JP7296691B2 - Transition metal compound, catalyst for olefin polymerization, and method for producing olefin polymer - Google Patents

Description

The present invention provides a transition metal compound having a specific structure useful as a catalyst or catalyst component for olefin polymerization (also referred to as a metallocene compound in the present invention), an olefin polymerization catalyst containing the transition metal compound, and in the presence of the catalyst A method for producing an olefin polymer, in particular, a method for producing an olefin polymer by homopolymerizing ethylene or copolymerizing ethylene and an α-olefin, homopolymerizing propylene or copolymerizing propylene and an α-olefin. method for producing an olefin polymer by copolymerizing ethylene, a cyclic olefin, and an aromatic vinyl compound, or homopolymerization of 1-butene or copolymerization of 1-butene and α-olefin The present invention relates to a method for producing an olefin polymer that undergoes polymerization.

Metallocene catalysts are composed of a transition metal atom and an organic compound called a ligand. By changing the structure of this ligand and the position of the substituent and the steric and electronic effect of the substituent, the polymerization reaction The physical properties of the polymer obtained in the process are widely controlled. A large number of bridged metallocene compounds having specific structures have been synthesized in order to synthesize characteristic polymers.

For example, Patent Document 1 discloses an olefin polymerization catalyst comprising a transition metal complex having a ligand in which indene is bridged with dimethylsilylene and methylalumoxane, and Patent Documents 2 and 3 disclose A technique for highly controlling the stereoregularity and regioregularity of the resulting polyolefin by introducing an aromatic substituent in is disclosed.

Further, in Patent Document 4, using an azulene skeleton with an aromatic substituent introduced at the 4-position as a ligand, and in Patent Document 5, by introducing a heterocyclic substituent at the 2-position of the indene ring , disclose techniques for controlling the polymerization activity and the molecular weight and regularity of the resulting polyolefins.

Thus, various polymers have been synthesized by changing the structure of the ligand in the metallocene catalyst. Furthermore, synthesis of metallocene complexes with various structures is expected in order to synthesize more characteristic polymers and to achieve higher activation.

In Non-Patent Document 1, the introduction of electron-donating substituents into cyclopentadienyl-type ligands, particularly the introduction of highly electron-donating substituents containing heteroatoms, is in terms of polymerization activity in quantum scientific model calculations. reportedly desirable.

However, in the actual study of using a metallocene complex into which a heteroatom-containing electron-donating substituent was introduced as an olefin polymerization catalyst, it was far from industrial use in terms of catalytic activity and polyolefin molecular weight produced. , the interaction between the heteroatom of the electron-donating substituent and the aluminum compound in the polymerization system has been suggested as the cause (Non-Patent Documents 2 and 3).

Patent Documents 6 and 7 disclose metallocene complexes with specific structures as methods for solving these problems, but require complicated and long synthetic steps.
Patent Document 8 also discloses a metallocene complex having a ligand in which indene is bridged with isopropylidene, which is similar to the one described in the present claims. There is no mention or description of examples.

JP-A-4-268307 JP-A-6-100579 JP-A-7-286005 JP-A-10-226712 Japanese Unexamined Patent Application Publication No. 2004-2259 Japanese translation of PCT publication No. 2014-525950 Japanese Patent Publication No. 2014-505136 JP 2014-193846 A

Organometallics 2001, 20, 5375. Organometallics 1992, 11, 2115. J. Organomet. Chem. 1996, 520, 63.

The present invention has been made to solve the above problems, and its object is to use a metallocene catalyst containing a transition metal compound having a specific structure to produce polyolefins of sufficient molecular weight and various high market value products. A method for producing various olefin polymers such as a high-density linear low-density olefin polymer with good olefin polymerization activity, a transition metal compound suitable for the olefin polymer, and a catalyst containing the transition metal compound to provide. That is, the object of the present invention is to provide a transition metal compound, a catalyst containing the same, and a method for producing an olefin polymer, which can easily react with (higher) α-olefins whose molecular weight can be increased and whose density can be adjusted, and which has high polymerization activity.

Another object of the present invention is to provide a transition metal compound capable of polymerizing propylene or 1-butene with high stereoregularity, a catalyst containing the same, and a method for producing an olefin polymer. be done.

As a result of intensive research in view of this situation, the present inventors have found that by introducing a specific group of substituents, that is, heteroatom-containing electron-donating substituents and proximal substituents into metallocene complexes, particularly excellent α- It has been found that a transition metal compound can be obtained which has copolymerizability with olefins and which gives an olefin polymer having a high molecular weight and a relatively narrow molecular weight distribution with good olefin polymerization activity. That is, the present inventors have found catalysts and methods for producing olefin polymers that are advantageous for producing various olefin polymers such as ethylene-based copolymers having sufficient molecular weight and low density, thereby completing the present invention.
The transition metal compound [A] of the present invention is represented by the following general formula [1].

In the general formula [1], M is a Group 4 transition metal atom of the periodic table, n is an integer of 1 to 4 that satisfies the valence of M, and X is a hydrogen atom, a halogen atom, or a hydrocarbon group. , an anionic ligand or a neutral ligand capable of coordinating with a lone pair, wherein the anionic ligand is a halogen-containing group, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a phosphorus containing group, boron-containing group, aluminum-containing group or conjugated diene-based divalent derivative group, and when n is 2 or more, the multiple groups represented by X may be the same or different and are bonded to each other. may form a ring, Q is a divalent hydrocarbon group, a divalent silicon-containing group or a divalent germanium-containing group, R ¹ to R ⁴ are each independently a hydrogen atom, a to 40 hydrocarbon, halogen-containing, silicon-containing, oxygen-containing, nitrogen-containing or sulfur-containing groups, each of which may be the same or different, and the adjacent substituents of R ¹ to R ⁴ are , may be bonded to each other to form a ring, R ¹¹ to R ¹⁴ are each independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms and may be the same or different, and R ^a1 to Each R ^a4 independently represents a hydrocarbon group having 1 to 20 carbon atoms, an aromatic hydrocarbon group having 6 ^to 40 carbon atoms or a silicon-containing group, and may be the same or ^different . R ^a2 and R ¹² , R ^a3 and R ¹³ , R ^a4 and R ¹⁴ may combine with each other to form a ring, and R ^b1 and R ^b2 are substituents represented by the following general formula [2]; Alternatively, an optionally substituted heterocyclic aromatic group having a five-membered ring with a mother skeleton containing at least one atom selected from nitrogen, oxygen, and sulfur, which may be the same or different Well, Z ¹ and Z ² are each independently a C ³ or ⁴ saturated or represents an unsaturated hydrocarbon group, the substituents on Z ¹ may be combined with R ¹¹ and R ¹² and the substituents on Z ² with R ¹³ and R ¹⁴ to form a ring.

In general formula [2], V is an atom selected from nitrogen, oxygen or sulfur, m is an integer of 1 or 2 that satisfies the valence of V, R ^c is each independently a hydrogen atom, is a hydrocarbon group having 1 to 40 carbon atoms, a silicon-containing group, an ether bond-containing hydrocarbon group or a tertiary amino group-containing hydrocarbon group, and R ^c forming R ^b1 is at least selected from R ^a1 and R ^a2 One of them and at least one of R ^c forming R ^b2 and selected from R ^a3 and R ^a4 may combine with each other to form an optionally substituted ring, and when m is 2 , may be the same or different, and R ^c may combine with each other to form a ring which may have a substituent.
The transition metal compound [A] is preferably represented by the following general formula [3].

