formula between Tg and TD content measured above. The ethylene / TD copolymer used to create the relational formula was analyzed as follows: In accordance with the descriptions in sections

[0216] to

[0219] of Japanese Patent Publication No. 2011-122146, 13 The TD content of the polymer was determined by 13C-NMR spectroscopy. The relationship was obtained by measuring the Tg at each TD content for these samples and translating these results into a relational equation.

[0193] [Intrinsic viscosity of polymers [η]] The intrinsic viscosity [η] (dl / g) of the olefin polymer was measured in decalin at 135°C according to the method specified in JIS K7367.

[0194] [Weight-average molecular weight (Mw), molecular weight distribution (Mw / Mn) of polymers] The weight-average molecular weight (Mw) and number-average molecular weight (Mn) of the olefin polymer were determined by gel permeation chromatography (GPC). These values ​​were calculated from molecular weight distribution curves obtained using a Tosoh HLC-8321 GPC / HT gel permeation chromatograph (high-temperature size exclusion chromatograph), under the following operating conditions:

[0195] <Equipment and conditions used> Measuring device: Gel permeation chromatograph HLC-8321 GPC / HT type (manufactured by Tosoh Corporation) Analysis software; Chromatography data system Empower (trademark, Waters Inc.) Column; TSKgel GMH6-HT x 2 + TSKgel GMH6-HT x 2 (inner diameter 7.5mm x length 30cm, Tosoh Corporation) Mobile phase: o-dichlorobenzene [ODCB] Detector; differential refractometer (built into the device) Column temperature: 140°C Flow rate; 1.0mL / min Injection volume; 400μL Sampling time interval: 0.5 seconds Sample concentration: 0.15% (w / v) Molecular weight calibration for monodisperse polystyrene (Tosoh Corporation) / Molecular weight #3 std set

[0196] <Production of transition metal compounds> [Synthesis Example 1] (i) Synthesis of ligand I The target substance represented by the following formula (hereinafter also referred to as "ligand I") was synthesized using the method described in Angew. Chem. Int. Ed. 2019, 58, 1.

[0197] [ka]

[0198] (ii) Synthesis of transition metal compound A Under a nitrogen atmosphere, 1605 mg (3.97 mmol) of ligand I was placed in a 100 mL Schlenk flask, and 30 mL of toluene was added. While cooling the Schlenk flask in a dry ice / methanol bath, 2.65 mL (4.16 mmol of n-butyllithium) of 1.57 M n-butyllithium / hexane solution was gradually added, and the temperature was gradually raised to room temperature. The mixture was stirred at room temperature under a nitrogen atmosphere for 4 hours. The solvent was removed under reduced pressure, and the resulting solid was washed with hexane and dried under reduced pressure to obtain 1372 mg of white solid a. Under a nitrogen atmosphere, 175 mg (0.80 mmol) of cyclopentadienyltitanium trichloride was placed in a 100 mL Schlenk flask, and 30 mL of toluene was added. The Schlenk flask was cooled in a dry ice / methanol bath. To this solution, 20 mL of a toluene solution of 328 mg of the white solid a obtained in the previous reaction was added over 10 minutes, washing with 5 mL of toluene. The temperature was gradually raised to room temperature and stirred under a nitrogen atmosphere for 17 hours. The solvent was removed by vacuum distillation, extracted with dichromemethane using Celite, and then concentrated under vacuum. The red solid obtained by extraction with hexane was recovered by filtration. The filtrate was concentrated under vacuum. The red solid was dissolved in hexane and recrystallized at -10°C. The resulting red crystals were recovered by filtration and washed with hexane to obtain 91 mg of the target product represented by the following formula (hereinafter also referred to as "transition metal compound A"). The solid obtained from the filtrate in the previous vacuum concentration was dissolved in hexane and recrystallized at -10°C. The resulting red solid was removed by filtration. The filtrate was concentrated to half its volume under vacuum, and the resulting red crystals were washed with hexane to obtain 85 mg of transition metal compound A represented by the following formula. Total 176 mg, yield 38%. 1 The target substance was identified by 1H-NMR (CDCl3) and FD-MS measurements. The measurement results are shown below. 1 H-NMR(270MHz,CDCl3)δ 1.23(12H,d,J=7Hz),1.29(12H,d,J=7Hz),3.14(4H,sep,J=7Hz),6.03(2H,s),6.17(5H,s),7.23-7.36(6H,m)ppm FD-MS: m / z = 586.2(M + )

[0199] [ka]

[0200] [Synthesis Example 2] (i) Synthesis of transition metal compound B Under a nitrogen atmosphere, 215 mg (0.80 mmol) of indenyltitanium trichloride was placed in a 100 mL Schlenk flask, and 20 mL of toluene was added. The Schlenk flask was cooled in a dry ice / methanol bath. To this solution, 20 mL of a toluene solution of 328 mg of white solid a obtained in the reaction of Synthesis Example 1 was added over 5 minutes while washing with 5 mL of toluene. The temperature was gradually raised to room temperature and stirred under a nitrogen atmosphere for 17 hours. The solvent was removed by vacuum distillation, extracted with dichromemethane using Celite, and then concentrated under vacuum. The obtained solid was dissolved in hexane and recrystallized at -10°C. The resulting red crystals were removed by filtration. The filtrate was concentrated under vacuum, dissolved again in hexane, and recrystallized at -10°C. The resulting red crystals were recovered by filtration, washed with hexane, and dried under vacuum to obtain 82 mg of the target product represented by the following formula (hereinafter also referred to as "transition metal compound B"). 1 The target substance was identified by 1H-NMR (CDCl3) and FD-MS measurements. The measurement results are shown below. 1 H-NMR(270MHz,CDCl3)δ 1.23(12H,d,J=7Hz),1.30(12H,d,J=7Hz),3.16(4H,sep,J=7Hz),5.56(1H,t, J=3Hz),6.04(2H,s),6.28(2H,d,J=3Hz),6.17(5H,s),7.23-7.36(8H,m)ppm, 7.52-7.55(2H,m)ppm FD-MS: m / z = 636.2(M + )

