JP2023133255A - Transition metal compound, catalyst for olefin polymerization, and method for producing olefin polymer - Google Patents

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

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

As a catalyst for producing olefin polymers such as ethylene/α-olefin copolymers, catalysts comprising a metallocene compound and a cocatalyst such as an organoaluminumoxy compound are known.

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

（式中、ＭはＴｉ等の周期表４族の遷移金属を表し、Ｌは周期表１５族の元素が配位原子となる１価のアニオン性配位子を表し、Ｘはハロゲン等を表し、ｍは１～３の整数を表し、Ｒ¹～Ｒ⁵は、水素、ハロゲン又は炭素原子数１～２０のアルキル基等を表す。）

(In the formula, M represents a transition metal of group 4 of the periodic table such as Ti, L represents a monovalent anionic ligand whose coordination atom is an element of group 15 of the periodic table, and X represents a halogen etc. , m represents an integer of 1 to 3, and R ¹ to R ⁵ represent hydrogen, halogen, or an alkyl group having 1 to 20 carbon atoms, etc.)

ethylene and/or an α-olefin having 3 to 20 carbon atoms and at least one cyclic A method for producing a cyclic olefin copolymer that is copolymerized with an olefin compound is described, and specific examples of the transition metal compound (A) include CpTi(t-Bu ₂ C=N)Cl ₂ and Cp as a comparative example. ^* Ti(2,6- ⁱ Pr ₂ PhO)Cl ₂ is mentioned. (Cp represents a cyclopentadienyl group, and Cp ^* represents an η ⁵ -pentamethylcyclopentadienyl group.)

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

The applicant has reported a metal complex with a new structure and a method for producing an olefin polymer using the same. (For example, Patent Document 3)

Japanese Patent Application Publication No. 2007-63409 Special table 2016-534165 publication JP 2021-116302 Publication

The market continues to demand polymerization catalysts with excellent polymerization activity, high molecular weight, and copolymerizability, and olefin polymers produced using the catalysts.
Therefore, an object of the present invention is to provide a novel transition metal compound useful as a catalyst for olefin (co)polymerization.

The present invention also provides catalysts for olefin polymerization that are suitable for producing various olefin copolymers (for example, suitable for one or more of the following performances: polymerization activity, high molecular weight of polymers, and olefin copolymerizability) and olefin polymerization catalysts suitable for producing various olefin copolymers. A further object is to provide a method for producing an olefin polymer using a polymerization catalyst.

As a result of studies in view of the above-mentioned problems and objectives, the present inventors have discovered that a compound having a specific complex structure exhibits a preferable effect as a component of an olefin polymerization catalyst, and has completed the present invention. That is, the present invention has the following configuration.

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

〔式（１）において、
Ｌ(ｌ)は、水素と、周期表の第１３族元素、第１４族元素、および第１５族元素からなる群から選ばれる元素とを含むアニオン系配位子であり、ｌは前記アニオン系配位子の価数と同一の正の整数である。
ｌが２以上の場合は、複数あるＬ(ｌ)は、それぞれ独立に、前記アニオン系配位子であり、互いに結合して環を形成しているか、または互いに結合していない。
Ｍは、周期表の第３～１１族遷移金属元素の原子である。
ｎは、正の整数である。
Ｘは、水素原子、ハロゲン原子、または炭化水素基、酸素含有基、イオウ含有基、窒素含有基、ホウ素含有基、アルミニウム含有基、リン含有基、ハロゲン含有基、ヘテロ環式化合物残基、ケイ素含有基、ゲルマニウム含有基、およびスズ含有基からなる群から選ばれる置換基を示す。ｎが２以上の場合は、複数あるＸは、それぞれ独立に、水素原子、ハロゲン原子、または前記置換基であり、互いに結合して環を形成しているか、または互いに結合していない。
Ｅは、酸素原子、または硫黄原子を示す。
Ｚは、ホウ素原子を示す。
２つあるＱは、それぞれ独立に、周期表の第１５族元素の原子を示す。
ｍは正の整数である。
ｍが２以上の場合は、複数ある下式（１’）で表される基は、互いに同一であるか、または相違し、互いに結合して環を形成しているか、または互いに結合していない。

[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; It is a positive integer that is the same as the valence of the ligand.
When l is 2 or more, each of the plurality of L(l)s is independently the above-mentioned anionic ligand, and either is bonded to each other to form a ring or not bonded to each other.
M is an atom of a transition metal element belonging to groups 3 to 11 of the periodic table.
n is a positive integer.
X is a hydrogen atom, a halogen atom, a hydrocarbon group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a boron-containing group, an aluminum-containing group, a phosphorus-containing group, a halogen-containing group, a heterocyclic compound residue, silicon represents a substituent selected from the group consisting of a containing group, a germanium-containing group, and a tin-containing group. When n is 2 or more, the plurality of X's are each independently a hydrogen atom, a halogen atom, or the above-mentioned substituent, and either bond to each other to form a ring or do not bond to each other.
E represents an oxygen atom or a sulfur atom.
Z represents a boron atom.
The two Q's each independently represent an atom of a Group 15 element in the periodic table.
m is a positive integer.
When m is 2 or more, the plurality of groups represented by the following formula (1') are the same or different, and are bonded to each other to form a ring, or are not bonded to each other. .

ｌ、ｍ、およびｎの和は、Ｍの価数と同一である。
複数あるＲｈおよびＲｐは、それぞれ独立に、水素原子、置換もしくは無置換の炭素数１～２０の炭化水素基、またはハロゲン原子であり、あるいは
複数あるＲｈおよびＲｐは、それぞれ独立に、炭化水素基であって、前記炭化水素に含まれる水素原子、炭素原子、またはその両方は、窒素原子、酸素原子、リン原子、ハロゲン原子、およびケイ素原子からなる群より選ばれる少なくとも１種の原子を含む構造で置換されているか、または前記構造で置換されていない。
ＲｈおよびＲｐの内の２つ以上は、互いに結合して単環または多環を形成しているか、または互いに結合しておらず、ＲｈおよびＲｐの内の２つ以上が互いに結合する場合、隣接する置換基同士は、互いに直接結合して共有結合（多重結合を含む）形成しているか、または互いに直接結合していない。〕

The sum of l, m, and n is the same as the valence of M.
A plurality of Rh and Rp are each independently a hydrogen atom, a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, or a halogen atom, or a plurality of Rh and Rp are each independently a hydrocarbon group. A structure in which the hydrogen atom, carbon atom, or both contained in the hydrocarbon contains at least one type of atom selected from the group consisting of a nitrogen atom, an oxygen atom, a phosphorus atom, a halogen atom, and a silicon atom. or unsubstituted with the above 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 The substituents are either directly bonded to each other to form a covalent bond (including multiple bonds), or are not directly bonded to each other. ]

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

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

[4]
The transition metal compound (A) according to any one of [1] to [3] above, wherein E is an oxygen atom.

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

〔式（２）において、
Ｌ、Ｍ、Ｘ、Ｅ、Ｚ、Ｑ、Ｒｈ、ｌ、ｎおよびｍは、それぞれ前記式（１）におけるＬ、Ｍ、Ｘ、Ｅ、Ｚ、Ｑ、Ｒｈ、ｌ、ｎおよびｍと同義であり、
Ｒｒは、置換もしくは無置換の炭素数１～２０の炭化水素基、またはＣとＣとの共有結合を示し、あるいは
Ｒｒは、炭化水素基であって、前記炭化水素に含まれる水素原子、炭素原子、またはその両方は、窒素原子、酸素原子、リン原子、ハロゲン原子、およびケイ素原子からなる群より選ばれる少なくとも１種の原子を含む構造で置換されているか、または前記構造で置換されていない。
複数あるＲｓは、それぞれ独立に、水素原子、置換もしくは無置換の炭素数１～２０の炭化水素基、またはハロゲン原子であり、あるいは
複数あるＲｓは、それぞれ独立に、炭化水素基であって、前記炭化水素に含まれる水素原子、炭素原子、またはその両方は、窒素原子、酸素原子、リン原子、ハロゲン原子、およびケイ素原子からなる群より選ばれる少なくとも１種の原子を含む構造で置換されているか、または前記構造で置換されていない。
Ｒｒ、Ｒｓ、およびＲｈの内の２つ以上は、互いに結合して単環または多環を形成しているか、または互いに結合しておらず、Ｒｒ、Ｒｓ、およびＲｈの内の２つ以上が互いに結合する場合、隣接する置換基同士は、互いに直接結合して共有結合（多重結合を含む）形成しているか、または互いに直接結合していない。〕

[In formula (2),
L, M, X, E, Z, Q, Rh, 1, n and m are synonymous with L, M, can be,
Rr is a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, or a covalent bond between C and C, or Rr is a hydrocarbon group, and the hydrogen atom, carbon The atom, or both, is 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 is not substituted with the above structure. .
A plurality of Rs is each independently a hydrogen atom, a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, or a halogen atom, or a plurality of Rs is each independently a hydrocarbon group, Hydrogen atoms, carbon atoms, 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 not substituted with the above 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 two or more of Rr, Rs, and Rh are When bonded to each other, adjacent substituents are either directly bonded to each other to form a covalent bond (including multiple bonds), or are not directly bonded to each other. ]

[6]
The transition metal compound (A) of [5] above, which is a transition metal compound (A2) specified by the following formula (3) or the following formula (4).

〔式（３）および（４）において、
Ｍ、Ｘ、Ｅ、Ｚ、Ｑ、Ｒｈ、Ｒｒ、Ｒｓ、ｎおよびｍは、それぞれ前記式（２）におけるＭ、Ｘ、Ｅ、Ｚ、Ｑ、Ｒｈ、Ｒｒ、Ｒｓ、ｎおよびｍと同義であり、
複数あるＲは、それぞれ独立に、水素原子、置換もしくは無置換の炭素数１～２０の炭化水素基、またはハロゲン原子であり、あるいは
複数あるＲは、それぞれ独立に、炭化水素基であって、前記炭化水素に含まれる水素原子、炭素原子、またはその両方は、窒素原子、酸素原子、リン原子、ハロゲン原子、およびケイ素原子からなる群より選ばれる少なくとも１種の原子を含む構造で置換されているか、または前記構造で置換されていない。〕

[In formulas (3) and (4),
M, X, E, Z, Q, Rh, Rr, Rs, n and m are respectively synonymous with M, X, E, Z, Q, Rh, Rr, Rs, n and m in the above formula (2). can be,
A plurality of R's are each 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 are each independently a hydrocarbon group, Hydrogen atoms, carbon atoms, 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 not substituted with the above structure. ]

[7]
The transition metal compound (A) of any one of [1] to [6] above,
(B-1) organometallic compound,
(B-2) an organoaluminumoxy compound; and (B-3) at least one compound (B) selected from the group consisting of a compound that reacts with the transition metal compound to form an ion pair. catalyst.

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

[9]
The method for producing an olefin polymer according to [8] above, wherein the olefin contains an α-olefin having 2 to 30 carbon atoms.

The transition metal compound of the present invention is useful as a catalyst for olefin (co)polymerization.
When the transition metal compound of the present invention is used as a catalyst for the polymerization or copolymerization of ethylene or olefins having 3 or more carbon atoms, it exhibits characteristics in one or more of the following performances: polymerization activity, high molecular weight of the polymer, and olefin copolymerizability. For example, high molecular weight polyolefins, olefin copolymers whose melting points can be lowered, cyclic olefin copolymers exhibiting a high glass transition temperature, etc. can be provided with high activity.

The transition metal compound according to the present invention is specified by the following structure. Further, when the transition metal compound is used in an olefin polymerization reaction, it is preferably used in combination with an organometallic compound containing an element of Group 1, Group 2, or Group 13 of the periodic table, such as an organoaluminum compound. Each component will be explained below.

[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).

The above L (l) is an anionic ligand containing hydrogen and an element selected from Group 13 elements, Group 14 elements, and Group 15 elements of the periodic table, and l is the valence of the anionic ligand. are the same positive integer. When l is 2 or more, the plurality of anionic ligands represented by L(l) may be the same or different, and the plurality of anionic ligands represented by L(l) may bond to each other. Contains a structure that forms a ring.

Examples of such L(l) include hydrocarbon-based anionic ligands such as cyclopentadienyl and fluorenyl groups. In addition, anionic ligands containing a heteroatom such as a halogen or a heteroatom-containing substituent such as an alkoxy group, an amino group, an imino group, a phosphino group, or a silyl group in the hydrocarbon type anionic ligand are also suitable. There may be cases where this is the case. As a substituent for such a substituent-containing hydrocarbon ligand, a halogen atom is preferable in some cases, and fluorine is more preferable.

Examples of other ligands include elements selected from Group 13 elements, Group 14 elements, and Group 15 elements of the periodic table, such as phosphine imino type, phosphine amino type, and phosphine oxy type. Examples include anionic ligands and anionic polydentate ligands such as trispyrazolylborate. These structures are often monovalent anionic ligands, but polyvalent anionic ligands can also be used.
Among the above, preferred structures are a (substituted) cyclopentadienyl type ligand and a phosphineimino group ligand.

The above M is an atom of a transition metal element of Groups 3 to 11 of the periodic table. Such transition metal elements also include lanthanide and actinide type elements. Preferably, the element is selected from transition metal elements of Groups 4 and 5 of the periodic table. Specific examples include titanium, zirconium, hafnium, and vanadium. Such an element may be a component having excellent polymerization activity in the olefin polymerization catalyst described below, for example. Particularly preferred is titanium. Titanium, for example, may be a component of an olefin polymerization catalyst from which a high molecular weight product is easily obtained.
The above n is a positive integer.