In general formula [3], M, X, n, Q, R ¹ to R ⁴ , R ¹¹ to R ¹⁴ , R ^a1 to R ^a4 , R ^b1 and R ^b2 are respectively M, X , n, Q, R ¹ to R ⁴ , R ¹¹ to R ¹⁴ , R ^a1 to R ^a4 , R ^b1 and R ^b2 , and R ⁵ to R ¹⁰ each independently represent a hydrogen atom and 1 carbon atom. to 40 hydrocarbon, halogen-containing, silicon-containing, oxygen-containing, nitrogen-containing or sulfur-containing groups, each of which may be the same or different, and adjacent substituents from R ⁵ to R ¹⁰ ; R ⁵ and R ¹¹ or R ¹² , R ⁸ and R ¹³ or R ¹⁴ may combine with each other to form a ring.

In general formula [3], R ^b1 and R ^b2 are preferably substituents represented by general formula [2].
In the general formula [3], M is a zirconium atom or a hafnium atom, X is each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms or an oxygen-containing group, and Q is , a divalent hydrocarbon group or a divalent silicon-containing group.

In the general formula [3], R ¹ and R ³ are each independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms and may be the same or different, and R ² and R ⁴ are a hydrogen atom, and R ⁵ to R ¹⁰ each independently represent a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms or an oxygen-containing group, which may be the same or different, and R ⁵ and R ⁶ , When R ⁸ and R ⁹ form a ring structure, it is a saturated ring, and in the substituent represented by the general formula [2], V is preferably an atom selected from nitrogen and oxygen.

In the general formula [3], R ¹¹ to R ¹⁴ are hydrogen atoms, R ⁵ to R ¹⁰ are hydrogen atoms or hydrocarbon groups having 1 to 20 carbon atoms, and R ^a1 to R ^a4 are carbon atoms. A hydrocarbon group having a number of 1 to 20, an aromatic hydrocarbon group having a carbon number of 6 to 40 or a silicon-containing group, and in the substituent represented by the general formula [2], R ^c is a hydrogen atom or a carbon number 1 to 20 hydrocarbon groups, wherein R ^c forming R ^b1 is at least one selected from R ^a1 and R ^a2 and R ^c forming R ^b2 is at least one selected from R ^a3 and R ^a4 and are bonded together to form a ring structure, it is a saturated ring. When m is 2, it is preferably a saturated ring when R ^c is bonded together to form a ring structure.

In the general formula [3], R ⁵ to R ¹⁰ are hydrogen atoms, R ^a1 to R ^a4 are hydrocarbon groups having 1 to 10 carbon atoms, R ^b1 and R ^b2 are alkoxy groups, dialkyl An amino group or a pyrrolidinyl group is preferred.

The olefin polymerization catalyst of the present invention is characterized by containing the transition metal compound [A] of the present invention.
Further, the method for producing an olefin polymer of the present invention is characterized by including a step of polymerizing an olefin in the presence of the olefin polymerization catalyst of the present invention.

In the present specification, the term "polymerization" is used in the sense of including not only homopolymerization but also copolymerization, and the term "polymer" includes not only homopolymers but also copolymers. Used in an inclusive sense.

The olefin polymerization catalyst containing the transition metal compound (A) according to the present invention exhibits good olefin polymerization activity when olefin polymerization, particularly ethylene homopolymerization or ethylene and α-olefin copolymerization is carried out. , while being able to produce an olefin polymer having a sufficient molecular weight, it exhibits particularly excellent α-olefin copolymerizability. Also, preferably in regions of low density, the resulting polymer tends to have a relatively narrow molecular weight distribution.

In the method for producing an olefin polymer according to the present invention, homopolymerization of propylene, copolymerization of propylene and α-olefin, copolymerization of ethylene, a cyclic olefin, and an aromatic vinyl compound, homopolymerization of 1-butene, Copolymerization of -butene with α-olefins can also be carried out with good polymerization activity.
Further, when propylene or 1-butene is polymerized using the olefin polymerization catalyst containing the transition metal compound (A) according to the present invention, the resulting polymer has high stereoregularity.

Next, the present invention will be specifically described.
<Catalyst for Olefin Polymerization>
The olefin polymerization catalyst of the present invention is specifically described below.
The olefin polymerization catalyst according to the present invention contains a novel transition metal compound [A] represented by the general formula [1], preferably general formula [3], and [B] an organometallic compound (B- 1), at least one compound selected from the group consisting of an organoaluminumoxy compound (B-2), and a compound (B-3) that forms an ion pair by reacting with the transition metal compound [A]. preferable. The transition metal compound [A] is also provided by the present invention. In this specification, olefin refers to any compound having a polymerizable double bond. The transition metal compound [A] and the compound [B] ((B-1) to (B-3)) will be described in detail below.

[[A] transition metal compound]
The transition metal compound [A] constituting the olefin polymerization catalyst of the present invention is a compound represented by the above general formula [1], preferably a compound represented by the above general formula [3].
In the general formula [1], M is a Group 4 transition metal atom of the periodic table, specifically a titanium atom, a zirconium atom or a hafnium atom, preferably a zirconium atom or a hafnium atom, particularly preferably a zirconium atom. is.

n is an integer of 1 to 4, preferably 1 or 2, which satisfies the valence of M;
X is a hydrogen atom, a halogen atom (X), a hydrocarbon group (G1), an anionic ligand, or a neutral ligand (L1) capable of coordinating with a lone pair, and the anionic ligand is , halogen-containing groups (H1), silicon-containing groups (Si1), oxygen-containing groups (O1), sulfur-containing groups (S1), nitrogen-containing groups (N1), phosphorus-containing groups (P), boron-containing groups (B), It is an aluminum-containing group (Al) or a conjugated diene-based divalent derivative group (DE). X is preferably a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms or an oxygen-containing group.

When n is 2 or more, multiple groups represented by X may be the same or different, and may be combined to form a ring. Moreover, when there are a plurality of the rings, they may be the same or different.

Specific examples of the halogen atom (X) include fluorine, chlorine, bromine, and iodine, with chlorine or bromine being preferred.
The hydrocarbon group (G1) is not particularly limited as long as the effect of the present invention is exhibited, but examples include methyl group, ethyl group, 1-propyl group, 1-butyl group, 1-pentyl group, 1-hexyl group, 1-heptyl group, 1-octyl group, iso-propyl group, sec-butyl (butan-2-yl) group, tert-butyl (2-methylpropan-2-yl) group, iso-butyl (2-methylpropyl ) group, pentan-2-yl group, 2-methylbutyl group, iso-pentyl (3-methylbutyl) group, neopentyl (2,2-dimethylpropyl) group, siamyl (1,2-dimethylpropyl) group, iso-hexyl (4-methylpentyl) group, 2,2-dimethylbutyl group, 2,3-dimethylbutyl group, 3,3-dimethylbutyl group, thexyl(2,3-dimethylbut-2-yl) group, 4,4 - a linear or branched alkyl group such as a dimethylpentyl group;
vinyl group, allyl group, propenyl group (prop-1-en-1-yl group), iso-propenyl group (prop-1-en-2-yl group), allenyl (prop-1,2-diene-1- yl group) group, but-3-en-1-yl group, crotyl (but-2-en-1-yl) group, but-3-en-2-yl group, methallyl (2-methylallyl) group, erythrenyl (but-1,3-dienyl) group, pent-4-en-1-yl group, pent-3-en-1-yl group, pent-2-en-1-yl group, iso-pentenyl (3- methylbut-3-en-1-yl) group, 2-methylbut-3-en-1-yl group, pent-4-en-2-yl group, prenyl (3-methylbut-2-en-1-yl) linear or branched alkenyl groups or unsaturated double bond-containing groups such as groups;
linear or branched alkynyl groups or unsaturated triple bond-containing groups such as ethynyl groups, prop-2-yn-1-yl groups, propargyl (prop-1-yn-1-yl) groups;
benzyl group, 2-methylbenzyl group, 4-methylbenzyl group, 2,4,6-trimethylbenzyl group, 3,5-dimethylbenzyl group, cuminyl (4-iso-propylbenzyl) group, 2,4,6- Aromatic-containing linear or branched groups such as tri-iso-propylbenzyl, 4-tert-butylbenzyl, 3,5-di-tert-butylbenzyl, 1-phenylethyl, benzhydryl (diphenylmethyl) groups Alkyl groups and unsaturated double bond-containing groups;
Cyclic saturated hydrocarbon groups such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cycloheptatrienyl group, a norbornyl group, a norbornenyl group, a 1-adamantyl group, and a 2-adamantyl group;
phenyl group, tolyl (methylphenyl) group, xylyl (dimethylphenyl) group, mesityl (2,4,6-trimethylphenyl) group, cumenyl (iso-propylphenyl) group, juryl (2,3,5,6-tetra methylphenyl) group, 2,6-di-iso-propylphenyl group, 2,4,6-tri-iso-propylphenyl group, 4-tert-butylphenyl group, 3,5-di-tert-butylphenyl group , naphthyl group, biphenyl group, ter-phenyl group, binaphthyl group, acenaphthalenyl group, phenanthryl group, anthracenyl group, pyrenyl group, ferrocenyl group, and other aromatic substituted (aryl) groups;