[0201] [ka]

[0202] [Synthesis Example 3] (i) Synthesis of transition metal compound C Under a nitrogen atmosphere, 231 mg (0.80 mmol) of pentamethylcyclopentadienyltitanium trichloride was placed in a 100 mL Schlenk flask, and 20 mL of toluene was added. The Schlenk flask was cooled in a dry ice / methanol bath. To this solution, 20 mL of a toluene solution of 328 mg of white solid a obtained in the reaction of Synthesis Example 1 was added over 10 minutes while washing with 5 mL of toluene. The temperature was gradually raised to room temperature and stirred under a nitrogen atmosphere for 17 hours. The solvent was removed by distillation under reduced pressure, and the mixture was extracted with dichromemethane using Celite, followed by extraction with hexane using Celite. The obtained solid was dissolved in hexane and recrystallized at -10°C. The resulting red crystals were removed by filtration. The filtrate was concentrated under reduced pressure, dissolved again in hexane, and recrystallized at -10°C. This procedure was performed a total of two times. The resulting red crystals were recovered by filtration, washed with hexane, and then dried under reduced pressure to obtain 122 mg of the target product represented by the following formula (hereinafter also referred to as "transition metal compound C"). 1 The target substance was identified by 1H-NMR (CDCl3) and FD-MS measurements. The measurement results are shown below. 1 H-NMR(270MHz,CDCl3)δ 1.18(12H,d,J=7Hz),1.29(12H,d,J=7Hz),1.86(15H,s), 3.20(4H,sep,J=7Hz),5.97(2H,s),7.16-7.29(6H,m)ppm FD-MS: m / z = 656.3(M + )

[0203] [ka]

[0204] [Synthesis Example 4] (i) Synthesis of transition metal compound D Under a nitrogen atmosphere, 283 mg (0.80 mmol) of adamantylcyclopentadienyl titanium trichloride was placed in a 100 mL Schlenk flask, and 25 mL of toluene was added. The Schlenk flask was cooled in a dry ice / methanol bath. To this solution, 20 mL of a toluene solution of 328 mg of white solid a obtained in the reaction of Synthesis Example 1 was added over 10 minutes while washing with 5 mL of toluene. The temperature was gradually raised to room temperature and stirred under a nitrogen atmosphere for 16 hours. The solvent was removed by distillation under reduced pressure, and the mixture was extracted with dichromemethane using Celite, followed by extraction with hexane using Celite. The obtained solid was dissolved in hexane and concentrated under reduced pressure until the solution was reduced to 1 / 10 of its original volume. The resulting red crystals were recovered by filtration, washed with hexane, and dried under reduced pressure to obtain 218 mg (yield 38%) of the target product represented by the following formula (hereinafter also referred to as "transition metal compound D"). 1 The target substance was identified by 1H-NMR (CDCl3) and FD-MS measurements. The measurement results are shown below. 1 H-NMR(270MHz,CDCl3)δ 1.24(12H,d,J=7Hz),1.31(12H,d,J=7Hz),1.62-1.98(15H,m)ppm, 3.18(4H,sep,J=7Hz),5.58(2H,t,J=3Hz),6.03(2H,s),6.48(2H,t,J=3Hz),7.23-7.36(6H,m)ppm FD-MS: m / z = 720.3(M + )

[0205] [ka]

[0206] [Synthesis Example 5] (i) Synthesis of transition metal compound E Under a nitrogen atmosphere, 280 mg (0.70 mmol) of pentafluorophenylmethyl cyclopentadienyl titanium trichloride was placed in a 100 mL Schlenk flask, and 20 mL of toluene was added. The Schlenk flask was cooled in a dry ice / methanol bath. To this solution, 20 mL of a toluene solution of 287 mg of white solid a obtained in the reaction of Synthesis Example 1 was added over 10 minutes while washing with 10 mL of toluene. The temperature was gradually raised to room temperature and stirred under a nitrogen atmosphere for 20 hours. The solvent was removed by distillation under reduced pressure, and the mixture was extracted with dichromemethane using Celite, followed by extraction with hexane using Celite. The obtained solid was dissolved in hexane and recrystallized at -35°C. The resulting red crystals were recovered by filtration, washed with hexane, and dried under reduced pressure to obtain 39 mg of the target product represented by the following formula (hereinafter also referred to as "transition metal compound E"). The filtrate was concentrated under reduced pressure, redissolved in hexane, and recrystallized at -35°C. The resulting red crystals were recovered by filtration, washed with hexane, and dried under reduced pressure to obtain 229 mg of transition metal compound E represented by the following formula. Total 268 mg. Yield 50%. 1 The target substance was identified by 1H-NMR (CDCl3) and FD-MS measurements. The measurement results are shown below. 1 H-NMR(270MHz,CDCl3)δ 1.23(12H,d,J=7Hz),1.29(12H,d,J=7Hz),3.15(4H,sep,J=7Hz),3.88(2H,s ),5.89(2H,t,J=3Hz),6.05(2H,s),6.08(2H,t,J=3Hz),7.23-7.36(6H,m)ppm FD-MS: m / z = 766.3(M + )

[0207] [ka]

[0208] [Synthesis Example 6] (i) Synthesis of ligand precursor II The target product represented by the following formula (hereinafter also referred to as "ligand precursor II") was synthesized using the method described in Tetrahedron Lett. 2004, 45, 6851.