The above X is 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, Indicates a substituent selected from the group consisting of a silicon-containing group, a germanium-containing group, and a tin-containing group, and when n is 2 or more, multiple groups represented by X may be the same or different, and The plurality of groups shown include structures that are bonded to each other to form a ring. Preferred examples of X include a halogen atom or a hydrocarbon group. Examples of the halogen atom include fluorine, chlorine, bromine and iodine, preferably chlorine and bromine, particularly preferably chlorine. Examples of the hydrocarbon group 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, and n-butyl group. and isopropyl group. Further, when a plurality of Xs are linked to form a ring, examples thereof include a butylene group, a pentamethylene group, and a hexamethylene group.

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

The above Q represents an atom selected from Group 15 elements of the periodic table, and two Q's may be the same or different. Among these, nitrogen is particularly preferred from the viewpoints of availability, performance-cost balance, and the like.

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 the plurality of groups represented by the following formula (1') may be bonded to each other to form a ring. Contains structures that form.

The above 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, particularly preferably 1. m is preferably 1 to 3, more preferably 1 to 2, particularly preferably 1. n is preferably 1-4, more preferably 1-3, particularly preferably 1-2. Further, the sum of l, m, and n is preferably 6 or less.

Each of the plurality of Rh and Rp is a group 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 Rh and Rp can include a structure substituted with at least one kind of atom selected from the group consisting of a nitrogen atom, an oxygen atom, a phosphorus atom, a halogen atom, and a silicon atom.

More detailed examples of the above-mentioned substituents containing nitrogen, oxygen, phosphorus, halogen and silicon include hydrocarbon groups having substituents containing nitrogen, oxygen, phosphorus, halogen and silicon. Such substituents can be selected from known structures. More specifically, carbonyl structure-containing groups such as carboxylic acid ester groups, aldehyde groups, acetyl groups, and oxycarbonyl alkyl groups, alkoxy groups, substituted or unsubstituted alkoxy groups, substituted or unsubstituted alkenyloxy groups, and substituted or unsubstituted cycloalkyloxy group, substituted or unsubstituted cycloalkenyloxy group, substituted or unsubstituted aryloxy group, substituted or unsubstituted heteroaryl group, substituted or unsubstituted heteroaryloxy group, or siloxy group etc. can be cited as suitable examples. The above heteroatoms are preferably nitrogen and oxygen, more preferably oxygen.

Among the above-mentioned heteroatom-containing substituents, aryl groups containing an oxygen-containing substituent, specifically, alkoxy groups, aryloxy groups, alkoxyalkyl groups, aryloxyalkyl groups in the aromatic skeleton, and Examples include a structure in which an oxygen-containing substituent such as a substituent substituted with a carbonyl group or a carboxyl group is bonded to an aromatic group. Among the above, substituents in which an alkoxy group or aryloxy 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 still more preferably 1 to 6. More specifically, in addition to the above-mentioned methoxyphenyl group, preferred examples include ethoxyphenyl group, propyloxyphenyl group, isopropyloxyphenyl group, butoxyphenyl group, and phenoxyphenyl group.
In addition, an aryl group containing a halogen atom may also be suitable, and fluorine is a preferred example of the halogen.

Further, it may be preferable that at least one substituent of Rh and Rp described above is a substituent other than hydrogen from the viewpoint of balance of activity, high molecular weight, copolymerizability, and the like. Specific examples of such substituents will be described later, but substituents with bulky structures may be preferable, such as hydrocarbon groups containing secondary carbons and tertiary carbons, aromatic substituents containing bulky alkyl groups, etc. (a group having a so-called hindered structure), and the like. Such a bulky substituent structure may be preferable from the viewpoint of controlling the electron density and steric effect of the transition metal compound (A), and from the viewpoint of activity, high molecular weight, and copolymerizability.
More specific examples of substituents will be given below.

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

A suitable example of Rh and Rp may be a cyclic saturated hydrocarbon group having 3 to 20 carbon atoms. Specifically, hydrogen atoms of cyclic saturated hydrocarbon groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, norbornenyl group, 1-adamantyl group, 2-adamantyl group, etc. Examples include 3-methylcyclopentyl group, 3-methylcyclohexyl group, 4-methylcyclohexyl group, 4-cyclohexylcyclohexyl group, 4-phenylcyclohexyl group, which is a group in which is replaced with a hydrocarbon group having 1 to 17 carbon atoms. Ru. The number of carbon atoms in the cyclic saturated hydrocarbon group is preferably 5 to 11.

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

Examples of the cyclic unsaturated hydrocarbon group having 3 to 20 carbon atoms include cyclopentadienyl group, norbornyl group, phenyl group, naphthyl group, indenyl group, azulenyl group, phenanthryl group, anthracenyl group, etc. 3-methylphenyl group (m-tolyl group), 4-methylphenyl group (p-tolyl group), 4-ethylphenyl group, which is a group in which the hydrogen atom of the group is replaced with a hydrocarbon group having 1 to 15 carbon atoms. , 4-t-butylphenyl group, 4-cyclohexylphenyl group, biphenylyl group, 3,4-dimethylphenyl group, 3,5-dimethylphenyl group, 2,4,6-trimethylphenyl group (mesityl group), etc. Examples include a benzyl group and a cumyl group, which are groups in which a hydrogen atom of a chain hydrocarbon group or a branched saturated hydrocarbon group is replaced with a cyclic saturated hydrocarbon group or a cyclic unsaturated hydrocarbon group having 3 to 19 carbon atoms. Ru. The number of carbon atoms in the cyclic unsaturated hydrocarbon group is preferably 6 to 10.

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

Examples of the arylene group having 6 to 20 carbon atoms include o-phenylene group, m-phenylene group, p-phenylene group, and 4,4'-biphenylylene group. The arylene group preferably has 6 to 12 carbon atoms.

Examples of aryl groups include phenyl groups, 1-naphthyl groups, and 2-naphthyl groups, which are substituents derived from aromatic compounds, although some overlap with the examples of cyclic unsaturated hydrocarbon groups having 3 to 20 carbon atoms described above. Examples include anthracenyl group, phenanthrenyl group, tetracenyl group, chrysenyl group, pyrenyl group, indenyl group, azulenyl group, pyrrolyl group, pyridyl group, furanyl group, and thiophenyl group. The aryl group is preferably a phenyl group or a 2-naphthyl group.

Examples of the 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. be done.

The substituted aryl group partially overlaps with the above-mentioned example of the cyclic unsaturated hydrocarbon group having 3 to 20 carbon atoms, but the aryl group includes a hydrocarbon group in which one or more hydrogen atoms have 1 to 20 carbon atoms, Examples include groups substituted with substituents selected from aryl groups, silicon-containing groups, nitrogen-containing groups, oxygen-containing groups, halogen atoms, and halogen-containing groups, specifically 3-methylphenyl groups (m-tolyl groups). ), 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, 4-aminophenyl group, 4-(dimethylamino)phenyl group, 4-(diethylamino)phenyl group, 4-morpholinylphenyl group, 4-methoxyphenyl group, 4-ethoxyphenyl group, 4-phenoxyphenyl group group, 3,4-dimethoxyphenyl group, 3,5-dimethoxyphenyl group, 3-methyl-4-methoxyphenyl group, 3,5-dimethyl-4-methoxyphenyl group, 3-(trifluoromethyl)phenyl group, Examples include 4-(trifluoromethyl)phenyl group, 3-chlorophenyl group, 4-chlorophenyl group, 3-fluorophenyl group, 4-fluorophenyl group, 5-methylnaphthyl group, 2-(6-methyl)pyridyl group, etc. be done. Preferred aryl groups other than those mentioned above include substituted aryl groups containing so-called higher alkyl groups such as isopropyl, s-butyl, and t-butyl, and particularly preferred are hindered aryl groups having a bulky structure. Further, examples of the substituted aryl group include "electron-donating group-containing substituted aryl group" described below.

Examples of silicon-containing groups include alkyl groups such as trimethylsilyl group, triethylsilyl group, t-butyldimethylsilyl group, and triisopropylsilyl group, which are groups in which a carbon atom is replaced with a silicon atom in a hydrocarbon group having 1 to 20 carbon atoms. Examples include arylsilyl groups such as silyl group, dimethylphenylsilyl group, methyldiphenylsilyl group, and t-butyldiphenylsilyl group, pentamethyldisilanyl group, and trimethylsilylmethyl group. The alkylsilyl group preferably has 1 to 10 carbon atoms, and the arylsilyl group preferably has 6 to 18 carbon atoms.

Examples of the nitrogen-containing group include an amino group, a nitro group, an N-morpholinyl group, a group in which the =CH- structural unit in the above-mentioned hydrocarbon group having 1 to 20 carbon atoms or a silicon-containing group is replaced with a nitrogen atom, - A group in which the CH ₂ - structural unit is replaced with a nitrogen atom to which a hydrocarbon group having 1 to 20 carbon atoms is bonded, or a group in which the -CH ₃ structural unit is replaced by a nitrogen atom to which a hydrocarbon group having 1 to 20 carbon atoms is bonded, or Examples include groups substituted with nitrile groups such as dimethylamino group, diethylamino group, dimethylaminomethyl group, cyano group, pyrrolidinyl group, piperidinyl group, and pyridinyl group. As the nitrogen-containing group, a dimethylamino group and an N-morpholinyl group are preferred.

Examples of the oxygen-containing group include a hydroxyl group, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, or a nitrogen-containing group in which the -CH ₂ - structural unit is replaced with an oxygen atom or a carbonyl group, or - _Methoxy group, ethoxy group, t-butoxy group, phenoxy group, trimethylsiloxy group, methoxyethoxy group, hydroxy Methyl group, methoxymethyl group, ethoxymethyl group, t-butoxymethyl group, 1-hydroxyethyl group, 1-methoxyethyl group, 1-ethoxyethyl group, 2-hydroxyethyl group, 2-methoxyethyl group, 2-ethoxy Ethyl group, n-2-oxapentylene group, n-2-oxapentylene group, n-3-oxapentylene group, aldehyde group, acetyl group, propionyl group, benzoyl group, trimethylsilylcarbonyl group, carbamoyl group, methylamino Examples include a carbonyl group, a carboxy group, a methoxycarbonyl group, a carboxymethyl group, an ethocarboxymethyl group, a carbamoylmethyl group, a furanyl group, and a pyranyl group. As the oxygen-containing group, a methoxy group is preferred.

Examples of the halogen atom include atoms of Group 17 elements such as fluorine, chlorine, bromine, and iodine.
Examples of the halogen-containing group include a trifluoromethyl group, which is a group in which a hydrogen atom in the above-mentioned hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, a nitrogen-containing group, or an oxygen-containing group is substituted with a halogen atom, and a tribromo group. Examples include a methyl group, a pentafluoroethyl group, and a pentafluorophenyl group.

At least one of Rh and Rp is preferably a substituent according to the above preferred embodiment.
Two or more of Rh and Rp can be bonded to each other to form a monocyclic or polycyclic ring, and adjacent substituents can be directly bonded to form a multiple bond. In the present invention, a transition metal compound having a structure in which a plurality of Rp's bond together to form a ring structure is preferred. Examples of such compounds include compounds having the structure of formula (2) below.

The above Rr represents a hydrogen atom, a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, or simply a covalent bond, and the hydrogen atom, carbon atom, or both may be a nitrogen atom, an oxygen atom, a phosphorus atom, It can include a structure substituted with at least one type of atom selected from the group consisting of a halogen atom and a silicon atom.

Examples of such structures include structures corresponding to the divalent substituents Rh and Rp described above. Further, when Rr is a mere covalent bond, it may be either a single bond or a double bond. Preferably, it is in the form of a double bond. In the case of a double bond, the above formula (2) is represented by the following formula (2'), and when Rs bonded to two carbons in the above formula (2) directly bond to each other to form a covalent bond. It can be considered that this applies to

A more preferred embodiment in which Rr forms a double bond is an embodiment in which Rs bonded to adjacent carbons further bond to each other to form a cyclic structure. The cyclic structure in this case is preferably an aryl type structure in addition to a cycloalkene structure.
Each of the plurality of Rs above is a group 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, the carbon atom, or both of Rs are nitrogen atoms. atomic, oxygen atom, phosphorus atom, halogen atom, and silicon atom. Specific examples of Rs are the same as Rh and Rp.

Two or more of the above Rr, Rs, and Rh can be bonded to each other to form a monocyclic or polycyclic ring, and adjacent substituents can also be directly bonded to form a multiple bond.
More preferable embodiments of the structure of the above formula (2) include structures of the following formulas (3) and (4).

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, performance such as activity, high molecular weight, and copolymerizability tends to be easily adjusted by changing the structures of various substituents.
Specific examples of the transition metal compound (A) satisfying the above requirements include compounds having the following structures.

（Ａｄｍは、１－アダマンチル基、または２－アダマンチル基を表す。）

(Adm represents a 1-adamantyl group or a 2-adamantyl group.)

In the present invention, the above transition metal compound (A) may be used alone or in combination of two or more.
The transition metal compound (A) can be manufactured with reference to "Synthesis Experimental Examples" etc. described later. More specifically, for example, a method may be mentioned in which an anion at a site represented by the formula (1') is reacted with a transition metal halide corresponding to another site.

The latter transition metal halide is a commercially available product, but it can also be produced by a well-known method of reacting an anion corresponding to L(l) with a transition metal halide. Further, when X in formula (1) is a hydrocarbon group or the like, it can be synthesized by a well-known method of reacting the above-mentioned halide with a corresponding Grignard reagent or an organometallic compound such as alkyllithium.

As another method, for example, when X is an alkyl group, a compound is generated by alkylating a transition metal halide corresponding to the other moiety, and the compound is reacted with a hydroxy compound corresponding to the moiety represented by formula (1') above. Here are some ways to do it. An example of a synthesis reaction formula corresponding to the above method can be expressed by the following formula. (This is an example of a method for synthesizing a transition metal compound different from Synthesis Example 9 described later.)