Among the above hydrocarbon groups, preferably methyl group, iso-butyl (2-methylpropyl) group, neopentyl (2,2-dimethylpropyl) group, siamyl (1,2-dimethylpropyl) group, benzyl group, phenyl group, tolyl (methylphenyl) group, xylyl (dimethylphenyl) group, mesityl (2,4,6-trimethylphenyl) group, and cumenyl (iso-propylphenyl) group.

The halogen-containing group (H1) is not particularly limited as long as the effect of the present invention is exhibited, but examples include fluoromethyl group, trifluoromethyl group, trichloromethyl group, pentafluoroethyl group, 2,2,2-trifluoro Examples include ethyl group, fluorophenyl group, difluorophenyl group, trifluorophenyl group, tetrafluorophenyl group, pentafluorophenyl group, trifluoromethylphenyl group, bistrifluoromethylphenyl group, hexachloroantimonate anion, and the like.

Pentafluorophenyl group is preferred among the halogen-containing groups.
The silicon-containing group (Si1) is not particularly limited as long as the effect of the present invention is exhibited, but examples thereof include a trimethylsilyl group, a triethylsilyl group, a tri-iso-propylsilyl group, a diphenylmethylsilyl group and a tert-butyldimethylsilyl group. , tert-butyldiphenylsilyl group, triphenylsilyl group, tris(trimethylsilyl)silyl group, trimethylsilylmethyl group and the like.

Among the silicon-containing groups, preferred is a trimethylsilylmethyl group.
The oxygen-containing group (O1) is not particularly limited as long as the effect of the present invention is exhibited, but examples thereof include methoxy group, ethoxy group, n-propoxy group, iso-propoxy group, allyloxy group, n-butoxy group, sec- butoxy group, iso-butoxy group, tert-butoxy group, benzyloxy group, methoxymethoxy group, phenoxy group, 2,6-dimethylphenoxy group, 2,6-di-iso-propylphenoxy group, 2,6-di- tert-butylphenoxy group, 2,4,6-trimethylphenoxy group, 2,4,6-tri-iso-propylphenoxy group, acetoxy group, pivaloyloxy group, benzoyloxy group, trifluoroacetoxy group, perchlorate anion, A periodate anion and the like can be mentioned.

Among the oxygen-containing groups, methoxy, ethoxy, iso-propoxy and tert-butoxy groups are preferred.
The sulfur-containing group (S1) is not particularly limited as long as the effect of the present invention is exhibited, but examples include mesyl (methanesulfonyl) group, phenylsulfonyl group, tosyl (p-toluenesulfonyl) group, triflyl (trifluoromethanesulfonyl) group, nonafryl (nonafluorobutanesulfonyl) group, mesylate (methanesulfonate) group, tosylate (p-toluenesulfonate) group, triflate (trifluoromethanesulfonate) group, nonaflate (nonafluorobutanesulfonate) group, etc. be able to.

Preferred among the sulfur-containing groups are triflate (trifluoromethanesulfonate) groups.
The nitrogen-containing group (N1) is not particularly limited as long as the effect of the present invention is exhibited, but examples include amino group, cyano group, methylamino group, dimethylamino group, ethylamino group, diethylamino group, allylamino group, diallylamino group, benzylamino group, dibenzylamino group, pyrrolidinyl group, piperidinyl group, morpholyl group, pyrrolyl group, bistrifurylimide group and the like.

Among the nitrogen-containing groups, preferred are dimethylamino group, diethylamino group, pyrrolidinyl group, pyrrolyl group and bistrifurylimide group.
The phosphorus-containing group (P) is not particularly limited as long as the effects of the present invention are achieved, and examples thereof include hexafluorophosphate anions.

The boron-containing group (B) is not particularly limited as long as the effect of the present invention is achieved, but examples include tetrafluoroborate anion, tetrakis(pentafluorophenyl)borate anion, (methyl)(tris(pentafluorophenyl) )borate anion, (benzyl)(tris(pentafluorophenyl))borate anion, tetrakis((3,5-bistrifluoromethyl)phenyl)borate anion, BR ₄ (R is hydrogen, an alkyl group, or a substituent an aryl group or a halogen atom, etc., which may be possessed).

The aluminum-containing group (Al) is not particularly limited as long as the effect of the present invention is exhibited, but for example, (M-halogen atom-aluminum atom-hydrocarbon group) four-membered ring, or (M-hydrocarbon group-aluminum atom-hydrocarbon group) AlR ₄ (R represents hydrogen, an alkyl group, an optionally substituted aryl group, a halogen atom, or the like) capable of forming a four-membered ring.

The conjugated diene-based divalent derivative group (DE) is not particularly limited as long as the effects of the present invention are exhibited, but examples thereof include a 1,3-butadienyl group, an isoprenyl (2-methyl-1,3-butadienyl) group, and a piperylenenyl group. Metallocyclopentene groups such as (1,3-pentadienyl) group, 2,4-hexadienyl group, 1,4-diphenyl-1,3-pentadienyl group and cyclopentadienyl group can be mentioned.

The neutral ligand (L1) capable of coordinating with a lone pair is not particularly limited as long as the effect of the present invention is exhibited, but examples thereof include ethers such as diethyl ether, tetrahydrofuran, dioxane, and 1,2-dimethoxyethane. , triethylamine, diethylamine and other amines, pyridine, picoline, lutidine, oxazoline, oxazole, thiazole, imidazole, thiophene and other heterocyclic compounds, triphenylphosphine, tricyclohexylphosphine, tri-tert-butylphosphine and other organophosphorus compounds can be mentioned.

Q is a divalent group linking two ligands, specifically Q is a divalent hydrocarbon group, a divalent silicon-containing group or a divalent germanium-containing group. Q is preferably a divalent hydrocarbon group or a divalent silicon-containing group.