[0209] [ka]

[0210] (ii) Synthesis of ligand II Under a nitrogen atmosphere, 2.52 g (5.88 mmol) of ligand precursor II, 386 mg (9.17 mmol) of calcium hydride, and 35 mL of toluene were added to a 100 mL Schlenk flask. While cooling the Schlenk flask in an ice bath, 7.1 mL (7.1 mmol) of 1 M boron tribromide methylene chloride solution was gradually added, and the temperature was gradually raised to room temperature. The mixture was stirred at room temperature under a nitrogen atmosphere for 24 hours. 2.05 mL (11.77 mmol) of diisopropylethylamine was added and the mixture was stirred for 30 minutes, then methanol was added and the mixture was stirred for 18 hours. The organic phase was separated by adding saturated ammonium chloride aqueous solution, water, and saturated brine, and then dried over magnesium sulfate. The solvent was concentrated under reduced pressure, and the resulting solid was washed with hexane and dried under reduced pressure to obtain 332 mg (11% yield) of ligand II represented by the following formula. 1 The target substance was identified using 1H-NMR (CDCl3). The measurement results are shown below.

[0211] [ka] 1 H-NMR(270MHz,CDCl3)δ 1.14(12H,d,J=7Hz),1.17(12H,d,J=7Hz),2.92(4H,sep,J=7Hz),3.49(1H,s),6.46-6.49(2H,m),6.83-6.86(2H,m),7.29-7.43(6H,m)ppm

[0212] (iii) Synthesis of transition metal compound F Under a nitrogen atmosphere, 454 mg (1.0 mmol) of ligand II was placed in a 50 mL Schlenk flask, and 15 mL of toluene was added. While cooling the Schlenk flask in an ice bath, 0.7 mL of 1.58 M n-butyllithium / hexane solution (1.11 mmol of n-butyllithium) was gradually added, and the temperature was gradually raised to room temperature. The mixture was then stirred at room temperature under a nitrogen atmosphere for 4 hours.

[0213] Under a nitrogen atmosphere, 219 mg (1.0 mmol) of cyclopentadienyltitanium trichloride was placed in a 100 mL Schlenk flask, and 30 mL of toluene was added. The Schlenk flask was cooled in an ice bath. To this solution, the solution obtained in the previous reaction was added over 5 minutes while washing with 5 mL of toluene. The temperature was gradually raised to room temperature and stirred under a nitrogen atmosphere for 18 hours. The solvent was removed by distillation under reduced pressure, and the solution was extracted with dichloromethane using Celite, followed by extraction with hexane using Celite. The obtained solid was dissolved in a small amount of dichloromethane, and recrystallized at -35°C with the addition of hexane. The resulting red crystals were recovered by filtration and washed with hexane to obtain 256 mg of the target product represented by the following formula (hereinafter also referred to as "transition metal compound F"). Yield: 40%. 1 The target substance was identified by 1H-NMR (CDCl3) and FD-MS measurements. The measurement results are shown below. 1 H-NMR(270MHz,CDCl3)δ 1.00(12H,d,J=7Hz),1.17(12H,d,J=7Hz),2.87(4H,sep,J=7Hz),6.15(5H,s),6.46-6.49(2H,m),6.79-6.84(2H,m),7.17-7.36(6H,m)ppm FD-MS: m / z = 636.3(M + )

[0214] [ka]

[0215] [Synthesis Example 7] (i) Synthesis of transition metal compound G Under a nitrogen atmosphere, 331 mg (0.73 mmol) of ligand II synthesized in Synthesis Example 6 was placed in a 50 mL Schlenk flask, and 20 mL of toluene was added. While cooling the Schlenk flask in a dry ice / methanol bath, 0.55 mL (0.86 mmol of n-butyllithium) of 1.57 M n-butyllithium / hexane solution was gradually added, and the temperature was gradually raised to room temperature. The mixture was stirred at room temperature under a nitrogen atmosphere for 4 hours. Under a nitrogen atmosphere, 257 mg (0.73 mmol) of admantylcyclopentadienyl titanium trichloride was placed in a 100 mL Schlenk flask, and 25 mL of toluene was added. The Schlenk flask was cooled in a dry ice / methanol bath. To this solution, the solution obtained in the previous reaction was added over 10 minutes while washing with 10 mL of toluene. The temperature was gradually raised to room temperature, and the mixture was stirred at room temperature under a nitrogen atmosphere for 41 hours. The solvent was removed by vacuum distillation, and the mixture was extracted with dichromemethane using Celite, followed by extraction with hexane using Celite. The resulting solid was dissolved in hexane and recrystallized at -35°C. The resulting red crystals were recovered by filtration, dissolved again in hexane, and recrystallized at -35°C. The resulting red crystals were recovered by filtration, washed with hexane, and dried under reduced pressure to obtain 49 mg of the target product represented by the following formula (hereinafter also referred to as "transition metal compound G"). The filtrate was concentrated under reduced pressure, dissolved in hexane, and recrystallized at -35°C. The resulting red crystals were recovered by filtration, washed with hexane, and dried under reduced pressure to obtain 62 mg of transition metal compound G represented by the following formula. Total 111 mg, yield 20%. 1 The target substance was identified by 1H-NMR (CDCl3) and FD-MS measurements. The measurement results are shown below. 1 H-NMR(270MHz,CDCl3)δ 1.01(12H,d,J=7Hz),1.20(12H,d,J=7Hz),1.54-1.91(15H,m)ppm, 2.91(4H,sep,J=7Hz),5.53(2H,t,J=3Hz),6.46-6.52(4H,m),6.81-6.84(2H,m),7.23-7.36(6H,m)ppm FD-MS: m / z = 770.3(M + )