In addition, it is also possible to synthesize the transition metal compound of the present invention using known reactions.
The former compound corresponding to the moiety represented by the above formula (1') is a compound corresponding to a structural moiety containing Q and Rp, specifically an anion of a group 15 element-containing compound such as an amine compound or an aniline compound. can be produced by a known method of reacting with a boron halide compound.

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

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

(Component (B) used in combination with transition metal compound (A))
As the above-mentioned component (B) of the present invention, the following components (B-1) to (B-3) can be mentioned.

((B-1) Organometallic compound)
Specifically, the organometallic compound (B-1) used in the present invention is a member of Groups 1, 2, 12, and 13 of the periodic table represented by the following general formulas (B-1a) to (B-1c). Compounds containing at least one element may be mentioned:
R ^ap _Al (OR ^b ) _q H _r Y _s ...(B-1a)
(In general formula (B-1a), R ^a and R ^b may be the same or different and represent a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, and Y is a halogen atom. , p is 0<p≦3, q is 0≦q<3, r is 0≦r<3, s is a number of 0≦s<3, and m+n+p+q=3). organoaluminum compounds;
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.) Complex alkylated products of Group 1 alkali metals and aluminum;
R ^d R ^e M ⁴ ...(B-1c)
(In general formula (B-1c), R ^d and R ^e may be the same or different and represent a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, and M ⁴ is Mg , Zn or Cd) or an alkaline earth metal of Group 2 of the periodic table or a metal of Group 12 of the periodic table.

Examples of the organoaluminum compound belonging to the general formula (B-1a) include the following compounds.
R ^ap _Al (OR ^b ) _3-p ...(B-1a-1)
(In formula (B-1a-1), 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, and p is preferably is a number of 1.5≦p≦3.) An organoaluminum compound represented by
R ^ap _{AlY 3-p} ...(B-1a-2)
(In 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 0<p<3 organoaluminum compound represented by
R ^ap AlH _{3-p ...} (B-1a-3)
(In 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.) Organoaluminum compounds represented,
R ^ap _Al (OR ^b ) _q Y _s ...(B-1a-4)
(In formula (B-1a-4), 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, and Y is a halogen an organoaluminum compound represented by an 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.

More specifically, the organoaluminum compounds belonging to the general formula (B-1a) include trimethylaluminum, triethylaluminum, tri-n-butylaluminum, tripropylaluminum, tripentylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum Tri-n-alkyl aluminum such as;
Triisopropylaluminium, triisobutylaluminum, trisec-butylaluminum, tritert-butylaluminum, tri2-methylbutylaluminum, tri3-methylbutylaluminum, tri2-methylpentylaluminum, tri3-methylpentylaluminium, tri-4 - tri-branched alkyl aluminum such as methylpentylaluminum, tri2-methylhexylaluminum, tri3-methylhexylaluminum, tri2-ethylhexylaluminum;
Tricycloalkyl aluminum such as tricyclohexyl aluminum and tricyclooctyl aluminum;
triaryl aluminum such as triphenyl aluminum and tritolyl aluminum;
Dialkyl aluminum hydride such as diisobutyl aluminum hydride;
Triisoprenyl aluminum represented by (i-C ₄ H ₉ ) _x Al _y (C ₅ H ₁₀ ) _z (wherein x, y, and z are positive numbers, and z≧2x), etc. Trialkenyl aluminum such as;
Alkylaluminium alkoxides such as isobutylaluminum methoxide, isobutylaluminum ethoxide, isobutylaluminum isopropoxide;
Dialkyl aluminum alkoxides such as dimethyl aluminum methoxide, diethylaluminum ethoxide, dibutyl aluminum butoxide;
Alkylaluminium sesquialkoxides such as ethylaluminum sesquiethoxide and butylaluminum sesquibutoxide;
Partially alkoxylated alkylaluminum having an average composition of R ^a _2.5 Al(OR ^b ) _0.5 , where R ^a and R ^b may be the same or different from each other and the number of carbon atoms is 1 to 15, preferably 1 to 4 hydrocarbon groups);
Diethylaluminium phenoxide, diethylaluminium (2,6-di-t-butyl-4-methylphenoxide), ethylaluminum bis(2,6-di-t-butyl-4-methylphenoxide), diisobutylaluminum (2,6- dialkyl aluminum aryoxides such as di-t-butyl-4-methylphenoxide) and isobutylaluminum bis(2,6-di-t-butyl-4-methylphenoxide);
Dialkyl aluminum halides such as dimethylaluminum chloride, diethylaluminum chloride, dibutylaluminum chloride, diethylaluminum bromide, diisobutylaluminum chloride;
Alkylaluminum sesquihalides such as ethylaluminum sesquichloride, butylaluminum sesquichloride, ethylaluminum sesquibromide;
Partially halogenated aluminum alkyls such as alkyl aluminum dihalides such as ethyl aluminum dichloride, propyl aluminum dichloride, butyl aluminum dibromide;
Dialkyl aluminum hydride such as diethylaluminum hydride and dibutyl aluminum hydride;
Other partially hydrogenated alkyl aluminum dihydrides such as ethyl aluminum dihydride, propyl aluminum dihydride;
Mention may be made of partially alkoxylated and halogenated alkylaluminiums, such as ethylaluminum ethoxy chloride, butylaluminum butoxychloride, ethylaluminum ethoxybromide, and the like.

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. Specific examples of such compounds include (C ₂ H ₅ ) ₂ AlN(C ₂ H ₅ )Al(C ₂ H ₅ ) ₂ and the like.

Examples of the compound belonging to the general formula (B-1b) include LiAl(C ₂ H ₅ ) ₄ and LiAl(C ₇ H ₁₅ ) ₄ .
Examples of the compounds belonging to the general formula (B-1c) include dimethylmagnesium, diethylmagnesium, dibutylmagnesium, butylethylmagnesium, dimethylzinc, diethylzinc, diphenylzinc, di-n-propylzinc, diisopropylzinc, di-n- Examples include butylzinc, diisobutylzinc, bis(pentafluorophenyl)zinc, dimethylcadmium, diethylcadmium, and the like.

In addition, examples of the organometallic compound (B-1) include methyllithium, ethyllithium, propyllithium, butyllithium, methylmagnesium bromide, methylmagnesium chloride, ethylmagnesium bromide, ethylmagnesium chloride, propylmagnesium bromide, propylmagnesium Chloride, butylmagnesium bromide, butylmagnesium chloride, etc. can also be used.

In addition, a compound that forms the organoaluminum compound in the polymerization system, such as a combination of aluminum halide and alkyl lithium, or a combination of aluminum halide and alkyl magnesium, is added to the organometallic compound (B-1). It can also be used as

Among the organometallic compounds (B-1), organoaluminum compounds are preferred from the viewpoint of catalytic activity.
The above organometallic compounds (B-1) may be used alone or in combination of two or more.

((B-2) Organoaluminumoxy compound)
The organoaluminumoxy compound (B-2) used in the present invention may be a conventionally known aluminoxane, or may be a benzene-insoluble organoaluminumoxy compound as exemplified in JP-A-2-78687. It's okay.

Conventionally known aluminoxanes can be produced, for example, by the following method, and are usually obtained as a solution in a hydrocarbon solvent.

(1) Compounds containing adsorbed water or salts containing crystal water, such as magnesium chloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate, ceric chloride hydrate, etc. A method in which an organic aluminum compound such as trialkylaluminium is added to a suspension in a hydrocarbon medium, and the adsorbed water or water of crystallization is reacted with the organic aluminum compound.

(2) A method in which water, ice, or steam is directly applied to an organic aluminum compound such as trialkylaluminum in a medium such as benzene, toluene, ethyl ether, or tetrahydrofuran.

(3) A method in which an organoaluminum compound such as trialkylaluminum is reacted with an organotin oxide such as dimethyltin oxide or dibutyltin oxide in a medium such as decane, benzene, or toluene.

Note that the aluminoxane may contain a small amount of an organic metal component. Alternatively, after removing the solvent or unreacted organoaluminum compound by distillation from the recovered aluminoxane solution, the obtained aluminoxane may be redissolved in a solvent or suspended in a poor solvent for aluminoxane.

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

Among these, trialkylaluminum and tricycloalkylaluminum are preferred, and trimethylaluminum is particularly preferred.
The above organoaluminum compounds may be used alone or in combination of two or more.

Solvents used in the preparation of aluminoxane include aromatic hydrocarbons such as benzene, toluene, xylene, cumene, and cymene, aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, hexadecane, and octadecane, and cyclopentane. , alicyclic hydrocarbons such as cyclohexane, cyclooctane, and methylcyclopentane, petroleum fractions such as gasoline, kerosene, and light oil, or halides of the above-mentioned aromatic hydrocarbons, aliphatic hydrocarbons, and alicyclic hydrocarbons, especially chlorine. Examples include hydrocarbon solvents such as compounds and bromides. Furthermore, ethers such as ethyl ether and tetrahydrofuran can also be used. Among these solvents, aromatic hydrocarbons or aliphatic hydrocarbons are particularly preferred. These solvents can be used alone or in combination.

The organoaluminumoxy compound (B-2) used in the present invention is an aluminoxane having a structure represented by the following general formula (B-2a) or (B-2b), and an aluminoxane having a structure represented by the following general formula (B-2c). and a repeating unit represented by the following general formula (B-2d).

（一般式中、Ｒ^cは、それぞれ独立に、炭素原子数１～１０、好ましくは１～４の炭化水素基であり、具体的にはメチル基、エチル基、プロピル基、イソプロピル基、イソプロペニル基、ｎ－ブチル基、ｓｅｃ－ブチル基、ｔｅｒｔ－ブチル基、ペンチル基、ヘキシル基、オクチル基、デシル基、ドデシル基、トリデシル基、テトラデシル基、ヘキサデシル基、オクタデシル基、エイコシル基、シクロヘキシル基、シクロオクチル基、フェニル基、トリル基、エチルフェニル基などの炭化水素基を例示することができる。これら例示したもののうちで、メチル基、エチル基、イソブチル基が好ましく、特にメチル基が好ましく、前記一般式（Ｂ－２ａ）、（Ｂ－２ｂ）および（Ｂ－２ｃ）中、Ｒ^cの一部が塩素、臭素などのハロゲン原子で置換され、かつハロゲン含有率が４０重量％以下であってもよい。

(In the general formula, R ^c is each independently a hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms, specifically methyl group, ethyl group, propyl group, isopropyl group, isopropenyl group) 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, Hydrocarbon groups such as a cyclooctyl group, a phenyl group, a tolyl group, and an ethylphenyl group can be exemplified.Among these examples, a methyl group, an ethyl group, and an isobutyl group are preferred, and a methyl group is particularly preferred; In general formulas (B-2a), (B-2b) and (B-2c), a part of R ^c is substituted with a halogen atom such as chlorine or bromine, and the halogen content is 40% by weight or less. Good too.

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

The aluminoxane having the repeating unit represented by the general formula (B-2c) and the repeating unit represented by the general formula (B-2d) has a molecular weight in the range of 200 to 2000 as measured by the benzene freezing point depression method. Preferably within.

Furthermore, the benzene-insoluble organoaluminumoxy compound used in the present invention has an Al component that dissolves in benzene at 60°C in terms of Al atoms, usually 10% or less, preferably 5% or less, particularly preferably 2% or less, That is, it is preferably insoluble or poorly soluble in benzene. )

As the organoaluminumoxy compound (B-2) used in the present invention, there can also be mentioned an organoaluminumoxy compound containing boron represented by the following general formula (B-2e).

（一般式（Ｂ－２ｅ）中、Ｒ¹⁵は炭素原子数が１～１０の炭化水素基を示し、４つのＲ¹⁶は、互いに同一でも異なっていてもよく、それぞれ独立に、水素原子、ハロゲン原子または炭素原子数が１～１０の炭化水素基を示す。）

(In general formula (B-2e), R ¹⁵ represents a hydrocarbon group having 1 to 10 carbon atoms, and the four R ^16s may be the same or different, and each independently represents a hydrogen atom, a halogen Indicates an atom or a hydrocarbon group having 1 to 10 carbon atoms.)

The boron-containing organoaluminumoxy compound represented by the general formula (B-2e) is prepared by combining an alkylboronic acid represented by the following general formula (B-2f) and an organoaluminum compound under an inert gas atmosphere. It can be produced by reacting in an inert solvent at a temperature of -80°C to room temperature for 1 minute to 24 hours.

R ¹⁵ -B (OH) ₂ ... (B-2f)
(In general formula (B-2f), R ¹⁵ represents the same group as R ¹⁵ in general formula (B-2e) above.)

Specific examples of the alkylboronic acid represented by the general formula (B-2f) include methylboronic acid, ethylboronic acid, isopropylboronic acid, n-propylboronic acid, n-butylboronic acid, isobutylboronic acid, n- Examples include 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 may be used alone or in combination of two or more.

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

As the organic aluminum compound, trialkylaluminum and tricycloalkylaluminum are preferable, and trimethylaluminum, triethylaluminum, and triisobutylaluminum are particularly preferable. These may be used alone or in combination of two or more.

When an organic aluminum oxy compound (B-2) such as methylaluminoxane is used as a co-catalyst component in addition to the transition metal compound (A), extremely high polymerization activity is exhibited for olefin compounds.
The above organoaluminumoxy compounds (B-2) may be used alone or in combination of two or more.