Examples of divalent hydrocarbon groups include hydrocarbon groups having 1 to 20 carbon atoms such as alkylene groups, substituted alkylene groups, cycloalkylene groups and alkylidene groups.
Specific examples of divalent alkylene groups having 1 to 20 carbon atoms, substituted alkylene groups, cycloalkylene groups and alkylidene groups include alkylene groups such as methylene, ethylene, propylene and butylene;
Isopropylidene, dimethylmethylene, diethylmethylene, dipropylmethylene, diisopropylmethylene, dibutylmethylene, methylethylmethylene, methylbutylmethylene, methyl-t-butylmethylene, dihexylmethylene, dicyclohexylmethylene, methylcyclohexylmethylene, methylphenylmethylene, diphenylmethylene , ditolylmethylene, methylnaphthylmethylene, dinaphthylmethylene, benzylphenylmethylene, dibenzylmethylene, 1-methylethylene, 1,2-dimethylethylene, 1-ethyl-2-methylethylene, substituted alkylene groups;
cycloalkylene groups such as cyclopropylidene, cyclobutylidene, cyclopentylidene, cyclohexylidene, cycloheptylidene, bicyclo[3.3.1]nonylidene, norbornylidene, adamantylidene, tetrahydronaphtylidene, dihydroindanidene; ;
Examples include alkylidene groups such as ethylidene, propylidene and butylidene.

Divalent silicon-containing groups include silylene, methylsilylene, dimethylsilylene, diisopropylsilylene, dibutylsilylene, methylbutylsilylene, methyl-t-butylsilylene, dicyclohexylsilylene, methylcyclohexylsilylene, methylphenylsilylene, diphenylsilylene, ditolyl. silylene, methylnaphthylsilylene, dinaphthylsilylene, cyclodimethylsilylene, cyclotrimethylenesilylene, cyclotetramethylenesilylene, cyclopentamethylenesilylene, cyclohexamethylenesilylene, and cycloheptamethylenesilylene groups, preferably dimethylsilylene, They are dibutylsilylene, diphenylsilylene, cyclotrimethylenesilylene, cyclotetramethylenesilylene, and cyclopentamethylenesilylene.

Examples of divalent germanium-containing groups include groups in which silicon is converted to germanium in the above divalent silicon-containing groups.
Preferred groups for Q include alkylene groups having 1 to 20 carbon atoms, substituted alkylene groups, cycloalkylene groups, and silicon-containing groups.

R ¹ to R ⁴ each independently represents a hydrogen atom, a hydrocarbon group having 1 to 40 carbon atoms (G2), a halogen-containing group (H2), a silicon-containing group (Si2), an oxygen-containing group (O2), a nitrogen-containing group (N2) or sulfur-containing hydrocarbon group (S2), each of which may be the same or different, and adjacent substituents of R ¹ to R ⁴ may combine with each other to form a ring. Moreover, when there are a plurality of the rings, they may be the same or different.

The hydrocarbon group having 1 to 40 carbon atoms (G2) preferably includes a hydrocarbon group having 1 to 20 carbon atoms (excluding an aromatic hydrocarbon group) and an aromatic hydrocarbon group having 6 to 40 carbon atoms. group hydrocarbon group (aryl group). More specifically, the hydrocarbon group having 1 to 20 carbon atoms is preferably an aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms. The hydrocarbon group having 1 to 20 carbon atoms also includes a substituent having an aromatic structure such as an arylalkyl group.