[0216] [ka]

[0217] [Synthesis Example 8] (i) Synthesis of ligand precursor III (i-1) Synthesis of N-(2-chlorophenyl)-2,6-diisopropylaniline Under a nitrogen atmosphere, 5.95 g (25.0 mmol) of 1-chloro-2-iodobenzene, 4.43 g (25.0 mmol) of 2,6-diisopropylaniline, 256 mg (0.05 mmol) of bis(tri-tert-butylphosphine)palladium, 3.60 g (37.5 mmol) of sodium tert-butoxide, and 80 mL of toluene were added to a 100 mL three-necked flask. The flask was immersed in an oil bath at 110 °C and stirred for 19 hours. The organic phase was separated by adding saturated ammonium chloride aqueous solution, and the aqueous phase was extracted with hexane. The combined organic phase was washed with water and saturated brine, and then dried over magnesium sulfate. The solvent was concentrated under reduced pressure to obtain a black liquid, which was purified by silica gel chromatography (solvent: hexane) to obtain the target product as a colorless liquid (6.61 g, yield 92%). 1 The target substance was identified by the results of 1H-NMR (CDCl3) measurement. The measurement results are shown below. 1 H-NMR(270MHz,CDCl3)δ 1.11(6H,d,J=7Hz),1.18(6H,d,J=7Hz),3.11(2H,sep,J=7Hz),5.66(1H,s), 6.14-6.18(1H,m),6.61-6.66(1H,m), 6.93-6.99(1H,m),7.21-7.35(5H,m)ppm

[0218] (i-2) Synthesis of ligand precursor III Under a nitrogen atmosphere, 2878 mg (10.0 mmol) of N-(2-chlorophenyl)-2,6-diisopropylaniline, 1291 mg (10.0 mmol) of 2,6-difluoroaniline, 204 mg (0.40 mmol) of bis(tri-tert-butylphosphine)palladium, 1.44 g (15.0 mmol) of sodium tert-butoxide, and 50 mL of toluene were added to a 100 mL three-necked flask. The flask was immersed in an oil bath at 110 °C and stirred for 18 hours. After returning to room temperature, saturated ammonium chloride aqueous solution was added to separate the organic phase, and the aqueous phase was extracted with hexane. The combined organic phase was washed with water and saturated brine, and then dried over magnesium sulfate. The solvent was concentrated under reduced pressure to obtain a black-green liquid, which was cooled in a refrigerator. The resulting solid was washed with methanol and dried under reduced pressure to obtain the target product represented by the following formula (hereinafter also referred to as "ligand precursor III") as a gray solid. (1.55g, yield 41%). 1 The target substance was identified by the results of 1H-NMR (CDCl3) measurement. The measurement results are shown below. 1 H-NMR(270MHz,CDCl3)δ 1.16(12H,s),3.16(2H,sep,J=7Hz),5.23(1H,s),5.62(1H,s),6.23(1H,s),6.22-6.26(1H,m), 6.66-6.72(1H,m),6.82-6.97(5H,m),7.17-7.31(4H,m)ppm

[0219] [ka]

[0220] (ii) Synthesis of ligand III Under a nitrogen atmosphere, 1522 mg (4.0 mmol) of ligand precursor III, 262 mg (6.24 mmol) of calcium hydride, and 30 mL of toluene were added to a 100 mL Schlenk flask. While cooling the Schlenk flask in an ice bath, 4.8 mL (4.8 mmol) of 1 M boron tribromide methylene chloride solution was gradually added, and the temperature was gradually raised to room temperature. The mixture was stirred at room temperature under a nitrogen atmosphere for 19 hours. 1.20 mL (6.89 mmol) of diisopropylethylamine was added and the mixture was stirred for 90 minutes, then cooled in an ice bath. 1 mL of pyridine and 30 mL of distilled water were added and the mixture was stirred for 20 hours. The organic phase was separated by adding saturated ammonium chloride aqueous solution and washed three times with saturated ammonium chloride aqueous solution. The combined aqueous phase was extracted twice with hexane. The combined organic phase was washed with saturated ammonium chloride aqueous solution, water, and saturated brine, and then dried over magnesium sulfate. The solvent was concentrated under reduced pressure, and the resulting solid was washed with hexane and dried under reduced pressure to obtain 998 mg (yield 61%) of ligand III represented by the following formula. 1 The target substance was identified using 1H-NMR (CDCl3). The measurement results are shown below. 1 H-NMR(270MHz,CDCl3)δ 1.10(6H,d,J=7Hz),1.17(6H,d,J=7Hz),2.90(2H,sep,J=7Hz),3.68(1H,s),6.43-6.46 (1H,m),6.73-6.77(1H,m),6.85-6.95(2H,m),7.05-7.14(2H,m),7.27-7.44(5H,m)ppm

[0221] [ka]