((B-3) Compound that reacts with transition metal compound (A) to form an ion pair)
The compound (B-3) that reacts with the transition metal compound (A) to form an ion pair (hereinafter referred to as "ionized ionic compound") used in the present invention is disclosed in Japanese Patent Publication No. 1-501950. , described in 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. Examples include Lewis acids, ionic compounds, borane compounds, and carborane compounds. Furthermore, mention may also be made of heteropoly compounds and isopoly compounds.

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

Examples of the ionic compounds include compounds represented by the following general formula (B-3a).

（一般式（Ｂ－３ａ）中、Ｒ¹⁷はＨ⁺、カルボニウムカチオン、オキソニウムカチオン、アンモニウムカチオン、ホスホニウムカチオン、シクロヘプチルトリエニルカチオンまたは遷移金属を有するフェロセニウムカチオンであり、Ｒ¹⁸～Ｒ²¹は、互いに同一でも異なっていてもよく、有機基、好ましくはアリール基または置換アリール基である。）

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

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

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

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

As R ¹⁷ , carbonium cations and ammonium cations are preferred, and triphenylcarbonium cations, N,N-dimethylanilinium cations, and N,N-diethylanilinium cations are particularly preferred.

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

Specifically, the trialkyl-substituted ammonium salts include triethylammoniumtetra(phenyl)boron, tripropylammoniumtetra(phenyl)boron, tri(n-butyl)ammoniumtetra(phenyl)boron, trimethylammoniumtetra(p-tolyl), and triethylammoniumtetra(phenyl)boron. ) boron, trimethylammoniumtetra(o-tolyl)boron, tri(n-butyl)ammoniumtetra(pentafluorophenyl)boron, tripropylammoniumtetra(o,p-dimethylphenyl)boron, tri(n-butyl)ammoniumtetra (m,m-dimethylphenyl)boron, tri(n-butyl)ammoniumtetra(p-trifluoromethylphenyl)boron, tri(n-butyl)ammoniumtetra(3,5-ditrifluoromethylphenyl)boron, tri( Examples include n-butyl)ammoniumtetra(o-tolyl)boron.

Specifically, the N,N-dialkylanilinium salts include N,N-dimethylaniliniumtetra(phenyl)boron, N,N-diethylaniliniumtetra(phenyl)boron, N,N,2,4, Examples include 6-pentamethylanilinium tetra(phenyl)boron.

Specific examples of the dialkylammonium salt include di(1-propyl)ammoniumtetra(pentafluorophenyl)boron, dicyclohexylammoniumtetra(phenyl)boron, and the like.

Furthermore, as ionic compounds, triphenylcarbenium tetrakis(pentafluorophenyl)borate, N,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate, ferroceniumtetra(pentafluorophenyl)borate, triphenylcarbeniumpentaphenyl Also included are a cyclopentadienyl complex, an N,N-diethylanilinium pentaphenylcyclopentadienyl complex, and a boron compound represented by the following formula (B-3b) or (B-3c).

（式（Ｂ－３ｂ）中、Ｅｔはエチル基を示す。）

(In formula (B-3b), Et represents an ethyl group.)

（式（Ｂ－３ｃ）中、Ｅｔはエチル基を示す。）

(In formula (B-3c), Et represents an ethyl group.)

Specifically, borane compounds that are examples of ionizable ionic compounds (compound (B-3)) include, for example, decaborane;
Bis[tri(n-butyl)ammonium]nonaborate, bis[tri(n-butyl)ammonium]decaborate, bis[tri(n-butyl)ammonium]undecaborate, bis[tri(n-butyl)ammonium]dodecaborate , bis[tri(n-butyl)ammonium]decachlorodecaborate, bis[tri(n-butyl)ammonium]dodecachlorododecaborate, and other salts of anions;
of metal borane anions such as tri(n-butyl)ammonium bis(dodecahydride dodecaborate) cobaltate (III), bis[tri(n-butyl)ammonium]bis(dodecahydride dodecaborate) nickelate (III), etc. Examples include salt.

Specific examples of carborane compounds that are examples of ionizable ionic compounds include 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-dicarbaundecaborane, 2 ,7-dicarbaundecaborane, undecahydride-7,8-dimethyl-7,8-dicarbaundecaborane, dodecahydride-11-methyl-2,7-dicarbaundecaborane, tri(n-butyl)ammonium 1-carbadecaborate, tri(n-butyl)ammonium 1-carbaundecaborate, tri(n-butyl)ammonium 1-carbadodecaborate, tri(n-butyl)ammonium 1-trimethylsilyl-1-carbadecaborate, Tri(n-butyl)ammonium bromo-1-carbadodecaborate, tri(n-butyl)ammonium 6-carbadodecaborate, tri(n-butyl)ammonium 6-carbadodecaborate, tri(n-butyl)ammonium 7- Carbaundecaborate, tri(n-butyl)ammonium 7,8-dicarbaundecaborate, tri(n-butyl)ammonium 2,9-dicarbaundecaborate, tri(n-butyl)ammonium dodecahydride-8-methyl -7,9-dicarbaundecaborate, tri(n-butyl)ammonium undecahydride-8-ethyl-7,9-dicarbaundecaborate, tri(n-butyl)ammonium undecahydride-8-butyl-7 ,9-dicarbaundecaborate, tri(n-butyl)ammonium undecahydride-8-allyl-7,9-dicarbaundecaborate, tri(n-butyl)ammonium undecahydride-9-trimethylsilyl-7,8 - salts of anions such as dicarbaundecaborate, tri(n-butyl)ammonium undecahydride-4,6-dibromo-7-carbaundecaborate;
Tri(n-butyl)ammonium bis(nonahydride-1,3-dicarbanonaborate) cobaltate (III), tri(n-butyl)ammonium bis(undecahydride-7,8-dicarbaundecaborate) Ferrate (III), tri(n-butyl)ammonium bis(undecahydride-7,8-dicarbaundecaborate) cobaltate(III), tri(n-butyl)ammonium bis(undecahydride-7) , 8-dicarbaundecaborate) nickelate (III), tri(n-butyl) ammonium bis(undecahydride-7,8-dicarbaundecaborate) cuprate (III), tri(n-butyl) Ammonium bis(undecahydride-7,8-dicarbaundecaborate)aurate (III), tri(n-butyl)ammonium bis(nonahydride-7,8-dimethyl-7,8-dicarbaundecaborate) Ferrate (III), tri(n-butyl)ammonium bis(nonahydride-7,8-dimethyl-7,8-dicarbaundecaborate)chromate(III), tri(n-butyl)ammonium bis( tribromooctahydride-7,8-dicarbaundecaborate) cobaltate (III), tris[tri(n-butyl)ammonium]bis(undecahydride-7-carbaundecaborate) chromate (III) , bis[tri(n-butyl)ammonium]bis(undecahydride-7-carbaundecaborate) manganate (IV), bis[tri(n-butyl)ammonium]bis(undecahydride-7-carbaundecaborate) Examples include salts of metal carborane anions such as cobaltate (III), bis[tri(n-butyl)ammonium]bis(undecahydride-7-carbaundecaborate) nickelate (IV), etc. It will be done.

A heteropoly compound, which is an example of an ionizable ionic compound, contains atoms selected from silicon, phosphorus, titanium, germanium, arsenic, and tin, and one or more atoms selected from vanadium, niobium, molybdenum, and tungsten. It is a compound. Specifically, phosphovanadate, germanovanadate, arsenic vanadate, phosphoniobic acid, germanoniobic acid, siliconomolybdic acid, phosphomolybdic acid, titanium molybdic acid, germanomolybdic acid, arsenic molybdic acid, tin molybdic acid, phosphorus Tungstic acid, germanotungstic acid, tintungstic acid, phosphomolybdovanadate, phosphotungstovanadate, germanotungstovanadate, phosphomolybdotungstovanadate, germanomolybdotungstovanadate, phosphomolybdotungstic acid , phosphomolybdoniobic acid, and salts of these acids. In addition, the salt includes, for example, an alkali metal of Group 1 of the periodic table or an alkaline earth metal of Group 2 of the periodic table, specifically lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, Examples include salts with strontium, barium, etc., and organic salts such as triphenylethyl salts.

An isopoly compound, which is an example of an ionizable ionic compound, is a compound composed of a metal ion of one type of atom selected from vanadium, niobium, molybdenum, and tungsten, and is considered to be a molecular ionic species of a metal oxide. I can do it. Specific examples include, but are not limited to, vanadic acid, niobic acid, molybdic acid, tungstic acid, and salts of these acids. The salts include, for example, salts of the acid with metals of Group 1 or Group 2 of the periodic table, specifically lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium, etc. Examples include organic salts such as salts and triphenylethyl salts.

The above-mentioned ionizable ionic compounds (compounds (B-3) that react with the transition metal compound (A) to form ion pairs) may be used alone or in combination of two or more.
Further, the olefin polymerization catalyst according to the present invention comprises the above transition metal compound (A) (hereinafter sometimes abbreviated as "component (A)"), an organometallic compound (B-1), an organoaluminum oxy Along with at least one compound (B) (hereinafter sometimes abbreviated as "component (B)") selected from the group consisting of compound (B-2) and ionizable ionic compound (B-3), necessary Depending on the situation, the following carrier (C) may be included.

((C) carrier)
The carrier (C) used in the present invention is an inorganic or organic compound, and is a granular or particulate solid. By supporting the transition metal compound (A) and compound (B) on the carrier (C), a polymer with good morphology can be obtained.

The inorganic compound is preferably a porous oxide, a solid aluminoxane compound, an inorganic halide, clay, clay mineral, or an ion-exchangeable layered compound.
Examples of the porous oxide include _SiO2 , _Al2O3 , MgO, ZrO, _TiO2 , _B2O3 , CaO, ZnO, BaO, ThO2 _, etc., or composites _or mixtures containing these _. Furthermore, natural or synthetic zeolites can be used, for example SiO ₂ -MgO, SiO ₂ -Al ₂ O ₃ , SiO ₂ -TiO ₂ , SiO ₂ -V ₂ O ₅ , SiO ₂ -Cr ₂ O ₃ , SiO ₂ -TiO ₂ -MgO etc. can be used. Among these porous oxides, those containing SiO ₂ and/or Al ₂ O ₃ as main components are preferred.

The above porous oxide contains a small amount of Na ₂ CO ₃ , K ₂ CO ₃ , CaCO ₃ , MgCO ₃ , Na ₂ SO ₄ , Al ₂ (SO ₄ ) ₃ , BaSO ₄ , KNO ₃ , Mg (NO _{3 )} . ) ₂ , Al(NO ₃ ) ₃ , Na ₂ O, K ₂ O, Li ₂ O, and other carbonate, sulfate, nitrate, and oxide components may be contained.

The properties of such porous oxides vary 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 The pore volume is preferably in the range of 50 to 1000 m ² /g, preferably 100 to 700 m ² /g, and the pore volume is preferably in the range of 0.3 to 3.0 cm ³ /g. Such a porous oxide is used after being fired at a temperature of 100 to 1000°C, preferably 150 to 700°C, if necessary.

Examples of the solid aluminoxane compound include aluminoxanes selected from at least one of the aluminoxanes shown in (B-2a) to (B-2d) above.
Unlike conventionally known carriers for olefin polymerization catalysts, the solid aluminoxane used in the present invention does not contain inorganic solid components such as silica or alumina or organic polymer components such as polyethylene or polystyrene, and has an alkyl aluminum compound as its main component. The solid state is shown as . As used herein, "solid" means that the aluminoxane remains substantially solid under the reaction environment in which it is used. More specifically, for example, when preparing a solid catalyst component for olefin polymerization by bringing component (A) and component (B) into contact as described below, an inert hydrocarbon solvent such as hexane or toluene used in the reaction. Component (B) is in a solid state under a specific temperature and pressure environment. For example, when carrying out suspension polymerization using a solid catalyst component for olefin polymerization prepared using component (B) as described below, it is possible to perform suspension polymerization at a specific temperature and pressure in a hydrocarbon solvent such as hexane, heptane, or toluene. It is also a necessary requirement that component (B) contained in the catalyst component be in a solid state in the environment. The same applies to bulk polymerization in which polymerization is performed in a liquefied monomer instead of a solvent, and gas phase polymerization in which polymerization is performed in monomer gas.

Visual confirmation is the easiest way to determine whether component (B) is in a solid state under the above environment, but visual confirmation is often difficult, for example during polymerization. In that case, it is possible to judge from, for example, the properties of the polymer powder obtained after polymerization and the state of adhesion to the reactor. On the other hand, as long as the polymer powder has good properties and is less likely to adhere to the reactor, even if a portion of component (B) is eluted to some extent in the polymerization environment, this does not depart from the spirit of the present invention. Indices for determining the properties of the polymer powder include bulk density, particle shape, surface shape, degree of presence of amorphous polymer, etc., but polymer bulk density is preferred from the quantitative viewpoint. The bulk density in the present invention is usually in the range of 0.01 to 0.9, preferably 0.05 to 0.6, more preferably 0.1 to 0.5.

The solid aluminoxane used in the present invention has a dissolution rate in n-hexane maintained at a temperature of 25°C, usually 0 to 40 mol%, preferably 0 to 20 mol%, particularly preferably 0 to 10 mol%. % range.

The dissolution rate of solid aluminoxane used in the present invention in n-hexane is determined by adding 2 g of solid aluminoxane carrier to 50 ml of n-hexane kept at 25°C, stirring for 2 hours, and then using a G-4 glass. The aluminum concentration in the filtrate was determined by separating the solution part using a manufactured filter. Therefore, the dissolution rate 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.

As the solid aluminoxane, any known solid aluminoxane can be used without limit. Known manufacturing methods include, for example, JP-A No. 7-42301, JP-A-6-220126, JP-A-6-220128, JP-A-11-140113, JP-A-11-310607, and JP-A-2000. -38410, JP-A-2000-95810, and WO2010/55652.