The hydrocarbon group (G2) having 1 to 40 carbon atoms is not particularly limited as long as the effect of the present invention is exhibited, but examples thereof include methyl group, ethyl group, 1-propyl group, 1-butyl group and 1-pentyl group. , 1-hexyl group, 1-heptyl group, 1-octyl group, 1-nonyl group, 1-decanyl group, 1-undecanyl group, 1-dodecanyl group, 1-eicosanyl, iso-propyl group, sec-butyl (butane -2-yl) group, tert-butyl (2-methylpropan-2-yl) group, iso-butyl (2-methylpropyl) group, pentan-2-yl group, 2-methylbutyl group, iso-pentyl (3 -methylbutyl) group, neopentyl (2,2-dimethylpropyl) group, tert-pentyl (1,1-dimethylpropyl) group, siamyl (1,2-dimethylpropyl) group, pentan-3-yl group, 2-methyl Pentyl group, 3-methylpentyl group, iso-hexyl (4-methylpentyl) group, 1,1-dimethylbutyl (2-methylpentan-2-yl) group, 3-methylpentan-2-yl group, 4- methylpentan-2-yl group, 2,2-dimethylbutyl group, 2,3-dimethylbutyl group, 3,3-dimethylbutyl group, thexyl (2,3-dimethylbut-2-yl) group, 3-methyl Pentan-3-yl group, 3,3-dimethylbut-2-yl group, hexane-3-yl group, 2-methylpentan-3-yl group, heptane-4-yl group, 2,4-dimethylpentane- 3-yl group, 3-ethylpentan-3-yl group, 4,4-dimethylpentyl group, 4-methylheptan-4-yl group, 4-propylheptan-4-yl group, 2,3,3-trimethyl linear or branched alkyl groups having 1 to 20 carbon atoms such as butan-2-yl group and 2,3,4-trimethylpentan-3-yl group;
vinyl group, allyl group, propenyl group (prop-1-en-1-yl group), iso-propenyl group (prop-1-en-2-yl group), allenyl (prop-1,2-diene-1- yl group) group, but-3-en-1-yl group, crotyl (but-2-en-1-yl) group, but-3-en-2-yl group, methallyl (2-methylallyl) group, erythrenyl (but-1,3-dienyl) group, pent-4-en-1-yl group, pent-3-en-1-yl group, pent-2-en-1-yl group, iso-pentenyl (3- methylbut-3-en-1-yl) group, 2-methylbut-3-en-1-yl group, pent-4-en-2-yl group, prenyl (3-methyl-but-2-en-1- yl) group, 2-methyl-but-2-en-1-yl group, pent-3-en-2-yl group, 2-methyl-but-3-en-2-yl group, pent-1-ene -3-yl group, penta-2,4-dien-1-yl group, penta-1,3-dien-1-yl group, penta-1,4-dien-3-yl group, iso-prenyl (2 -methyl-but-1,3-dien-1-yl) group, pent-2,4-dien-2-yl group, hex-5-en-1-yl group, hex-4-en-1-yl group, hex-3-en-1-yl group, hex-2-en-1-yl group, 4-methyl-pent-4-en-1-yl group, 3-methyl-pent-4-en-1 -yl group, 2-methyl-pent-4-en-1-yl group, hex-5-en-2-yl group, 4-methyl-pent-3-en-1-yl group, 3-methyl-penta -3-en-1-yl group, 2,3-dimethyl-but-2-en-1-yl group, 2-methylpent-4-en-2-yl group, 3-ethylpent-1-en-3- yl group, hex-3,5-dien-1-yl group, hex-2,4-dien-1-yl group, 4-methylpent-1,3-dien-1-yl group, 2,3-dimethyl- buta-1,3-dien-1-yl group, hexa-1,3,5-trien-1-yl group, 2-(cyclopentadienyl)propan-2-yl group, 2-(cyclopentadienyl ) a linear or branched alkenyl group or an unsaturated double bond-containing group having 2 to 40 carbon atoms such as an ethyl group;
ethynyl group, prop-2-yn-1-yl group, propargyl (prop-1-yn-1-yl) group, but-1-yn-1-yl group, but-2-yn-1-yl group, but-3-yn-1-yl group, pent-1-yn-1-yl group, pent-2-yn-1-yl group, pent-3-yn-1-yl group, pent-4-yn- 1-yl group, 3-methyl-but-1-yn-1-yl group, pent-3-yn-2-yl group, 2-methyl-but-3-yn-1-yl group, pent-4- yn-2-yl group, hex-1-yn-1-yl group, 3,3-dimethyl-but-1-yn-1-yl group, 2-methyl-pent-3-yn-2-yl group, straight chain having 2 to 40 carbon atoms such as 2,2-dimethyl-but-3-yn-1-yl group, hex-4-yn-1-yl group, hex-5-yn-1-yl group; linear or branched alkynyl groups or unsaturated triple bond-containing groups;
benzyl group, 2-methylbenzyl group, 4-methylbenzyl group, 2,4,6-trimethylbenzyl group, 3,5-dimethylbenzyl group, cuminyl (4-iso-propylbenzyl) group, 2,4,6- tri-iso-propylbenzyl group, 4-tert-butylbenzyl group, 3,5-di-tert-butylbenzyl group, 1-phenylethyl group, benzhydryl (diphenylmethyl) group, cumyl (2-phenylpropane-2- yl) group, 2-(4-methylphenyl)propan-2-yl group, 2-(3,5-dimethylphenyl)propan-2-yl group, 2-(4-tert-butylphenyl)propane-2- yl group, 2-(3,5-di-tert-butylphenyl)propan-2-yl group, 3-phenylpentan-3-yl group, 4-phenylhepta-1,6-dien-4-yl group, 1,2,3-triphenylpropan-2-yl group, 1,1-diphenylethyl group, 1,1-diphenylpropyl group, 1,1-diphenyl-but-3-en-1-yl group, 1, 1,2-triphenylethyl group, trityl (triphenylmethyl) group, tri-(4-methylphenyl)methyl group, 2-phenylethyl group, styryl (2-phenylvinyl) group, 2-(2-methylphenyl) ) ethyl group, 2-(4-methylphenyl)ethyl group, 2-(2,4,6-trimethylphenyl)ethyl group, 2-(3,5-dimethylphenyl)ethyl group, 2-(2,4, 6-tri-iso-propylphenyl)ethyl group, 2-(4-tert-butylphenyl)ethyl group, 2-(3,5-di-tert-butylphenyl)ethyl group, 2-methyl-1-phenylpropane -2-yl group, 3-phenylpropyl group, 2-cinnamyl (3-phenylallyl) group, neophyll (2-methyl-2-phenylpropyl) group, 3-methyl-3-phenylbutyl group, 2-methyl- 4-phenylbutan-2-yl group, cyclopentadienyldiphenylmethyl group, 2-(1-indenyl)propan-2-yl group, (1-indenyl)diphenylmethyl group, 2-(1-indenyl)ethyl group , 2-(tetrahydro-1-indacenyl)propan-2-yl group, (tetrahydro-1-indacenyl)diphenylmethyl group, 2-(tetrahydro-1-indacenyl)ethyl group, 2-(1-benzoindenyl)propane -2-yl group, (1-benzoindenyl)diphenylmethyl group, 2-(1-benzoindenyl)ethyl group, 2-(9-fluorenyl)propan-2-yl group, (9-fluorenyl)diphenylmethyl group, 2-(9-fluorenyl)ethyl group, 2-(1-azulenyl)propan-2-yl group, (1-azulenyl)diphenylmethyl group, 2-(1-azulenyl)ethyl group, etc. 7-40 aromatic-containing linear or branched alkyl groups and unsaturated double bond-containing groups;
cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclopentenyl group, cyclopentadienyl group, dimethylcyclopentadienyl group, n-butylcyclopentadienyl group, n-butyl-methylcyclopentadienyl group, tetramethylcyclo pentadienyl group, 1-methylcyclopentyl group, 1-allylcyclopentyl group, 1-benzylcyclopentyl group, cyclohexyl group, cyclohexenyl group, cyclohexadienyl group, 1-methylcyclohexyl group, 1-allylcyclohexyl group, 1-benzyl cyclohexyl group, cycloheptyl group, cycloheptenyl group, cycloheptatrienyl group, 1-methylcycloheptyl group, 1-allylcycloheptyl group, 1-benzylcycloheptyl group, cyclooctyl group, cyclooctenyl group, cyclooctadienyl group, cyclooctatrienyl group, 1-methylcyclooctyl group, 1-allylcyclooctyl group, 1-benzylcyclooctyl group, 4-cyclohexyl-tert-butyl group, norbornyl group, norbornenyl group, norbornadienyl group, 2- methylbicyclo[2.2.1]heptan-2-yl group, 7-methylbicyclo[2.2.1]heptan-7-yl group, bicyclo[2.2.2]octan-1-yl group, bicyclo [2.2.2] octan-2-yl group, 1-adamantyl group, 2-adamantyl group, 1-(2-methyladamantyl), 1-(3-methyladamantyl), 1-(4-methyladamantyl) , 1-(2-phenyladamantyl), 1-(3-phenyladamantyl), 1-(4-phenyladamantyl), 1-(3,5-dimethyladamantyl), 1-(3,5,7-trimethyladamantyl) ), 1-(3,5,7-triphenyladamantyl), pentalenyl group, indenyl group, fluorenyl group, indacenyl group, tetrahydroindacenyl group, benzoindenyl group, azulenyl group, etc. having 3 to 40 carbon atoms cyclic saturated and unsaturated hydrocarbon groups of;
phenyl group, tolyl (methylphenyl) group, xylyl (dimethylphenyl) group, mesityl (2,4,6-trimethylphenyl) group, cumenyl (iso-propylphenyl) group, juryl (2,3,5,6-tetra methylphenyl) group, 2,6-di-iso-propylphenyl group, 2,4,6-tri-iso-propylphenyl group, 4-tert-butylphenyl group, 3,5-di-tert-butylphenyl group , allylphenyl group, (but-3-en-1-yl)phenyl group, (but-2-en-1-yl)phenyl group, methallylphenyl group, prenylphenyl group, 4-adamantylphenyl group, 3, 5-Di-adamantylphenyl group, naphthyl group, biphenyl group, ter-phenyl group, binaphthyl group, acenaphthalenyl group, phenanthryl group, anthracenyl group, pyrenyl group, ferrocenyl group, etc. Aromatic substitution having 6 to 40 carbon atoms ( aryl) group; and the like.

Among the linear or branched alkyl groups having 1 to 40 carbon atoms, preferably methyl group, ethyl group, 1-propyl group, 1-butyl group, 1-pentyl group, 1-hexyl group, 1-heptyl group, 1-octyl group, iso-propyl group, sec-butyl (butan-2-yl) group, tert-butyl (2-methylpropan-2-yl) group, iso-butyl (2-methylpropyl ) group, iso-pentyl (3-methylbutyl) group, neopentyl (2,2-dimethylpropyl) group, tert-pentyl (1,1-dimethylpropyl) group, pentan-3-yl group, iso-hexyl (4- methylpentyl) group, 1,1-dimethylbutyl (2-methylpentan-2-yl) group, 3,3-dimethylbutyl group, thexyl (2,3-dimethylbut-2-yl) group, 3-methylpentane -3-yl group, heptane-4-yl group, 2,4-dimethylpentan-3-yl group, 3-ethylpentan-3-yl group, 4,4-dimethylpentyl group, 4-methylheptane-4- yl group, 4-propylheptan-4-yl group and the like, more preferably methyl group, ethyl group, 1-propyl group, 1-butyl group, 1-pentyl group, 1-hexyl group, iso -propyl group and tert-butyl (2-methylpropan-2-yl) group.

Among the linear or branched alkenyl groups or unsaturated double bond-containing groups having 2 to 40 carbon atoms, preferably vinyl group, allyl group, but-3-en-1-yl group, crotyl (but-2-en-1-yl) group, methallyl (2-methylallyl) group, pent-4-en-1-yl group, prenyl (3-methyl-but-2-en-1-yl) group, Pent-1,4-dien-3-yl group, hex-5-en-1-yl group, 2-methylpent-4-en-2-yl group, 2-(cyclopentadienyl)propan-2-yl group, 2-(cyclopentadienyl)ethyl group and the like, more preferably vinyl group, allyl group, but-3-en-1-yl group, pent-4-en-1-yl group , prenyl (3-methyl-but-2-en-1-yl) group, and hex-5-en-1-yl group.