[0222] (iii) Synthesis of transition metal compound H Under a nitrogen atmosphere, 488 mg (1.20 mmol) of ligand III was placed in a 50 mL Schlenk flask, and 15 mL of toluene was added. While cooling the Schlenk flask in an ice bath, 0.9 mL of 1.58 M n-butyllithium / hexane solution (1.42 mmol of n-butyllithium) was gradually added, and the temperature was gradually raised to room temperature. The mixture was stirred at room temperature under a nitrogen atmosphere for 4 hours. Under a nitrogen atmosphere, 263 mg (1.20 mmol) of cyclopentadienyltitanium trichloride was placed in a 100 mL Schlenk flask, and 25 mL of toluene was added. The Schlenk flask was cooled in an ice bath. To this solution, the solution obtained in the previous reaction was added over 5 minutes while washing with 5 mL of toluene. The temperature was gradually raised to room temperature, and the mixture was stirred at room temperature under a nitrogen atmosphere for 21 hours. The solvent was removed by distillation under reduced pressure, and the solution was extracted with dichromemethane using Celite, followed by extraction with hexane using Celite. The obtained solid was dissolved in a small amount of dichromemethane, hexane was added, and recrystallization was performed at -35°C. The resulting orange solid and solution were separated by decantation, and the solution was concentrated under reduced pressure. The obtained solid was dissolved in a small amount of dichromemethane, hexane was added, and recrystallization was performed at -35°C. The resulting orange solid and solution were separated by decantation, and the solution was concentrated under reduced pressure. Washed with hexane and dried under reduced pressure, 352 mg of the target product represented by the following formula (hereinafter also referred to as "transition metal compound H") was obtained. Yield 50%. 1 The target substance was identified by 1H-NMR (CDCl3) and FD-MS measurements. The measurement results are shown below. 1 H-NMR(270MHz,CDCl3)δ 1.08(6H,d,J=7Hz),1.26(6H,d,J=7Hz),2.91(2H,sep,J=7Hz),6.17(5H,s),6.53-7.45(10H,m)ppm FD-MS: m / z = 588.1(M + )

[0223] [ka]

[0224] [Synthesis Example 9] Synthesis of transition metal compound I Under a nitrogen atmosphere, 370 mg (1.00 mmol) of Ti(N=P(t-Bu)3)Cl3 was placed in a 300 mL Schlenk flask, and 30 mL of toluene was added. While cooling the flask in a dry ice / methanol bath, 2.8 mL of 1.09 M methyllithium / diethyl ether solution (3.05 mmol of methyllithium) was gradually added, and the temperature was gradually raised to room temperature. The mixture was stirred under a nitrogen atmosphere at room temperature for 2 hours. To this solution, while cooling again in a dry ice / methanol bath, 30 mL of toluene solution containing 454 mg (1.00 mmol) of ligand II synthesized in Synthesis Example 6 was added over 30 minutes, washing with 15 mL of toluene. After gradually raising the temperature to room temperature, the mixture was stirred under a nitrogen atmosphere at room temperature for 21 hours to obtain a slurry. The solvent was removed by distillation under reduced pressure, and the mixture was extracted with dichromemethane using Celite, followed by extraction with hexane using Celite. The obtained solid was washed with pentane and dried under reduced pressure to obtain 288 mg of the target product represented by the following formula (hereinafter also referred to as "transition metal compound I"). Yield: 38%. 1 The target substance was identified by 1H-NMR (CDCl3) measurement. The measurement results are shown below. 1 H-NMR(270MHz,CDCl3)δ 0.10(6H,s)ppm, 1.11(12H,d,J=7Hz),1.20(12H,d,J=7Hz),1.27(27H,d,J=13Hz), 3.13(4H,sep,J=7Hz),6.45-6.48(4H,m),6.80-6.83(2H,m),7.23-7.34(6H,m)ppm

[0225] [ka]

[0226] [Comparative Example 1 of Synthesis] Synthesis of transition metal compound a A transition metal compound a having the structure of the following formula was synthesized by the method described in Organometallics, 1998, 17, 2152-2154.

[0227] [ka]

[0228] <Production of ethylene polymers> [Polymerization Example 1-1] A 500 mL glass reactor, thoroughly purged with nitrogen, was charged with 250 mL of toluene, and the liquid and gas phases were saturated with ethylene at a rate of 100 L / hr. Then, 0.1 mmol (in terms of aluminum atoms) of triisobutylaluminum, 0.2 μmol of transition metal compound C, and subsequently 0.8 μmol of triphenylcarbenium tetrakis(pentafluorophenyl) borate were added to initiate polymerization. Ethylene was continuously supplied at a rate of 100 L / hr, and polymerization was carried out at atmospheric pressure at 50°C for 5 minutes. Polymerization was then stopped by adding a small amount of methanol. After polymerization, the reaction mixture was added to 750 mL of methanol containing a small amount of hydrochloric acid to precipitate the polymer. After washing with the same solvent, the mixture was dried under reduced pressure at 80°C for 10 hours to obtain 1.985 g of ethylene polymer. The physical properties of the obtained polymer are shown in Table 1.

[0229] [Polymerization Examples 1-2] Polymerization was carried out in the same manner as in Polymerization Example 1-1, except that 0.05 μmol of transition metal compound D and 0.2 μmol of triphenylcarbenium tetrakis(pentafluorophenyl) borate were used instead of transition metal compound C, yielding 1.475 g of ethylene polymer. The physical properties of the polymer are shown in Table 1.