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, particularly preferably 1 to 200 μm.
The average particle diameter of solid aluminoxane is determined by observing the particles with a scanning electron microscope, measuring the particle diameters of 100 or more particles, and averaging them by weight. The particle size of the solid aluminoxane was determined by measuring the maximum length using the Pythagorean method from a particle image. That is, the length of the particle image sandwiched between two parallel lines is measured in both the horizontal and vertical directions, and calculated using the following formula.
Particle size = ((horizontal length) ² + (vertical length) ² ) ^0.5

The weight average particle diameter of solid aluminoxane is determined by the following formula using the particle diameter determined above.
Average particle size = Σnd ⁴ / Σnd ³ (where n: number of particles, d: particle size)

The solid aluminoxane preferably used in the present invention has a specific surface area of 50 to 1000 m ² /g, preferably 100 to 800 m ² /g, and a pore volume of 0.1 to 2.5 cm ³ /g. desirable.

As the inorganic halide, _MgCl2 , _MgBr2 , _MnCl2 , MnBr2 _, etc. are used. The inorganic halide may be used as it is, or after being pulverized using a ball mill or a vibration mill. Alternatively, an inorganic halide may be dissolved in a solvent such as alcohol, and then precipitated into fine particles using a precipitating agent.

The clay is usually composed mainly of clay minerals. The ion-exchangeable layered compound is a compound having a crystal structure in which surfaces constituted by ionic bonds or the like are stacked in parallel with each other with weak bonding force, and the ions contained therein can be exchanged. Most clay minerals are ion exchange layered compounds. In addition, these clays, clay minerals, and ion-exchange layered compounds are not limited to natural ones, and artificially synthesized ones can also be used.

Examples of the clay, clay mineral, or ion-exchange layered compound include ionic crystalline compounds having a layered crystal structure such as a hexagonal close packing type, an antimony type, a CdCl ₂ type, a CdI ₂ type, and the like.

Furthermore, clay and clay minerals include kaolin, bentonite, Kibushi clay, gyrome clay, allophane, hisingerite, pyrophyllite, Ummo group, montmorillonite group, vermiculite, Ryokudei group, palygorskite, kaolinite, nacrite, dickite, Examples include halloysite,
Ion-exchange layered compounds include α-Zr(HAsO ₄ ) ₂ ·H ₂ О, α-Zr(HPО ₄ ) ₂ , α-Zr(KPО ₄ ) ₂ ·3H ₂ О, α-Ti(HPО ₄ ) ₂ , α-Ti (HAsО ₄ ) ₂・H ₂ О, α-Sn (HPО ₄ ) ₂・H ₂ О, γ-Zr (HPО ₄ ) ₂ , γ-Ti (HPО ₄ ) ₂ , γ-Ti ( Examples include crystalline acid salts of polyvalent metals such as NH ₄ PO ₄ ) ₂ .H ₂ Ξ.

Such clay, clay mineral, or ion-exchange layered compound preferably has a pore volume of 0.1 cc/g or more, and preferably 0.3 to 5 cc/g, with a radius of 20 Å or more measured by mercury intrusion porosimetry. It is particularly preferable. Here, the pore volume is measured in a pore radius range of 20 to 30,000 Å by mercury intrusion method using a mercury porosimeter.
When a carrier having a radius of 20 Å or more and a pore volume smaller than 0.1 cc/g is used as a carrier, it tends to be difficult to obtain high polymerization activity.

It is also preferable to chemically treat the clay and clay mineral used in the present invention. As the chemical treatment, any of surface treatment to remove impurities adhering to the surface, treatment to affect the crystal structure of clay, etc. can be used. Specific examples of the chemical treatment include acid treatment, alkali treatment, salt treatment, and organic substance treatment. Acid treatment not only removes impurities on the surface, but also increases the surface area by eluting cations such as Al, Fe, and Mg in the crystal structure. Alkaline treatment destroys the crystal structure of the clay, resulting in changes in the structure of the clay. Furthermore, salt treatment and organic substance treatment can form ionic complexes, molecular complexes, organic derivatives, etc., and change the surface area and interlayer distance.

The ion-exchangeable layered compound used in the present invention may be a layered compound in which the interlayers are expanded by utilizing ion exchangeability and exchanging exchangeable ions between the layers with other large bulky ions. . These bulky ions play the role of pillars that support the layered structure and are usually called pillars. Furthermore, the introduction of another substance between the layers of a layered compound in this way is called intercalation. Examples of guest compounds to be intercalated include cationic inorganic compounds such as TiCl ₄ and ZrCl ₄ , and metal alkoxides (such as Ti(OR) ₄ , Zr(OR) ₄ , PO(OR) ₃ and B(OR) ₃ ). R is a hydrocarbon group, etc.), metal hydroxide ions such as [Al ₁₃ О ₄ (ОH) ₂₄ ] ⁷⁺ , [Zr ₄ (ОH) ₁₄ ] ²⁺ , [Fe ₃ О (ОCOCH ₃ ) ₆ ] ⁺ etc. Examples include. These compounds may be used alone or in combination of two or more. In addition, when intercalating these compounds, metal alkoxides such as Si(OR) ₄ , Al(OR) ₃ , Ge(OR) ₄ (R represents a hydrocarbon group, etc.) are hydrolyzed. The obtained polymer, a colloidal inorganic compound such as SiO ₂ , etc. can also be made to coexist. Further, examples of pillars include oxides produced by intercalating the metal hydroxide ions between layers and then heating and dehydrating them.

The clay, clay mineral, and ion-exchange layered compound used in the present invention may be used as they are, or may be used after being subjected to treatments such as ball milling and sieving. Alternatively, it may be used after newly adding and adsorbing water or after being heated and dehydrated. Furthermore, they may be used alone or in combination of two or more.
Among these, preferred are clays or clay minerals, and particularly preferred are montmorillonite, vermiculite, pectolite, taeniolite and synthetic mica.

As mentioned above, the carrier (C) is an inorganic or organic compound, and examples of the organic compound include granular or fine particulate solids having a particle size in the range of 10 to 300 μm. Specifically, (co)polymers produced mainly from α-olefins having 2 to 14 carbon atoms such as ethylene, propylene, 1-butene, 4-methyl-1-pentene, vinylcyclohexane, styrene, etc. Examples include (co)polymers produced using as a main component and modified products thereof.

The olefin polymerization catalyst according to the present invention contains the transition metal compound (A), the compound (B), and optionally a carrier (C), as well as the following specific organic compound component (D) as required. It can also be included.

((D) Organic compound component)
In the present invention, the organic compound component (D) improves the polymerization performance of the olefin polymerization catalyst of the present invention and the physical properties of the produced polymer (for example, the molecular weight of the produced polymer) (if the molecular weight is high, the molecular weight is increased). used for the purpose of Such organic compounds include, but are not limited to, alcohols, phenolic compounds, carboxylic acids, phosphorus compounds, and sulfonate salts.

As the alcohols and the phenolic compounds, those represented by R ²² -OH are usually used, where R ²² is a hydrocarbon group having 1 to 50 carbon atoms (in the case of phenols, a carbon atom 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).

As alcohols, those in which R ²² is a halogenated hydrocarbon group are preferred. Further, as the phenolic compound, one in which the α and α'-positions of the hydroxyl group are substituted with a hydrocarbon having 1 to 20 carbon atoms is preferable.

As the above-mentioned carboxylic acid, those represented by R ²³ -COH are usually 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 a halogenated hydrocarbon group having 1 to 50 carbon atoms is particularly preferred.

As the above-mentioned phosphorus compound, phosphoric acids having a P-O-H bond, P-OR, phosphate having a P=O bond, and phosphine oxide compounds are preferably used.
Examples of the sulfonate salt include those represented by the following general formula (Da).

（一般式（Ｄ－ａ）中、Ｍ⁵は周期表第１～１４族の原子であり、Ｒ²⁴は水素、炭素原子数１～２０の炭化水素基または炭素原子数１～２０のハロゲン化炭化水素基であり、Ｚは水素原子、ハロゲン原子、炭素原子数が１～２０の炭化水素基または炭素原子数が１～２０のハロゲン化炭化水素基であり、ｔは１～７の整数であり、ｕは１～７の整数であり、また、ｔ－ｕ≧１である。）

(In the general formula (D-a), M ⁵ is an atom of Groups 1 to 14 of the periodic table, and R ²⁴ is hydrogen, a hydrocarbon group having 1 to 20 carbon atoms, or a halogenated group having 1 to 20 carbon atoms. is a hydrocarbon group, Z is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a halogenated hydrocarbon group having 1 to 20 carbon atoms, and t is an integer of 1 to 7. (U is an integer from 1 to 7, and tu≧1.)

[Method for producing olefin polymer]
In the method for producing an olefin polymer according to the present invention, an olefin polymer is obtained by including a step of polymerizing or copolymerizing an olefin in the presence of an olefin polymerization catalyst as described above. In addition, as mentioned above, in this specification, olefin refers to any compound having a polymerizable double bond.

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

The solid catalyst component in which the transition metal compound (A) is supported on the carrier (C) and the solid catalyst component in which the transition metal compound (A) and the compound (B) are supported on the carrier (C) have an olefin in advance. The solid catalyst component may be polymerized, and a catalyst component may be further supported on the prepolymerized solid catalyst component.

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. Specifically, the inert hydrocarbon medium used in the liquid phase polymerization method includes aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; cyclopentane, cyclohexane, and methylcyclopentane. Alicyclic hydrocarbons such as benzene, toluene, xylene, etc.; halogenated hydrocarbons such as ethylene chloride, chlorobenzene, dichloromethane, or mixtures thereof; The olefin itself can also be used as a solvent.

When polymerizing olefins using the above catalyst for olefin polymerization, the transition metal compound (A) is usually 1×10 ⁻¹² to 1×10 −2 mol, preferably 1×10 ⁻² mol per 1 liter of reaction volume. It is used in an amount of ×10 ⁻¹⁰ to 1×10 ⁻³ mol.

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

The organic compound component (D) is mixed so that the molar ratio [(D)/(B-1)] with the organometallic compound (B-1) is usually 0.01 to 10, preferably 0.1 to 5. used in large quantities. The molar ratio [(D)/(B-2)] of the organic compound component (D) to the organoaluminumoxy compound (B-2) is usually 0.001 to 2, preferably 0.005 to 1. used in such amounts. The molar ratio [(D)/(B-3)] of the organic compound component (D) to the ionizable ionic compound (B-3) is usually 0.01 to 10, preferably 0.1 to 5. used in such amounts.

Further, the olefin polymerization temperature using such an olefin polymerization catalyst is usually in the range of -50 to +200°C, preferably 0 to 170°C. The polymerization pressure is usually 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 in any of the batch, semi-continuous, and continuous methods. can also be done. Furthermore, it is also possible to carry out the polymerization in two or more stages with different reaction conditions.

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

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

The olefin polymerization catalyst of the present invention can be used for homopolymerization of ethylene or 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. is more preferable. One type of α-olefin may be used alone, or two or more types may be used in combination.

In the case of copolymerization of ethylene and 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. However, for example, propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-octene, 1-decene preferable. These α-olefins may be used alone or in combination of two or more. Among these, at least one selected from 1-butene, 1-hexene, 4-methyl-1-pentene and 1-octene is more preferred.

When ethylene is used as the α-olefin and the above olefin A is used, the usage ratio of ethylene to the above olefin A is ethylene:the above olefin A (mole ratio), usually 1:10 to 5000:1, preferably The ratio is 1:5 to 1000:1.

The olefin polymerization catalyst of the present invention may (co)polymerize known chain unsaturated hydrocarbons having polar groups (for example, carbonyl groups, hydroxyl groups, ether bonding groups, etc.).
The olefin polymerization catalyst of the present invention may also (co)polymerize vinylcyclohexane, diene, polyene, or the like.

Examples of the diene or polyene include cyclic or chain compounds having 4 to 30 carbon atoms, preferably 4 to 20 carbon atoms, and having two or more double bonds. Specifically, butadiene, isoprene, 4-methyl-1,3-pentadiene, 1,3-pentadiene, 1,4-pentadiene, 1,5-hexadiene, 1,4-hexadiene, 1,3-hexadiene, 1 , 3-octadiene, 1,4-octadiene, 1,5-octadiene, 1,6-octadiene, 1,7-octadiene, ethylidenenorbornene, vinylnorbornene, dicyclopentadiene;
7-methyl-1,6-octadiene, 4-ethylidene-8-methyl-1,7-nonadiene, 5,9-dimethyl-1,4,8-decatriene;
Furthermore, aromatic vinyl compounds such as mono- or polystyrene such as styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, o,p-dimethylstyrene, o-ethylstyrene, m-ethylstyrene, p-ethylstyrene, etc. Alkylstyrene;
Styrene derivatives containing functional groups such as methoxystyrene, ethoxystyrene, vinylbenzoic acid, methyl vinylbenzoate, vinylbenzyl acetate, hydroxystyrene, o-chlorostyrene, p-chlorostyrene, divinylbenzene;
and 3-phenylpropylene, 4-phenylpropylene, α-methylstyrene, and the like.

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 are also used. I can do it.
In addition, compounds selected from the group consisting of compounds represented by the following general formula [ZI], general formula [Z-II], general formula [Z-III], general formula [Z-IV] or general formula [ZV] At least one type of cyclic olefin (Z) is mentioned.