Among the linear or branched alkynyl groups or unsaturated triple bond-containing groups having 2 to 40 carbon atoms, preferred are ethynyl, prop-2-yn-1-yl, propargyl (prop-1 -yn-1-yl) group, but-2-yn-1-yl group, but-3-yn-1-yl group, pent-3-yn-1-yl group, pent-4-yn-1- yl group, 3-methyl-but-1-yn-1-yl group, 3,3-dimethyl-but-1-yn-1-yl group, hex-4-yn-1-yl group, hex-5- yn-1-yl group and the like, more preferably prop-2-yn-1-yl group, propargyl (prop-1-yn-1-yl) group, but-2-yn-1- yl group and but-3-yn-1-yl group.

Among the aromatic-containing linear or branched alkyl groups and unsaturated double bond-containing groups having 7 to 40 carbon atoms, preferably benzyl group, 2-methylbenzyl group, 4-methylbenzyl group, 2,4,6-trimethylbenzyl group, 3,5-dimethylbenzyl group, cuminyl (4-iso-propylbenzyl) group, 2,4,6-tri-iso-propylbenzyl group, 4-tert-butylbenzyl group , 3,5-di-tert-butylbenzyl group, benzhydryl (diphenylmethyl) group, cumyl (2-phenylpropan-2-yl) group, 1,1-diphenylethyl group, trityl (triphenylmethyl) group, 2 -phenylethyl group, 2-(4-methylphenyl)ethyl group, 2-(2,4,6-trimethylphenyl)ethyl group, 2-(3,5-dimethylphenyl)ethyl group, 2-(2,4 ,6-tri-iso-propylphenyl)ethyl group, 2-(4-tert-butylphenyl)ethyl group, 2-(3,5-di-tert-butylphenyl)ethyl group, styryl(2-phenylvinyl) group, 2-methyl-1-phenylpropan-2-yl group, 3-phenylpropyl group, 2-cinnamyl (3-phenylallyl) group, neophyll (2-methyl-2-phenylpropyl) group, cyclopentadienyl Diphenylmethyl group, 2-(1-indenyl)propan-2-yl group, (1-indenyl)diphenylmethyl group, 2-(1-indenyl)ethyl group, 2-(9-fluorenyl)propan-2-yl group , (9-fluorenyl) diphenylmethyl group, 2-(9-fluorenyl) ethyl group and the like, more preferably benzyl group, benzhydryl (diphenylmethyl) group, cumyl (2-phenylpropan-2-yl ) group, 1,1-diphenylethyl group, trityl(triphenylmethyl) group, 2-phenylethyl group, 3-phenylpropyl group and 2-cinnamyl(3-phenylallyl) group.

Among the cyclic saturated and unsaturated hydrocarbon groups having 3 to 40 carbon atoms, cyclopropyl, cyclobutyl, cyclopentyl, cyclopentenyl, cyclopentadienyl, 1-methylcyclopentyl, 1 - allylcyclopentyl group, 1-benzylcyclopentyl group, cyclohexyl group, cyclohexenyl group, 1-methylcyclohexyl group, 1-allylcyclohexyl group, 1-benzylcyclohexyl group, cycloheptyl group, cycloheptenyl group, cycloheptatrienyl group, 1 -methylcycloheptyl group, 1-allylcycloheptyl group, 1-benzylcycloheptyl group, cyclooctyl group, cyclooctenyl group, cyclooctadienyl group, 4-cyclohexyl-tert-butyl group, norbornyl group, 2-methylbicyclo [ 2.2.1]heptan-2-yl group, bicyclo[2.2.2]octan-1-yl group, 1-adamantyl group, 2-adamantyl group, pentalenyl group, indenyl group, fluorenyl group and the like. Among them, more preferred are cyclopentyl group, cyclopentenyl group, 1-methylcyclopentyl group, cyclohexyl group, cyclohexenyl group, 1-methylcyclohexyl group and 1-adamantyl group.

Among the aromatic substituted (aryl) groups having 6 to 40 carbon atoms, preferably phenyl group, tolyl (methylphenyl) group, xylyl (dimethylphenyl) group, mesityl (2,4,6-trimethylphenyl) group, cumenyl (iso-propylphenyl) group, 2,6-di-iso-propylphenyl group, 2,4,6-tri-iso-propylphenyl group, 4-tert-butylphenyl group, 3,5-di -tert-butylphenyl group, allylphenyl group, prenylphenyl group, 4-adamantylphenyl group, naphthyl group, biphenyl group, ter-phenyl group, binaphthyl group, phenanthryl group, anthracenyl group, ferrocenyl group and the like, among which More preferably, phenyl group, tolyl (methylphenyl) group, xylyl (dimethylphenyl) group, mesityl (2,4,6-trimethylphenyl) group, cumenyl (iso-propylphenyl) group, 2,6-di-iso -propylphenyl group, 2,4,6-tri-iso-propylphenyl group, 4-tert-butylphenyl group, 3,5-di-tert-butylphenyl group, allylphenyl group, 4-adamantylphenyl group, naphthyl a biphenyl group, a phenanthryl group and an anthracenyl group.

The halogen-containing group (H2) is not particularly limited as long as the effect of the present invention is exhibited, but examples include fluoromethyl group, trifluoromethyl group, trichloromethyl group, pentafluoroethyl group, 2,2,2-trifluoro ethyl group, heptafluoropropyl group, 3,3,3-trifluoropropyl group, nonafluorobutyl group, 4,4,4-trifluorobutyl group, dodecafluorohexyl group, 6,6,6-trifluorohexyl group , chlorophenyl group, fluorophenyl group, difluorophenyl group, trifluorophenyl group, tetrafluorophenyl group, pentafluorophenyl group, di-tert-butyl-fluorophenyl group, trifluoromethylphenyl group, bistrifluoromethylphenyl group, tri fluoromethoxyphenyl group, bistrifluoromethoxyphenyl group, trifluoromethylthiophenyl group, bistrifluoromethylthiophenyl group, fluorobiphenyl group, difluorobiphenyl group, trifluorobiphenyl group, tetrafluorobiphenyl group, pentafluorobiphenyl group, di-tert- butyl-fluorobiphenyl group, trifluoromethylbiphenyl group, bistrifluoromethylbiphenyl group, trifluoromethoxybiphenyl group, bistrifluoromethoxybiphenyl group, trifluoromethyldimethylsilyl group, trifluoromethoxy group, pentafluoroethoxy group, fluorophenoxy group , difluorophenoxy group, trifluorophenoxy group, pentafluorophenoxy group, di-tert-butyl-fluorophenoxy group, trifluoromethylphenoxy group, bistrifluoromethylphenoxy group, trifluoromethoxyphenoxy group, bistrifluoromethoxyphenoxy group, difluoro A methylenedioxyphenyl group, a bistrifluoromethylphenyliminomethyl group, a trifluoromethylthio group, and the like can be mentioned.

Among the halogen-containing groups, fluoromethyl group, trifluoromethyl group, pentafluoroethyl group, 2,2,2-trifluoroethyl group, 3,3,3-trifluoropropyl group, 4,4,4 -trifluorobutyl group, fluorophenyl group, difluorophenyl group, trifluorophenyl group, tetrafluorophenyl group, pentafluorophenyl group, trifluoromethylphenyl group, bistrifluoromethylphenyl group, trifluoromethoxyphenyl group, pentafluorobiphenyl group, trifluoromethylbiphenyl group, bistrifluoromethylbiphenyl group, trifluoromethoxy group, pentafluorophenoxy group, bistrifluoromethylphenoxy group, bistrifluoromethylphenoxy group, difluoromethylenedioxyphenyl group, trifluoromethylthio group, etc. Among them, trifluoromethyl group, fluorophenyl group, pentafluorophenyl group, trifluoromethylphenyl group, bistrifluoromethylphenyl group, pentafluorobiphenyl group, trifluoromethoxy group and pentafluorophenoxy group are more preferred. be.