[0230] [Polymerization Examples 1-3] Polymerization was carried out in the same manner as in Polymerization Example 1-1, except that 0.2 μmol of transition metal compound E was used instead of transition metal compound C, and 0.782 g of ethylene polymer was obtained. The physical properties of the polymer are shown in Table 1.

[0231] [Polymerization Comparative Example 1-1] Polymerization was carried out in the same manner as in Polymerization Example 1-1, except that 1.25 mmol of triisobutylaluminum (calculated as aluminum atoms), 2.5 μmol of transition metal compound a instead of transition metal compound C, and 10 μmol of triphenylcarbenium tetrakis(pentafluorophenyl) borate were used, and 1.762 g of ethylene polymer was obtained. The physical properties of the obtained polymer are shown in Table 1.

[0232] [Table 1]

[0233] [Polymerization Example 2-1] A 500 mL glass reactor, thoroughly purged with nitrogen, was charged with 250 mL of toluene, and the liquid and gas phases were saturated with ethylene at a rate of 100 L / hr. Then, 0.5 mmol of triisobutylaluminum (in terms of aluminum atoms), 0.001 mmol of transition metal compound I, and subsequently 0.004 mmol of triphenylcarbenium tetrakis(pentafluorophenyl) borate were added to initiate polymerization. Ethylene was continuously supplied at a rate of 100 L / hr, and polymerization was carried out at atmospheric pressure and 50°C for 5 minutes. Polymerization was then stopped by adding a small amount of methanol. After polymerization, the reaction mixture was added to 750 mL of methanol containing a small amount of hydrochloric acid to precipitate the polymer. After washing with the same solvent, the mixture was dried under reduced pressure at 80°C for 10 hours to obtain 0.201 g of ethylene polymer. The physical properties of the obtained polymer are shown in Table 2.

[0234] [Table 2]

[0235] <Production of ethylene / 1-octene copolymer> [Polymerization Example 3-1] A 500 mL glass reactor, thoroughly purged with nitrogen, was charged with 250 mL of toluene, and the liquid and gas phases were saturated with ethylene at a rate of 100 L / hr. Then, 2 mL of 1-octene, 0.1 mmol of triisobutylaluminum (calculated as aluminum atoms), 0.05 μmol of transition metal compound D, and subsequently 0.2 μmol of triphenylcarbenium tetrakis(pentafluorophenyl) borate were added to initiate polymerization. Ethylene was continuously supplied at a rate of 100 L / hr, and polymerization was carried out at 60°C for 10 minutes under atmospheric pressure. Polymerization was then stopped by adding a small amount of methanol. After polymerization, the reaction mixture was added to a 1000 mL mixed solvent of methanol and acetone (2:1) containing a small amount of hydrochloric acid to precipitate the polymer. After washing with the solvent, the polymer was dried under reduced pressure at 120°C for 10 hours to obtain 0.454 g of ethylene / 1-octene copolymer. The physical properties of the obtained polymer are shown in Table 3.

[0236] [Polymerization Example 3-2] Polymerization was carried out in the same manner as in Polymerization Example 3-1, except that 0.1 mmol of triisobutylaluminum (calculated as aluminum atoms), 0.2 μmol of transition metal compound E instead of transition metal compound D, and 0.8 μmol of triphenylcarbenium tetrakis(pentafluorophenyl) borate were used, yielding 1.174 g of ethylene / 1-octene copolymer. The physical properties of the polymer are shown in Table 3.

[0237] [Polymerization Comparative Example 3-1] Polymerization was carried out in the same manner as in Polymerization Example 3-2, except that 0.2 μmol of transition metal compound a was used instead of transition metal compound E, yielding 1.158 g of ethylene / 1-octene copolymer. The physical properties of the polymer are shown in Table 3.

[0238] [Table 3]

[0239] <Production of ethylene / tetracyclododecene copolymer> [Polymerization Example 4-1] In a 500 mL glass reactor that has been thoroughly purged with nitrogen, add 250 mL of cyclohexane / hexane(9 / 1) mixed solution and tetracyclo[4.4.0.1 2,5 .1 7,10 10 g of ]-3-dodecene (hereinafter also simply referred to as "TD") was charged, and the liquid and gas phases were saturated with ethylene at a rate of 50 L / hr. Then, 1.0 mmol of triisobutylaluminum (calculated by aluminum atoms), 0.002 mmol of transition metal compound A, and subsequently 0.008 mmol of triphenylcarbenium tetrakis(pentafluorophenyl) borate were added to initiate polymerization. Ethylene was continuously supplied at a rate of 50 L / hr, and polymerization was carried out at atmospheric pressure and 50°C for 10 minutes. Polymerization was then stopped by adding a small amount of isobutanol. After polymerization was complete, the reaction mixture was added to 1 liter of acetone / methanol (3 / 1) mixed solvent containing a small amount of hydrochloric acid to precipitate the polymer. After washing with the same solvent, the mixture was dried under reduced pressure at 130°C for 10 hours to obtain 1.118 g of ethylene / TD copolymer. The physical properties of the obtained polymer are shown in Table 4.

[0240] [Polymerization Example 4-2] Polymerization was carried out in the same manner as in Polymerization Example 4-1, except that 0.5 mmol of triisobutylaluminum (calculated on an aluminum atom basis), 0.001 mmol of transition metal compound E was used instead of transition metal compound A, and 0.004 mmol of triphenylcarbenium tetrakis(pentafluorophenyl) borate was used, yielding 0.267 g of ethylene / TD copolymer. The physical properties of the polymer are shown in Table 4.