〔式［Z-I］中、ｕは０または１であり、
ｖは０または正の整数であり、
ｗは０または１であり、
Ｒ⁶¹～Ｒ⁷⁸ならびにＲ^a1およびＲ^b1は、それぞれ独立に水素原子、ハロゲン原子、および炭化水素基から選ばれ、Ｒ⁷⁵～Ｒ⁷⁸は、互いに結合して単環または、多環を形成していてもよく、かつ該単環または多環が二重結合を有していてもよく、またＲ⁷⁵とＲ⁷⁶とで、またはＲ⁷⁷とＲ⁷⁸とでアルキリデン基を形成していてもよい。〕

[In formula [ZI], u is 0 or 1,
v is 0 or a positive integer,
w is 0 or 1,
R ⁶¹ to R ⁷⁸ and R ^a1 and R ^b1 are each independently selected from a hydrogen atom, a halogen atom, and a hydrocarbon group, and R ⁷⁵ to R ⁷⁸ are bonded to each other to form a monocyclic or polycyclic ring. and the monocyclic or polycyclic ring may have a double bond, and R ⁷⁵ and R ⁷⁶ or R ⁷⁷ and R ⁷⁸ may form an alkylidene group. . ]

〔式［Z-II］中、ｘおよびｄは０または１以上の整数であり、
ｙおよびｚは０、１または２であり、
Ｒ⁸¹～Ｒ⁹⁹は、それぞれ独立に水素原子、ハロゲン原子、および炭化水素基から選ばれ、Ｒ⁸⁹およびＲ⁹⁰が結合している炭素原子と、Ｒ⁹³が結合している炭素原子またはＲ⁹¹が結合している炭素原子とは、直接あるいは炭素原子数１～３のアルキレン基を介して結合していてもよく、またｙ＝ｚ＝０のとき、Ｒ⁹⁵とＲ⁹²またはＲ⁹⁵とＲ⁹⁹とは互いに結合して単環または多環の芳香族環を形成していてもよい。〕

[In formula [Z-II], x and d are 0 or an integer of 1 or more,
y and z are 0, 1 or 2;
R ⁸¹ to R ⁹⁹ are each independently selected from a hydrogen atom, a halogen atom, and a hydrocarbon group, and the carbon atom to which R ⁸⁹ and R ⁹⁰ are bonded, the carbon atom to which R ⁹³ is bonded, or R ⁹¹ may be bonded directly or via an alkylene group having 1 to 3 carbon atoms, and when y=z=0, R ⁹⁵ and R ⁹² or R ⁹⁵ and R and ⁹⁹ may be bonded to each other to form a monocyclic or polycyclic aromatic ring. ]

〔式［Z-III］中、Ｒ¹⁰⁰およびＲ¹⁰¹は、それぞれ独立に水素原子または炭素原子数１～５の炭化水素基であり、ｆは１≦ｆ≦１８である。〕

[In formula [Z-III], R ¹⁰⁰ and R ¹⁰¹ are each independently a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms, and f is 1≦f≦18. ]

〔一般式［Z-IV］中、ｘは０または１以上の整数であり、
Ｒ¹¹¹～Ｒ¹¹⁸は、それぞれ独立に水素原子、ハロゲン原子、および炭化水素基から選ばれ、
Ｒ¹²¹～Ｒ¹²⁴は、それぞれ独立に水素原子、ハロゲン原子、および炭化水素基から選ばれ、隣接する２つの基は互いに結合し単環または複環の芳香族環を形成していてもよい。〕

〔一般式［Z-V］中、ｎおよびｍはそれぞれ独立に０、１または２であり、ｑは１、２または３であり、Ｒ¹⁸～Ｒ³¹はそれぞれ独立に、水素原子、フッ素原子を除くハロゲン原子、またはフッ素原子を除くハロゲン原子で置換されていてもよい炭素原子数１～２０の炭化水素基であり、またｑ＝１のときＲ²⁸とＲ²⁹、Ｒ²⁹とＲ³⁰、Ｒ³⁰とＲ³¹は互いに結合して単環または多環を形成していてもよく、またｑ＝２または３のときＲ²⁸とＲ²⁸、Ｒ²⁸とＲ²⁹、Ｒ²⁹とＲ³⁰、Ｒ³⁰とＲ³¹、Ｒ³¹とＲ³¹は互いに結合して単環または多環を形成していてもよく、前記単環または前記多環が二重結合を有していてもよく、また前記単環または前記多環が芳香族環であってもよい。〕

[In the general formula [Z-IV], x is 0 or an integer of 1 or more,
R ¹¹¹ to R ¹¹⁸ are each independently selected from a hydrogen atom, a halogen atom, and a hydrocarbon group,
R ¹²¹ to R ¹²⁴ are each independently selected from a hydrogen atom, a halogen atom, and a hydrocarbon group, and two adjacent groups may be bonded to each other to form a monocyclic or multicyclic aromatic ring. ]

[In the general formula [ZV], n and m are each independently 0, 1 or 2, q is 1, 2 or 3, and R ¹⁸ to R ³¹ are each independently excluding a hydrogen atom or a fluorine atom] A hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a halogen atom or a halogen atom excluding a fluorine atom, and when q=1, R ²⁸ and R ²⁹ , R ²⁹ and R ³⁰ , R ³⁰ and R ³¹ may combine with each other to form a monocyclic or polycyclic ring, and when q=2 or 3, R ²⁸ and R ²⁸ , R ²⁸ and R ²⁹ , R ²⁹ and R ³⁰ , R ³⁰ and R ³¹ , R ³¹ and R ³¹ may be combined with each other to form a monocyclic ring or a polycyclic ring, the monocyclic ring or the polycyclic ring may have a double bond, and the monocyclic ring or the polycyclic ring may have a double bond. The polycyclic ring may be an aromatic ring. ]

Specific examples of such cyclic olefins include compounds disclosed in JP-A No. 2020-164719 and the like. Among them, the most preferred specific example is tetracyclo[4.4.0.1 ^2,5 . 1 ^7,10 ]-3-dodecene.

The transition metal compound (A) of the present invention has a structure in which elements of different groups of the periodic table, namely E, Z, and Q, as shown in the above formula (1) are bonded in a specific positional relationship. This is a characteristic. The present inventor believes that by adopting such a structure, for example, it is possible to exhibit olefin polymerization catalyst performance with an excellent balance of polymerization activity, high molecular weight, and copolymerizability. In addition, by selecting the substituents (Rh, Rp in formula (1), Rr, Rh, Rs in formula (2)), the electron density, electron distribution, and steric hindrance of the transition metal compound can be controlled. It is also considered possible to adjust the performance balance of polymerization activity, high molecular weight, copolymerizability, etc. depending on the purpose.

When the transition metal compound (A) of the present invention is used as an olefin polymerization catalyst, it can be used particularly in the copolymerization of olefins with cyclic olefin compounds such as tetracyclododecene or cyclic diene compounds such as 5-ethylidene-2-norbornene. , these cyclic compounds are relatively easy to react, and there is a tendency to easily obtain an olefin copolymer having a relatively high content of structural units derived from these cyclic compounds. Although the reason for this tendency is not clear at present, the present inventors speculate as follows.

It is generally known that olefin polymerization using a transition metal compound catalyst involves a step in which the olefin is coordinated with the catalyst. As mentioned above, the transition metal compound (A) of the present invention is characterized in that it has a structure in which elements of different groups of the periodic table, namely E, Z, and Q, as shown in the above formula (1), are directly bonded. It is. Such sites where so-called heteroatoms are unevenly distributed are likely to have unique polarity, so that olefins and cyclic olefins are likely to be coordinated therewith. In addition, the rate of coordination is not easily influenced by the steric structure of compounds having olefin double bonds (hereinafter sometimes referred to as olefin compounds) due to the high polarity of the heteroatom unevenly distributed sites. It's predictable.

On the other hand, it is also known that transition metal compounds in which highly polar moieties exist have too strong coordination with olefins, making it difficult for olefin polymerization reactions to occur and resulting in low polymerization activity. However, since the transition metal compound (A) of the present invention has a structure in which elements of different groups of the periodic table are in a specific positional relationship, the difference in electron density and electronegativity is used as a driving force to coordinate It is thought that the olefin compound is sent to the transition metal side of M, which is considered to be the main active site, and the reaction is promoted. In this case, it is also considered preferable that the substituent bonded to Q has a propeller-like structure that is easily rotated, such as an aromatic group or a substituted aromatic group. This is because rotation of the substituents can be expected to promote the delivery of the olefin.

Since the transition metal compound (A) can be expected to have the above-mentioned characteristics, it can be expected to have the above-mentioned excellent balance of performance even in copolymerization using olefins with different structures in addition to ethylene polymerization. I can think. In particular, in the copolymerization of an olefin and an olefin having a cyclic structure, a characteristic polymerization reaction (for example, excellent copolymerizability) tends to occur. (For example, it has excellent copolymerizability.) In addition, it can be expected that even more characteristic performance will be exhibited by the combination with the ligand L(l).

[Olefin polymer]
According to the present invention, in the presence of an olefin polymerization catalyst containing the useful and novel transition metal compound (A) having the above-mentioned specific structure, one or more kinds of α-olefins having 2 to 30 carbon atoms are produced. By polymerizing an olefin selected from; Preferably, by homopolymerizing ethylene or copolymerizing ethylene with at least one olefin A selected from olefins having 3 to 20 carbon atoms. can be manufactured efficiently.

One embodiment of the olefin polymer is an ethylene polymer containing structural units derived from ethylene, preferably in a range of 50 to 100 mol%, more preferably 70 to 100 mol%, even more preferably 90 to 100 mol%. Can be mentioned. The ethylene polymer preferably contains structural units derived from the olefin A in a total amount of 0 to 50 mol%, more preferably 0 to 30 mol%, and still more preferably 0 to 10 mol%. However, the total content of the structural units derived from ethylene and the content of the structural units derived from the olefin A is 100 mol%. An ethylene polymer in which the constituent units derived from the olefin A are within the above range has excellent moldability. Further, 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, infrared spectroscopy, etc. if a reference substance is available.

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, ethylene/propylene/4-methyl-1-pentene polymer is particularly preferred. The above copolymers are usually random copolymers, but also so-called block copolymers (impact copolymers) obtained by mixing or continuously producing two or more selected from these polymers. ) is also fine.

Among the polymers having the above-mentioned structural units, the ethylene polymer is preferably an α-olefin polymer consisting essentially only of structural units derived from an α-olefin having 2 to 20 carbon atoms. "Substantially" means that the proportion of the structural units derived from α-olefin having 2 to 20 carbon atoms is 95% by weight or more with respect to all the structural units.

The weight average molecular weight of the olefin polymer 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, particularly preferably from 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, particularly preferably 1 to It is 5.

The density of the olefin polymer is not particularly limited, but is preferably 875 kg/m ³ or more and 975 kg/m ³ or less.
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, particularly preferably 1 to 10 dl. /g.

The melt mass flow rate (MFR; unit: g/10 min) of the olefin polymer measured according to ASTM D1238-89 at 190°C under a load of 2.16 kg is not particularly limited, but is preferably 0.001 g. /10 minutes or more and 300g/10 minutes or less, more preferably 0.001g/10 minutes or more and 200g/10 minutes or less.

In addition, according to ASTM D1238-89, the value (I10/I2) obtained by dividing the MFR value measured under the conditions of 190°C and 10 kg load by the MFR value measured under the conditions of 190°C and 2.16 kg load is 5. It is preferably .0 or more and less than 300.
Details of the measurement conditions for the above physical property values are as described in Examples.

Hereinafter, the present invention will be explained in more detail based on Examples, but the present invention is not limited to these Examples.

[Measuring method]
The transition metal compound was identified by measuring ¹ H-NMR spectrum (270 MHz, JEOL GSH-270), FD-mass (hereinafter referred to as FD-MS) spectrum (JEOL SX-102A), etc.

The physical properties of the ethylene/1-octene copolymer and the ethylene/propylene/5-ethylidene-2-norbornene copolymer were measured by the following method.
[Comonomer content]
The comonomer content of the physical properties of ethylene/1-octene copolymer and ethylene/propylene/5-ethylidene-2-norbornene copolymer is determined by FT-IR (JASCO Corporation FT-IR410 model infrared spectrophotometer) or ¹ Measured by H-NMR measurement.

(FT-IR measurement method)
FT-IR uses a film obtained by heating the polymer obtained in the example to 135°C, melting and stretching it in a hot press, and cooling it under pressure at room temperature as a measurement sample, and uses a calibration curve. The 1-octene structural unit content, propylene structural unit content, and 5-ethylidene-2-norbornene structural unit content were measured. The comonomer content of the ethylene/1-octene copolymer and ethylene/propylene/5-ethylidene-2-norbornene copolymer samples used to create the calibration curve was determined by ^13C -NMR measurement under the same conditions as above. .
( ^1H -NMR measurement)
o-Dichlorobenzene _d4 was used as the measurement solvent, or under the measurement conditions (500MHz, Bruker Bio ¹ H-NMR measurement was performed using a Spin AVANCE III cryo-500). Various signals such as methyl groups and ethylidene groups were assigned based on conventional methods, and the above-mentioned comonomer content was quantified based on the integrated value of signal intensity.
The physical properties of the ethylene/TD copolymer were measured by the following method.

[Tg of polymer]
DSC measurement was performed under the following conditions to determine the Tg of the polymer.
Equipment: SII Nanotechnology DSC6220
Measurement conditions: Tg was determined in the process of rapidly cooling a sample held at 300° C. for 5 minutes to 0° C. and then increasing the temperature to 250° C. at a heating rate of 20° C./min.

[TD content rate]
The TD content was calculated using the relational expression between Tg and TD content measured above.
The ethylene/TD copolymer used to create the relational equation was analyzed as follows. The TD content of the polymer was determined by ¹³ C-NMR spectrum according to the descriptions in [0216] to [0219] of JP-A-2011-122146. The relational expression was obtained by measuring Tg at each TD content using these samples, and converting these relationships into a relational expression.