The silicon-containing group (Si2) is not particularly limited as long as the effect of the present invention is exhibited, but examples thereof include trimethylsilyl group, triethylsilyl group, tri-iso-propylsilyl group, diphenylmethylsilyl group and tert-butyldimethylsilyl group. , a tert-butyldiphenylsilyl group, a triphenylsilyl group, a tris(trimethylsilyl)silyl group, a cyclopentadienyldimethylsilyl group, a di-n-butyl(cyclopentadienyl)silyl group, a cyclopentadienyldiphenylsilyl group, indenyldimethylsilyl group, di-n-butyl(indenyl)silyl group, indenyldiphenylsilyl group, fluorenyldimethylsilyl group, di-n-butyl(fluorenyl)silyl group, fluorenyldiphenylsilyl group, 4- trimethylsilylphenyl group, 4-triethylsilylphenyl group, 4-tri-iso-propylsilylphenyl group, 4-tert-butyldiphenylsilylphenyl group, 4-triphenylsilylphenyl group, 4-tris(trimethylsilyl)silylphenyl group, etc. can be mentioned.

Among the silicon-containing groups, trimethylsilyl group, triethylsilyl group, tri-iso-propylsilyl group, tert-butyldimethylsilyl group, triphenylsilyl group, cyclopentadienyldimethylsilyl group and cyclopentadienyldiphenylsilyl group are preferred. group, indenyldimethylsilyl group, indenyldiphenylsilyl group, fluorenyldimethylsilyl group, fluorenyldiphenylsilyl group, 4-trimethylsilylphenyl group, 4-triethylsilylphenyl group, 4-tri-iso-propylsilylphenyl group, 4-triphenylsilylphenyl group, and the like, more preferably trimethylsilyl group, triethylsilyl group, tert-butyldimethylsilyl group, 4-trimethylsilylphenyl group, 4-triethylsilylphenyl group, 4-tri -iso-propylsilylphenyl group.

The oxygen-containing group (O2) is not particularly limited as long as the effect of the present invention is achieved, but examples include methoxy group, ethoxy group, n-propoxy group, iso-propoxy group, allyloxy group, n-butoxy group, sec- butoxy group, iso-butoxy group, tert-butoxy group, methallyloxy group, prenyloxy group, benzyloxy group, methoxymethoxy group, methoxyethoxy group, phenoxy group, naphthoxy group, toluyloxy group, iso-propylphenoxy group, allylphenoxy group, tert-butylphenoxy group, methoxyphenoxy group, iso-propoxyphenoxy group, allyloxyphenoxy group, biphenyloxy group, binaphthyloxy group, methoxymethyl group, allyloxymethyl group, benzyloxymethyl group, phenoxymethyl group, methoxy ethyl group, allyloxyethyl group, benzyloxyethyl group, phenoxyethyl group, methoxypropyl group, allyloxypropyl group, benzyloxypropyl group, phenoxypropyl group, methoxyvinyl group, allyloxyvinyl group, benzyloxyvinyl group, phenoxy vinyl group, methoxyallyl group, allyloxyallyl group, benzyloxyallyl group, phenoxyallyl group, dimethoxymethyl group, di-iso-propoxymethyl group, dioxolanyl group, tetramethyldioxolanyl group, dioxanyl group, methoxyphenyl group, iso-propoxyphenyl group, allyloxyphenyl group, phenoxyphenyl group, methylenedioxyphenyl group, furyl group, methylfuryl group, tetrahydrofuryl group, pyranyl group, tetrahydropyranyl group, furfuryl group, benzofuryl group, dibenzofuryl group, etc. can be mentioned.

Among the oxygen-containing groups, methoxy group, ethoxy group, iso-propoxy group, allyloxy group, n-butoxy group, tert-butoxy group, prenyloxy group, benzyloxy group, phenoxy group, naphthoxy group and toluyloxy group are preferred. , iso-propylphenoxy group, allylphenoxy group, tert-butylphenoxy group, methoxyphenoxy group, biphenyloxy group, binaphthyloxy group, allyloxymethyl group, benzyloxymethyl group, phenoxymethyl group, methoxyethyl group, methoxyallyl group , benzyloxyallyl group, phenoxyallyl group, dimethoxymethyl group, dioxolanyl group, tetramethyldioxolanyl group, dioxanyl group, dimethyldioxanyl group, methoxyphenyl group, iso-propoxyphenyl group, allyloxyphenyl group, phenoxyphenyl group, methylenedioxyphenyl group, furyl group, methylfuryl group, tetrahydropyranyl group, furfuryl group, benzofuryl group, dibenzofuryl group and the like, more preferably methoxy group, iso-propoxy group, tert -butoxy group, allyloxy group, phenoxy group, dimethoxymethyl group, dioxolanyl group, methoxyphenyl group, iso-propoxyphenyl group, allyloxyphenyl group, phenoxyphenyl group, furyl group, methylfuryl group, benzofuryl group, dibenzofuryl group; be.

The nitrogen-containing group (N2) is not particularly limited as long as the effect of the present invention is exhibited, but examples include amino group, dimethylamino group, diethylamino group, allylamino group, diallylamino group, didecylamino group, benzylamino group, dibenzyl amino group, pyrrolidinyl group, piperidinyl group, morpholyl group, azepinyl group, dimethylaminomethyl group, dibenzylaminomethyl group, pyrrolidinylmethyl group, dimethylaminoethyl group, benzylaminomethyl group, benzylaminoethyl group, pyrrolidinyl ethyl group, dimethylaminovinyl group, benzylaminovinyl group, pyrrolidinylvinyl group, dimethylaminopropyl group, benzylaminopropyl group, pyrrolidinylpropyl group, dimethylaminoallyl group, benzylaminoallyl group, pyrrolidinylallyl group , aminophenyl group, dimethylaminophenyl group, pyrrolidinylphenyl group, pyrrolylphenyl group, pyridylphenyl group, quinolylphenyl group, isoquinolylphenyl group, indolinylphenyl group, indolylphenyl group, carbazolylphenyl group, di-tert-butylcarbazolylphenyl group, pyrrolyl group, methylpyrrolyl group, phenylpyrrolyl group, pyridyl group, quinolyl group, tetrahydroquinolyl group, iso-quinolyl group, tetrahydro-iso-quinolyl group, indolyl group, Examples include an indolinyl group, a carbazolyl group, a di-tert-butylcarbazolyl group, an imidazolyl group, a dimethylimidazolidinyl group, a benzimidazolyl group, an oxazolyl group, an oxazolidinyl group, and a benzoxazolyl group.

Among the nitrogen-containing groups, preferably amino group, dimethylamino group, diethylamino group, allylamino group, benzylamino group, dibenzylamino group, pyrrolidinyl group, piperidinyl group, morpholyl group, dimethylaminomethyl group, benzylaminomethyl group, pyrrolidinylmethyl group, dimethylaminoethyl group, pyrrolidinylethyl group, dimethylaminopropyl group, pyrrolidinylpropyl group, dimethylaminoallyl group, pyrrolidinylallyl group, aminophenyl group, dimethylaminophenyl group, pyrrolidinyl phenyl, pyrrolylphenyl, carbazolylphenyl, di-tert-butylcarbazolylphenyl, pyrrolyl, pyridyl, quinolyl, tetrahydroquinolyl, iso-quinolyl, tetrahydro-iso-quinolyl group, indolyl group, indolinyl group, carbazolyl group, di-tert-butylcarbazolyl group, imidazolyl group, dimethylimidazolidinyl group, benzimidazolyl group, oxazolyl group, oxazolidinyl group, benzoxazolyl group and the like. Among them, amino group, dimethylamino group, diethylamino group, pyrrolidinyl group, dimethylaminophenyl group, pyrrolidinylphenyl group, pyrrolyl group, pyridyl group, carbazolyl group and imidazolyl group are more preferable.