[0241] [Polymerization Example 4-3] Polymerization was carried out in the same manner as in Polymerization Example 4-1, except that 1.0 mmol of triisobutylaluminum (calculated on an aluminum atom basis), 0.002 mmol of transition metal compound F instead of transition metal compound A, and 0.008 mmol of triphenylcarbenium tetrakis(pentafluorophenyl) borate were used, yielding 0.172 g of ethylene / TD copolymer. The physical properties of the polymer are shown in Table 4.

[0242] [Polymerization Example 4-4] Polymerization was carried out in the same manner as in Polymerization Example 4-2, except that 250 mL of toluene was used instead of a cyclohexane / hexane(9 / 1) mixed solution, yielding 1.946 g of ethylene / TD copolymer. The physical properties of the polymer are shown in Table 4.

[0243] [Polymerization Examples 4-5] Polymerization was carried out in the same manner as in Polymerization Example 4-3, except that 250 mL of toluene was used instead of a cyclohexane / hexane(9 / 1) mixed solution, yielding 2.705 g of ethylene / TD copolymer. The physical properties of the polymer are shown in Table 4.

[0244] [Polymerization Examples 4-6] Polymerization was carried out in the same manner as in Polymerization Example 4-2, except that 250 mL of toluene was used instead of the cyclohexane / hexane(9 / 1) mixed solution, and 0.001 mmol of transition metal compound G was used instead of transition metal compound E, yielding 1.539 g of ethylene / TD copolymer. The physical properties of the polymer are shown in Table 4.

[0245] [Polymerization Comparative Example 4-1] Polymerization was carried out in the same manner as in Polymerization Example 4-1, except that 2.5 mmol of triisobutylaluminum (calculated in terms of aluminum atoms), 0.005 mmol of transition metal compound a instead of transition metal compound A, and 0.02 mmol of triphenylcarbenium tetrakis(pentafluorophenyl) borate were used, yielding 0.114 g of ethylene / TD copolymer. The physical properties of the polymer are shown in Table 4. Tg was not observed.

[0246] [Polymerization Comparative Example 4-2] Polymerization was carried out in the same manner as in Polymerization Comparative Example 4-1, except that 250 mL of toluene was used instead of a cyclohexane / hexane(9 / 1) mixed solution, and 0.224 g of ethylene / TD copolymer was obtained. The physical properties of the polymer are shown in Table 4.

[0247] [Table 4]

[0248] As described above, the olefin polymerization catalyst of the present invention exhibits excellent performance in any one of the following areas (preferably two or more) in the homopolymerization and copolymerization of olefins: high activity, high molecular weight formation, and copolymerizability.

[0249] [Polymerization Example 5-1] 1030 mL of hexane and 12 mL of 5-ethylidene-2-norbornene (ENB) were charged into a 2 L stainless steel autoclave that had been thoroughly purged with nitrogen. After raising the temperature of the system to 95°C, propylene was charged at a partial pressure of 0.30 MPa, and ethylene was supplied to bring the total pressure to 1.6 MPa-G. Next, 0.3 mmol of triisobutylaluminum, 0.0005 mmol of transition metal compound D prepared in Synthesis Example 4, and 0.002 mmol of triphenylcarbenium tetrakis(pentafluorophenyl) borate were injected under nitrogen pressure, and polymerization was started by increasing the stirring speed to 250 rpm. Subsequently, the total pressure was maintained at 1.6 MPa-G by continuously supplying only ethylene, and polymerization was carried out at 95°C for 15 minutes. After the predetermined time had elapsed, polymerization was stopped by adding a small amount of ethanol to the system, and then unreacted ethylene was purged. The obtained polymer solution was added to a large excess methanol / acetone mixture to precipitate the polymer. The polymer was recovered by filtration and dried overnight under reduced pressure at 120°C to obtain 2.33 g of ethylene / propylene / ENB copolymer. The physical properties of the obtained polymer are shown in Table 5.

[0250] [Polymerization Example 5-2] Polymerization was carried out in the same manner as in Polymerization Example 5-1, except that the partial pressure of propylene was set to 0.40 MPa, and 1.59 g of ethylene / propylene / ENB copolymer was obtained. The physical properties of the polymer are shown in Table 5.

[0251] [Polymerization Example 5-3] Polymerization was carried out in the same manner as in Polymerization Example 5-1, except that the partial pressure of propylene was set to 0.45 MPa, and 3.09 g of ethylene / propylene / ENB copolymer was obtained. The physical properties of the polymer are shown in Table 5.

[0252] [Polymerization Example 5-4] Polymerization was carried out in the same manner as in Polymerization Example 5-1, except that the partial pressure of propylene was set to 0.90 MPa, and 1.51 g of ethylene / propylene / ENB copolymer was obtained. The physical properties of the polymer are shown in Table 5.

[0253] [Polymerization Comparative Example 5-1] Polymerization was carried out in the same manner as in Polymerization Example 5-1, except that transition metal compound a was used instead of transition metal compound D, and 1.03 g of ethylene / propylene / ENB copolymer was obtained. The physical properties of the polymer are shown in Table 5.

[0254] [Polymerization Comparative Example 5-2] Polymerization was carried out in the same manner as in Polymerization Comparative Example 5-1, except that the partial pressure of propylene was set to 0.40 MPa, and 0.64 g of ethylene / propylene / ENB copolymer was obtained. The physical properties of the polymer are shown in Table 5.