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

[Weight average molecular weight (Mw), molecular weight distribution (Mw/Mn) of polymer]
The weight average molecular weight (Mw) and number average molecular weight (Mn) of the olefin polymer were determined by gel permeation chromatography (GPC). It was calculated from the molecular weight distribution curve obtained by Tosoh's "HLC-8321 GPC/HT type" gel permeation chromatograph (high temperature size exclusion chromatograph), and the operating conditions are as follows:

<Equipment used and conditions>
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 7.5 mm x length 30 cm, Tosoh Corporation)
Mobile phase; o-dichlorobenzene [ODCB]
Detector: Differential refractometer (built-in device)
Column temperature: 140℃
Flow rate: 1.0mL/min Injection volume: 400μL
Sampling time interval: 0.5 seconds Sample concentration: 0.15% (w/v)
Molecular weight calibration Monodisperse polystyrene (Tosoh Corporation) / Molecular weight #3 std set

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

(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 a 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 solid obtained by distilling off the solvent under reduced pressure was washed with hexane and then 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 with a dry ice/methanol bath. To this solution, 20 mL of a toluene solution containing 328 mg of the white solid a obtained in the previous reaction was added over 10 minutes while washing with 5 mL of toluene. The temperature was gradually raised to room temperature, and the mixture was stirred for 17 hours under a nitrogen atmosphere. The solvent was distilled off under reduced pressure, extracted with dichloromethane using Celite, and then concentrated under reduced pressure. A red solid produced by extraction with hexane was collected by filtration. The filtrate side was concentrated under reduced pressure. The red solid was dissolved in hexane and recrystallized at -10°C. The generated red crystals were collected by filtration and washed with hexane to obtain 91 mg of the target compound represented by the following formula (hereinafter also referred to as "transition metal compound A"). The solid in the filtrate obtained in the previous vacuum concentration was dissolved in hexane and recrystallized at -10°C, and the produced red solid was removed by filtration. The filtrate was concentrated to half its volume under reduced pressure, and the produced 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%. The target product was identified based on the measurement results of ¹ H-NMR (CDCl ₃ ) and FD-MS. The measurement results are shown below.
^1H -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 ⁺ )

[Synthesis Example 2]
(i) Synthesis of transition metal compound B
In 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 with a dry ice/methanol bath. To this solution, 20 mL of a toluene solution containing 328 mg of the 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 the mixture was stirred for 17 hours under a nitrogen atmosphere. The solvent was distilled off under reduced pressure, extracted with dichloromethane using Celite, and then concentrated under reduced pressure. The obtained solid was dissolved in hexane and recrystallized at -10°C. The generated red crystals were removed by filtration. The filtrate was concentrated under reduced pressure, dissolved again in hexane, and recrystallized at -10°C. The generated red crystals were collected by filtration, washed with hexane, and then dried under reduced pressure to obtain 82 mg of the target compound represented by the following formula (hereinafter also referred to as "transition metal compound B"). The target product was identified based on the measurement results of ¹ H-NMR (CDCl ₃ ) and FD-MS. The measurement results are shown below.
¹ H-NMR (270 MHz, CDCl ₃ ) δ 1.23 (12 H, d, J = 7 Hz), 1.30 (12 H, d, J = 7 Hz), 3.16 (4 H, sep, J = 7 Hz), 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 ⁺ )

[Synthesis Example 3]
(i) Synthesis of transition metal compound C
Under a nitrogen atmosphere, 231 mg (0.80 mmol) of (Pentamethylcyclopentadienyl)titanium trichloride was placed in a 100 mL Schlenk flask, and 20 mL of toluene was added. The Schlenk flask was cooled with a dry ice/methanol bath. To this solution, 20 mL of a toluene solution containing 328 mg of the 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 the mixture was stirred for 17 hours under a nitrogen atmosphere. The solvent was distilled off under reduced pressure, and the mixture was extracted with dichloromethane using Celite, and then extracted with hexane using Celite. The obtained solid was dissolved in hexane and recrystallized at -10°C. The generated red crystals were removed by filtration. The filtrate was concentrated under reduced pressure, dissolved again in hexane, and recrystallized at -10°C. This operation is performed twice in total, and the generated red crystals are collected by filtration, washed with hexane, and then dried under reduced pressure to obtain the target compound represented by the following formula (hereinafter also referred to as "transition metal compound C"). 122 mg was obtained. The target product was identified based on the measurement results of ¹ H-NMR (CDCl ₃ ) and FD-MS. The measurement results are shown below.
¹ H-NMR (270 MHz, CDCl ₃ ) δ 1.18 (12 H, d, J = 7 Hz), 1.29 (12 H, d, J = 7 Hz), 1.86 (15 H, 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 ⁺ )

[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 with a dry ice/methanol bath. To this solution, 20 mL of a toluene solution containing 328 mg of the 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 the mixture was stirred for 16 hours under a nitrogen atmosphere. The solvent was distilled off under reduced pressure, and the mixture was extracted with dichloromethane using Celite, and then extracted with hexane using Celite. The obtained solid was dissolved in hexane, and the solution was concentrated under reduced pressure until the volume became 1/10. The generated red crystals were collected by filtration, washed with hexane, and then dried under reduced pressure to obtain 218 mg (yield 38%) of the target compound represented by the following formula (hereinafter also referred to as "transition metal compound D"). Ta. The target product was identified based on the measurement results of ¹ H-NMR (CDCl ₃ ) and FD-MS. The measurement results are shown below.
^1H -NMR (270MHz, CDCl ₃ ) 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 ⁺ )

[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 with a dry ice/methanol bath. To this solution, 20 mL of a toluene solution containing 287 mg of the 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 the mixture was stirred for 20 hours under a nitrogen atmosphere. The solvent was distilled off under reduced pressure, and the mixture was extracted with dichloromethane using Celite, and then extracted with hexane using Celite. The obtained solid was dissolved in hexane and recrystallized at -35°C. The generated red crystals were collected by filtration, washed with hexane, and then dried under reduced pressure to obtain 39 mg of the target compound represented by the following formula (hereinafter also referred to as "transition metal compound E"). The filtrate was concentrated under reduced pressure, dissolved again in hexane, and recrystallized at -35°C. The generated red crystals were collected by filtration, washed with hexane, and then dried under reduced pressure to obtain 229 mg of transition metal compound E represented by the following formula. Total 268 mg Yield 50%. The target product was identified based on the measurement results of ¹ H-NMR (CDCl ₃ ) and FD-MS. The measurement results are shown below.
^1H -NMR (270MHz, CDCl ₃ ) 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 ⁺ )

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

(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 1M boron tribromide methylene chloride solution was gradually added, the temperature was gradually raised to room temperature, and the mixture was stirred at room temperature for 24 hours under a nitrogen atmosphere. did. After 2.05 mL (11.77 mmol) of diisopropylethylamine was added and stirred for 30 minutes, methanol was added and stirred for 18 hours. Saturated aqueous ammonium chloride solution was added, the organic phase was separated and the aqueous phase was extracted with hexane. The combined organic phases were washed with a saturated aqueous ammonium chloride solution, water, and saturated brine, and then dried over magnesium sulfate. The solid obtained by concentrating the solvent under reduced pressure was washed with hexane and dried under reduced pressure to obtain 332 mg (yield 11%) of ligand II represented by the following formula. ¹ H-NMR (CDCl ₃ ) The target product was identified. The measurement results are shown below.

¹Ｈ－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

¹ H-NMR (270 MHz, CDCl ₃ ) δ 1.14 (12 H, d, J = 7 Hz), 1.17 (12 H, d, J = 7 Hz), 2.92 (4 H, sep, J = 7 Hz), 3.49 (1H, s), 6.46-6.49 (2H, m), 6.83-6.86 (2H, m), 7.29-7.43 (6H, m) ppm

(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 (n-butyl lithium 1.11 mmol) of a 1.58 M n-butyl lithium/hexane solution was gradually added, and the temperature was gradually raised to room temperature, followed by a nitrogen atmosphere. The mixture was stirred at room temperature for 4 hours.

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 the mixture was stirred for 18 hours under a nitrogen atmosphere. The solvent was distilled off under reduced pressure, and the mixture was extracted with dichloromethane using Celite, and then extracted with hexane using Celite. The obtained solid was dissolved in a small amount of dichloromethane and recrystallized at -35°C by adding hexane. The generated red crystals were collected by filtration and washed with hexane to obtain 256 mg of the target compound represented by the following formula (hereinafter also referred to as "transition metal compound F"). Yield 40%. The target product was identified based on the measurement results of ¹ H-NMR (CDCl ₃ ) and FD-MS. The measurement results are shown below.
^1H -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 ⁺ )

[Synthesis Example 7]
(i) Synthesis of transition metal compound G
Under a nitrogen atmosphere, 331 mg (0.73 mmol) of the 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 a 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 adamantylcyclopentadienyl titanium trichloride was placed in a 100 mL Schlenk flask, and 25 mL of toluene was added. The Schlenk flask was cooled with a dry ice/methanol bath. The solution obtained in the previous reaction was added to this solution over 10 minutes while washing with 10 mL of toluene. The temperature was gradually raised to room temperature, and the mixture was stirred for 41 hours under a nitrogen atmosphere. The solvent was distilled off under reduced pressure, and the mixture was extracted with dichloromethane using Celite, and then extracted with hexane using Celite. The obtained solid was dissolved in hexane and recrystallized at -35°C. The produced red crystals were collected by filtration, dissolved again in hexane, and recrystallized at -35°C. The generated red crystals were collected by filtration, washed with hexane, and then dried under reduced pressure to obtain 49 mg of the target compound 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 generated red crystals were collected by filtration, washed with hexane, and then dried under reduced pressure to obtain 62 mg of transition metal compound G represented by the following formula. Total 111 mg, yield 20%. The target product was identified based on the measurement results of ¹ H-NMR (CDCl ₃ ) and FD-MS. The measurement results are shown below.
^1H -NMR (270MHz, CDCl ₃ ) 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 ⁺ )

[Synthesis Example 8]
(i) Synthesis of ligand precursor III
(i-1) Synthesis of N-(2-chlorophenyl)-2,6-diisopropylaniline In a 100 mL three-necked flask under a nitrogen atmosphere, 5.95 g (25.0 mmol) of 1-chloro-2-iodobenzene, 2,6-diisopropylaniline 4.43 g (25.0 mmol), 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. The flask was immersed in a 110°C oil bath and stirred for 19 hours. Saturated aqueous ammonium chloride solution was added, the organic phase was separated and the aqueous phase was extracted with hexane. The combined organic phases were washed with water and saturated brine, and then dried over magnesium sulfate. The black liquid obtained by concentrating the solvent under reduced pressure was purified by silica gel chromatography (solvent: hexane) to obtain the desired product as a colorless liquid. (6.61 g, yield 92%). The target product was identified based on the measurement results of ¹ H-NMR (CDCl ₃ ). The measurement results are shown below.
¹ H-NMR (270 MHz, CDCl ₃ ) δ 1.11 (6H, d, J = 7 Hz), 1.18 (6H, d, J = 7 Hz), 3.11 (2H, sep, J = 7 Hz), 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

(i-2) Synthesis of Ligand Precursor III In a 100 mL three-necked flask under a nitrogen atmosphere, 2878 mg (10.0 mmol) of N-(2-chlorophenyl)-2,6-diisopropylaniline, 1291 mg (1291 mg) of 2,6-difluoroaniline ( 10.0 mmol), 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. The flask was immersed in a 110°C oil bath and stirred for 18 hours. After returning to room temperature, a saturated aqueous ammonium chloride solution was added to separate the organic phase, and the aqueous phase was extracted with hexane. The combined organic phases were washed with water and saturated brine, and then dried over magnesium sulfate. The dark green liquid obtained by concentrating the solvent under reduced pressure was cooled in a refrigerator. The obtained solid was washed with methanol and dried under reduced pressure to obtain a gray solid, the target product represented by the following formula (hereinafter also referred to as "ligand precursor III"). (1.55g, yield 41%). The target product was identified based on the measurement results of ¹ H-NMR (CDCl ₃ ). The measurement results are shown below.
^1H -NMR (270MHz, CDCl ₃ ) 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

(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 1M boron tribromide methylene chloride solution was gradually added, the temperature was gradually raised to room temperature, and the mixture was stirred at room temperature for 19 hours under a nitrogen atmosphere. did. After adding 1.20 mL (6.89 mmol) of diisopropylethylamine and stirring for 90 minutes, the mixture was cooled in an ice bath. 1 mL of pyridine and 30 mL of distilled water were added and stirred for 20 hours. A saturated aqueous ammonium chloride solution was added, the organic phase was separated, and the organic phase was washed three times with a saturated aqueous ammonium chloride solution. The combined aqueous phases were extracted twice with hexane. The combined organic phases were washed with a saturated aqueous ammonium chloride solution, water, and saturated brine, and then dried over magnesium sulfate. The solid obtained by concentrating the solvent under reduced pressure was washed with hexane and dried under reduced pressure to obtain 998 mg (yield: 61%) of ligand III represented by the following formula. ¹ H-NMR (CDCl ₃ ) The target product was identified. The measurement results are shown below.
¹ H-NMR (270 MHz, CDCl ₃ ) δ 1.10 (6H, d, J = 7 Hz), 1.17 (6H, d, J = 7 Hz), 2.90 (2H, sep, J = 7 Hz), 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

(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 (n-butyl lithium 1.42 mmol) of a 1.58 M n-butyl lithium/hexane solution was gradually added, and the temperature was gradually raised to room temperature, followed by a nitrogen atmosphere. The mixture was stirred at room temperature 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 for 21 hours under a nitrogen atmosphere. The solvent was distilled off under reduced pressure, and the mixture was extracted with dichloromethane using Celite, and then extracted with hexane using Celite. The obtained solid was dissolved in a small amount of dichloromethane, hexane was added, and recrystallized at -35°C. The produced orange solid and the solution were separated by decantation, and the solution was concentrated under reduced pressure. The obtained solid was dissolved in a small amount of dichloromethane, hexane was added, and recrystallized at -35°C. The produced orange solid and the solution were separated by decantation, and the solution was concentrated under reduced pressure. It was washed with hexane and dried under reduced pressure to obtain 352 mg of the target compound represented by the following formula (hereinafter also referred to as "transition metal compound H"). Yield 50%. The target product was identified based on the measurement results of ¹ H-NMR (CDCl ₃ ) and FD-MS. The measurement results are shown below.
¹ H-NMR (270 MHz, CDCl ₃ ) δ 1.08 (6H, d, J = 7 Hz), 1.26 (6H, d, J = 7 Hz), 2.91 (2H, sep, J = 7 Hz), 6.17 (5H, s), 6.53-7.45 (10H, m) ppm
FD-MS: m/z=588.1 (M ⁺ )

[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 )Cl ₃ 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 a 1.09M methyllithium/diethyl ether solution (3.05 mmol of methyllithium) was gradually added, the temperature was gradually raised to room temperature, and the temperature was lowered to room temperature under a nitrogen atmosphere. The mixture was stirred for 2 hours. To this solution, while cooling again in a dry ice/methanol bath, add 30 mL of a toluene solution containing 454 mg (1.00 mmol) of the ligand II synthesized in Synthesis Example 6 for 30 minutes while washing with 15 mL of toluene. and added. After gradually raising the temperature to room temperature, the mixture was stirred at room temperature under a nitrogen atmosphere for 21 hours to obtain a slurry. The solvent was distilled off under reduced pressure, and the mixture was extracted with dichloromethane using Celite, and then extracted with hexane using Celite. The obtained solid was washed with pentane and dried under reduced pressure to obtain 288 mg of the target compound represented by the following formula (hereinafter also referred to as "transition metal compound I"). Yield 38%. The target product was identified based on the results of ¹ H-NMR (CDCl ₃ ) measurement. The measurement results are shown below.
^1H -NMR (270MHz, CDCl ₃ ) 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

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

<Production of ethylene polymer>
[Polymerization Example 1-1]
250 mL of toluene was charged into a glass reactor with an internal volume of 500 mL that was sufficiently purged with nitrogen, and the liquid phase and gas phase were saturated with ethylene at 100 L/hr. Thereafter, 0.1 mmol of triisobutylaluminum, 0.2 μmol of transition metal compound C, and 0.8 μmol of triphenylcarbenium tetrakis(pentafluorophenyl)borate were then added to initiate polymerization. Ethylene was continuously supplied at 100 L/hr and polymerization was carried out at 50° C. for 5 minutes under normal pressure, and then the polymerization was stopped by adding a small amount of methanol. After the polymerization was completed, the reaction product was added to 750 mL of methanol containing a small amount of hydrochloric acid to precipitate a polymer. After washing with the same solvent, it was dried under reduced pressure at 80° C. for 10 hours to obtain 1.985 g of ethylene polymer. Table 1 shows the physical properties of the obtained polymer.

[Polymerization Example 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. 1.475g of polymer was obtained. Table 1 shows the physical properties of the polymer.

[Polymerization Example 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. Table 1 shows the physical properties of the polymer.

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

[Polymerization Example 2-1]
250 mL of toluene was charged into a glass reactor with an internal volume of 500 mL that was sufficiently purged with nitrogen, and the liquid phase and gas phase were saturated with ethylene at 100 L/hr. Thereafter, 0.5 mmol of triisobutylaluminum, 0.001 mmol of transition metal compound I, and 0.004 mmol of triphenylcarbenium tetrakis(pentafluorophenyl)borate were then added to initiate polymerization. Ethylene was continuously supplied at 100 L/hr and polymerization was carried out at 50° C. for 5 minutes under normal pressure, and then the polymerization was stopped by adding a small amount of methanol. After the polymerization was completed, the reaction product was added to 750 mL of methanol containing a small amount of hydrochloric acid to precipitate a polymer. After washing with the same solvent, it was dried under reduced pressure at 80° C. for 10 hours to obtain 0.201 g of ethylene polymer. Table 2 shows the physical properties of the obtained polymer.

<Production of ethylene/1-octene copolymer>
[Polymerization Example 3-1]
250 mL of toluene was charged into a glass reactor with an internal volume of 500 mL that was sufficiently purged with nitrogen, and the liquid phase and gas phase were saturated with ethylene at 100 L/hr. Thereafter, 2 mL of 1-octene, 0.1 mmol of triisobutylaluminum in terms of aluminum atom, 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 100 L/hr and polymerization was carried out at 60° C. for 10 minutes under normal pressure, and then the polymerization was stopped by adding a small amount of methanol. After the polymerization was completed, the reactant was added to 1000 mL of a 2:1 mixed solvent of methanol and acetone containing a small amount of hydrochloric acid to precipitate a polymer. After washing with the same solvent, it was dried under reduced pressure at 120° C. for 10 hours to obtain 0.454 g of ethylene/1-octene copolymer. Table 3 shows the physical properties of the obtained polymer.

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

[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, and 1.158 g of ethylene/1-octene copolymer was obtained. Table 3 shows the physical properties of the polymer.

<Production of ethylene/tetracyclododecene copolymer>
[Polymerization Example 4-1]
In a glass reactor with an internal volume of 500 mL that was sufficiently purged with nitrogen, 250 mL of a cyclohexane/hexane (9/1) mixed solution and tetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ]-3-dodecene ( (hereinafter also simply referred to as "TD") was charged, and the liquid phase and gas phase were saturated with ethylene at 50 L/hr. Thereafter, 1.0 mmol of triisobutylaluminum in terms of 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 50 L/hr and polymerization was carried out at 50° C. for 10 minutes under normal pressure, and then the polymerization was stopped by adding a small amount of isobutanol. After the polymerization was completed, the reactant 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, it was dried under reduced pressure at 130° C. for 10 hours to obtain 1.118 g of ethylene/TD copolymer. Table 4 shows the physical properties of the obtained polymer.

[Polymerization Example 4-2]
Polymerization was carried out except that 0.5 mmol of triisobutylaluminum was used in terms of aluminum atom, 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. Polymerization was carried out in the same manner as in Example 4-1 to obtain 0.267 g of ethylene/TD copolymer. Table 4 shows the physical property values of the polymer.

[Polymerization Example 4-3]
Polymerization was carried out except that 1.0 mmol of triisobutylaluminum was used in terms of aluminum atoms, 0.002 mmol of transition metal compound F instead of transition metal compound A, and 0.008 mmol of triphenylcarbenium tetrakis(pentafluorophenyl)borate. Polymerization was carried out in the same manner as in Example 4-1 to obtain 0.172 g of ethylene/TD copolymer. Table 4 shows the physical property values of the polymer.

[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 the cyclohexane/hexane (9/1) mixed solution, and 1.946 g of ethylene/TD copolymer was obtained. Table 4 shows the physical property values of the polymer.

[Polymerization Example 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 the cyclohexane/hexane (9/1) mixed solution, and 2.705 g of ethylene/TD copolymer was obtained. Table 4 shows the physical property values of the polymer.

[Polymerization Example 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. 1.539 g of /TD copolymer was obtained. Table 4 shows the physical property values of the polymer.

[Polymerization Comparative Example 4-1]
Polymerization was carried out except that 2.5 mmol of triisobutylaluminum was used 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. Polymerization was carried out in the same manner as in Example 4-1 to obtain 0.114 g of ethylene/TD copolymer. Table 4 shows the physical property values of the polymer. Tg was not observed.

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

As mentioned above, when the olefin polymerization catalyst of the present invention is used, excellent performance can be achieved in any one of the following items (preferably two or more items): high activity, high molecular weight, and copolymerizability in olefin homopolymerization and copolymerization. It can be seen that this shows that

[Polymerization Example 5-1]
1030 mL of hexane and 12 mL of 5-ethylidene-2-norbornene (ENB) were charged into a stainless steel autoclave with an internal volume of 2 L that was sufficiently purged with nitrogen, and after raising the temperature inside the system to 95°C, propylene was added at partial pressure. The total pressure was set to 1.6 MPa-G by charging 0.30 MPa in portions and supplying ethylene. Next, 0.3 mmol of triisobutylaluminum, 0.0005 mmol of transition metal compound D produced in Synthesis Example 4, and 0.002 mmol of triphenylcarbenium tetrakis(pentafluorophenyl)borate were introduced under nitrogen pressure, and the stirring rotation speed was increased. Polymerization was initiated by increasing the speed to 250 rpm. Thereafter, 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 a predetermined period of time had passed, the polymerization was stopped by adding a small amount of ethanol into the system, and then unreacted ethylene was purged. The obtained polymer solution was poured into a large excess methanol/acetone mixed solution to precipitate the polymer. The polymer was collected by filtration and dried under reduced pressure at 120° C. overnight to obtain 2.33 g of ethylene/propylene/ENB copolymer. Table 5 shows the physical properties of the obtained polymer.

[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 0.40 MPa, and 1.59 g of ethylene/propylene/ENB copolymer was obtained. Table 5 shows the physical properties of the polymer.

[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 0.45 MPa, and 3.09 g of ethylene/propylene/ENB copolymer was obtained. Table 5 shows the physical properties of the polymer.

[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 0.90 MPa, and 1.51 g of ethylene/propylene/ENB copolymer was obtained. Table 5 shows the physical properties of the polymer.

[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. Table 5 shows the physical properties of the polymer.

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

From the results disclosed in Table 5, when copolymerizing an olefin and a cyclic diene compound using the olefin polymerization catalyst containing the transition metal compound (A) of the present invention, propylene and 5-ethylidene-2-norbornene (ENB) The result was that a copolymer with a relatively high content was obtained. That is, it can be seen that the olefin polymerization catalyst containing the transition metal compound (A) of the present invention is a catalyst with excellent copolymerizability.

Claims (9)

A transition metal compound (A) specified by the following formula (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; It is a positive integer that is the same as the valence of the ligand.
When l is 2 or more, each of the plurality of L(l)s is independently the above-mentioned anionic ligand, and either is bonded to each other to form a ring or not bonded to each other.
M is an atom of a transition metal element belonging to groups 3 to 11 of the periodic table.
n is a positive integer.
X is a hydrogen atom, a halogen atom, a hydrocarbon group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a boron-containing group, an aluminum-containing group, a phosphorus-containing group, a halogen-containing group, a heterocyclic compound residue, silicon represents a substituent selected from the group consisting of a containing group, a germanium-containing group, and a tin-containing group. When n is 2 or more, the plurality of X's are each independently a hydrogen atom, a halogen atom, or the above-mentioned substituent, and either bond to each other to form a ring or do not bond to each other.
E represents an oxygen atom or a sulfur atom.
Z represents a boron atom.
The two Q's each independently represent an atom of a Group 15 element in the periodic table.
m is a positive integer.
When m is 2 or more, the plurality of groups represented by the following formula (1') are the same or different, and are bonded to each other to form a ring, or are not bonded to each other. .

The sum of l, m, and n is the same as the valence of M.
A plurality of Rh and Rp are each independently a hydrogen atom, a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, or a halogen atom, or a plurality of Rh and Rp are each independently a hydrocarbon group. A structure in which the hydrogen atom, carbon atom, or both contained in the hydrocarbon contains at least one type of atom selected from the group consisting of a nitrogen atom, an oxygen atom, a phosphorus atom, a halogen atom, and a silicon atom. or unsubstituted with the above 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 The substituents are either directly bonded to each other to form a covalent bond (including multiple bonds), or are not directly bonded to each other. ] The transition metal compound (A) according to claim 1, wherein the M is an atom of a transition metal element in Group 4 or 5 of the periodic table. The transition metal compound (A) according to claim 2, wherein the M is a titanium atom. The transition metal compound (A) according to claim 1, wherein the E is an oxygen atom. The transition metal compound (A) according to claim 1, which is a transition metal compound (A1) specified by the following formula (2).

[In formula (2),
L, M, X, E, Z, Q, Rh, 1, n and m are synonymous with L, M, can be,
Rr is a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, or a covalent bond between C and C, or Rr is a hydrocarbon group, and the hydrogen atom, carbon The atom, or both, is 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 is not substituted with the above structure. .
A plurality of Rs is each independently a hydrogen atom, a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, or a halogen atom, or a plurality of Rs is each independently a hydrocarbon group, Hydrogen atoms, carbon atoms, 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 not substituted with the above 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 two or more of Rr, Rs, and Rh are When bonded to each other, adjacent substituents are either directly bonded to each other to form a covalent bond (including multiple bonds), or are not directly bonded to each other. ] 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).

[In formulas (3) and (4),
M, X, E, Z, Q, Rh, Rr, Rs, n and m are respectively synonymous with M, X, E, Z, Q, Rh, Rr, Rs, n and m in the above formula (2). can be,
A plurality of R's are each 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 are each independently a hydrocarbon group, Hydrogen atoms, carbon atoms, 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 not substituted with the above structure. ] The transition metal compound (A) according to any one of claims 1 to 6,
(B-1) organometallic compound,
(B-2) an organoaluminumoxy compound; and (B-3) at least one compound (B) selected from the group consisting of a compound that reacts with the transition metal compound to form an ion pair. catalyst. A method for producing an olefin polymer, comprising polymerizing an olefin in the presence of the olefin polymerization catalyst according to claim 7. The method for producing an olefin polymer according to claim 8, wherein the olefin includes an α-olefin having 2 to 30 carbon atoms.