[0255] [Table 5]

[0256] The results disclosed in Table 5 show that when copolymerization of an olefin and a cyclic diene compound is performed using the olefin polymerization catalyst containing the transition metal compound (A) of the present invention, copolymers with relatively high content of propylene and 5-ethylidene-2-norbornene (ENB) are obtained. In other words, the olefin polymerization catalyst containing the transition metal compound (A) of the present invention is a catalyst with excellent copolymerization properties.

Claims

1. A transition metal compound (A) defined by the following formula (1): 【Chemistry 1】 [In formula (1), L(l) is an anionic ligand containing hydrogen and an element selected from the group consisting of Group 13 elements, Group 14 elements, and Group 15 elements of the periodic table, and l is a positive integer that is the same as the valence of the anionic ligand. When l is 2 or more, the plural L(l) are each independently the anionic ligand, and are bonded to each other to form a ring, or are not bonded to each other. M is an atom of a transition metal element of Groups 3 to 11 of the periodic table. n is a positive integer. X represents a hydrogen atom, a halogen atom, or a substituent selected from the group consisting of a hydrocarbon group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a boron-containing group, an aluminum-containing group, a phosphorus-containing group, a halogen-containing group, a heterocyclic compound residue, a silicon-containing group, a germanium-containing group, and a tin-containing group. When n is 2 or more, the multiple Xs are each independently a hydrogen atom, a halogen atom, or the above-mentioned substituents, and may be bonded to each other to form a ring or may not be bonded to each other. E represents an oxygen atom or a sulfur atom. Z represents a boron atom. The two Qs each independently represent an atom of an element in Group 15 of the periodic table. m is a positive integer. When m is 2 or more, the plurality of groups represented by the following formula (1') may be the same or different and may be bonded to each other to form a ring or may not be bonded to each other. 【Chemistry 2】 The sum of l, m, and n is the same as the valence of M. A plurality of Rh's and Rp's are each independently a hydrogen atom, a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, or a halogen atom; The plurality of Rh's and Rp's are each independently a hydrocarbon group, and a hydrogen atom, a carbon atom, or both contained in the hydrocarbon are either substituted with a structure containing at least one atom selected from the group consisting of a nitrogen atom, an oxygen atom, a phosphorus atom, a halogen atom, and a silicon atom, or are not substituted with the structure. Two or more of Rh and Rp are bonded to each other to form a monocyclic or polycyclic ring, or are not bonded to each other, and when two or more of Rh and Rp are bonded to each other, adjacent substituents are directly bonded to each other to form a covalent bond (including a multiple bond), or are not directly bonded to each other.

2. 2. The transition metal compound (A) according to claim 1, wherein M is an atom of a transition metal element of Group 4 or 5 of the periodic table.

3. 3. The transition metal compound (A) according to claim 2, wherein M is a titanium atom.

4. The transition metal compound (A) according to claim 1, wherein E is an oxygen atom.

5. The transition metal compound (A) according to claim 1, which is a transition metal compound (A1) specified by the following formula (2): 【Transformation 3】 [In formula (2), L, M, X, E, Z, Q, Rh, l, n, and m are respectively defined as L, M, X, E, Z, Q, Rh, l, n, and m in formula (1); Rr represents a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, or a covalent bond between C and C; Rr is a hydrocarbon group, and a hydrogen atom, a carbon atom, or both contained in the hydrocarbon are either substituted with a structure containing at least one atom selected from the group consisting of a nitrogen atom, an oxygen atom, a phosphorus atom, a halogen atom, and a silicon atom, or are not substituted with the structure. Each of the multiple Rs independently represents a hydrogen atom, a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, or a halogen atom; The multiple Rs each independently represent a hydrocarbon group, and a hydrogen atom, a carbon atom, or both contained in the hydrocarbon are either substituted with a structure containing at least one atom selected from the group consisting of a nitrogen atom, an oxygen atom, a phosphorus atom, a halogen atom, and a silicon atom, or are not substituted with the structure. Two or more of Rr, Rs, and Rh are bonded to each other to form a monocyclic or polycyclic ring, or are not bonded to each other, and when two or more of Rr, Rs, and Rh are bonded to each other, adjacent substituents are directly bonded to each other to form a covalent bond (including a multiple bond), or are not directly bonded to each other.

6. The transition metal compound (A) according to claim 5, which is a transition metal compound (A2) specified by the following formula (3) or the following formula (4): 【Chemistry 4】 [In formulas (3) and (4), M, X, E, Z, Q, Rh, Rr, Rs, n, and m are respectively defined as M, X, E, Z, Q, Rh, Rr, Rs, n, and m in formula (2). Each of the multiple R's is independently a hydrogen atom, a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, or a halogen atom; or A plurality of R's each independently represent a hydrocarbon group, and a hydrogen atom, a carbon atom, or both contained in the hydrocarbon are either substituted with a structure containing at least one atom selected from the group consisting of a nitrogen atom, an oxygen atom, a phosphorus atom, a halogen atom, and a silicon atom, or are not substituted with the structure.

7. A transition metal compound (A) according to any one of claims 1 to 6, (B-1) organometallic compound, (B-2) an organoaluminum oxy compound, and (B-3) A compound that reacts with the transition metal compound to form an ion pair At least one compound (B) selected from the group consisting of A catalyst for olefin polymerization comprising:

8. A method for producing an olefin polymer, which comprises polymerizing an olefin in the presence of the olefin polymerization catalyst according to claim 7.

9. The method for producing an olefin polymer according to claim 8, wherein the olefin comprises an α-olefin having 2 to 30 carbon atoms.

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