The sulfur-containing group (S2) is not particularly limited as long as the effect of the present invention is exhibited, but examples include methylthio group, ethylthio group, benzylthio group, phenylthio group, naphthylthio group, methylthiomethyl group, benzylthiomethyl group, phenylthio methyl group, naphthylthiomethyl group, methylthioethyl group, benzylthioethyl group, phenylthioethyl group, naphthylthioethyl group, methylthiovinyl group, benzylthiovinyl group, phenylthiovinyl group, naphthylthiovinyl group, methylthiopropyl group, benzylthiopropyl group, phenylthiopropyl group, naphthylthiopropyl group, methylthioallyl group, benzylthioallyl group, phenylthioallyl group, naphthylthioallyl group, mercaptophenyl group, methylthiophenyl group, thienylphenyl group, methylthienylphenyl group , benzothienylphenyl group, dibenzothienylphenyl group, benzodithienylphenyl group, thienyl group, tetrahydrothienyl group, methylthienyl group, thienofuryl group, thienothienyl group, benzothienyl group, dibenzothienyl group, thienobenzofuryl group, benzodithienyl group, dithiolanyl group, dithianyl group, oxathiolanyl group, oxathianyl group, thiazolyl group, benzothiazolyl group, thiazolidinyl group, and the like.

Preferred among the sulfur-containing groups are thienyl, methylthienyl, thienofuryl, thienothienyl, benzothienyl, dibenzothienyl, thienobenzofuryl, benzodithienyl, thiazolyl and benzothiazolyl groups.

When adjacent substituents among R ¹ to R ⁴ are combined to form a ring, the ring is preferably a saturated ring. The ring may form a 5- to 8-membered saturated or unsaturated hydrocarbon group fused to the cyclopentadienyl ring portion, and is not particularly limited as long as the effect of the present invention is exhibited, but preferably 5 or a 6-membered ring, and in this case, the structure combined with the cyclopentadienyl moiety of the mother core is, for example, substituted cyclopentathiophene, substituted indene, substituted cyclopentatetrahydronaphthalene, substituted 4,5,6,7-tetrahydro and indene.

R ¹ and R ³ are each independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms among the hydrocarbon groups having 1 to 40 carbon atoms (G2), and R ² and R ⁴ are hydrogen atoms is preferably

R ¹¹ to R ¹⁴ are each independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and may be the same or different, and are preferably all hydrogen atoms. Examples of the hydrocarbon group having 1 to 20 carbon atoms include those having 1 to 20 carbon atoms among the hydrocarbon groups exemplified for the hydrocarbon group having 1 to 40 carbon atoms (G2). Preferred is a hydrocarbon group selected from aliphatic or alicyclic hydrocarbon groups having 1 to 20 carbon atoms. The hydrocarbon group having 1 to 20 carbon atoms also includes a substituent having an aromatic structure such as an arylalkyl group.

R ^a1 to R ^a4 are each independently a hydrocarbon group having 1 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 40 carbon atoms or a silicon-containing group, and may be the same or different. As the hydrocarbon group having 1 to 20 carbon atoms and the aromatic hydrocarbon group having 6 to 40 carbon atoms, for example, among the hydrocarbon groups exemplified for the hydrocarbon group having 1 to 40 carbon atoms (G2), Examples include hydrocarbon groups having 1 to 20 carbon atoms and aromatic hydrocarbon groups having 6 to 40 carbon atoms. Examples of the silicon-containing group include the silicon-containing groups exemplified for the silicon-containing group (Si2).

Examples of the hydrocarbon group having 1 to 20 carbon atoms include the aliphatic hydrocarbon group having 1 to 20 carbon atoms, the alicyclic hydrocarbon group having 1 to 20 carbon atoms, and the aryl group having 1 to 20 carbon atoms. Preferred groups include arylalkyl groups.

Among the hydrocarbon groups having 1 to 20 carbon atoms, preferably methyl group, ethyl group, 1-propyl group, 1-butyl group, 1-pentyl group, 1-hexyl group, 1-heptyl group, 1- Octyl group, iso-propyl group, sec-butyl (butan-2-yl) group, tert-butyl (2-methylpropan-2-yl) group, iso-butyl (2-methylpropyl) group, iso-pentyl ( 3-methylbutyl) group, neopentyl (2,2-dimethylpropyl) group, tert-pentyl (1,1-dimethylpropyl) group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclopentenyl group, cyclohexyl group, cyclohexenyl group , cycloheptyl group, cycloheptenyl group, cycloheptatrienyl group, cyclooctyl group, cyclooctenyl group, cyclooctadienyl group, norbornyl group, 2-methylbicyclo[2.2.1]heptan-2-yl group, bicyclo[ 2.2.2] octan-1-yl group, 1-adamantyl group, 2-adamantyl group, benzyl group, benzhydryl (diphenylmethyl) group, cumyl (2-phenylpropan-2-yl) group, 1,1- They are a diphenylethyl group, a trityl (triphenylmethyl) group, a 2-phenylethyl group, a 3-phenylpropyl group and a 2-cinnamyl (3-phenylallyl) group.

Among the aromatic hydrocarbon groups having 6 to 40 carbon atoms, phenyl group, tolyl (methylphenyl) group, xylyl (dimethylphenyl) group, mesityl (2,4,6-trimethylphenyl) group, cumenyl ( iso-propylphenyl) group, 2,6-di-iso-propylphenyl group, 2,4,6-tri-iso-propylphenyl group, 4-tert-butylphenyl group, 3,5-di-tert-butyl phenyl group, 4-adamantylphenyl group, naphthyl group, biphenyl group, ter-phenyl group, binaphthyl group, phenanthryl group, anthracenyl group and ferrocenyl group.

Among the silicon-containing groups, trimethylsilyl group, triethylsilyl group, tri-iso-propylsilyl group, tert-butyldimethylsilyl group, triphenylsilyl group, 4-trimethylsilylphenyl group, 3,5-bistrimethylsilylphenyl 4-triethylsilylphenyl group, 4-tri-iso-propylsilylphenyl group, 4-triphenylsilylphenyl group.

R ^a1 and R ¹¹ , R ^a2 and R ¹² , R ^a3 and R ¹³ , R ^a4 and R ¹⁴ may combine with each other to form a ring. The ring formed in this case preferably forms a ring as a 5- to 8-membered saturated or unsaturated hydrocarbon group fused to the aromatic ring portion. In addition, when a plurality of rings are present, they may be the same or different. Although it is not particularly limited as long as the effects of the present invention are exhibited, it is preferably a 5- or 6-membered ring. , substituted tetrahydronaphthalenes, and the like.

R ^a1 to R ^a4 are preferably each independently a hydrocarbon group having 1 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 40 carbon atoms or the silicon-containing group, more preferably 1 carbon atom. ~10 hydrocarbon groups.

R ^b1 and R ^b2 have a substituent represented by the general formula [2], or a substituent having a five-membered ring as a base skeleton containing at least one atom selected from nitrogen, oxygen and sulfur. are heteroaromatic groups which may be the same or different.

In the general formula [2], V is an atom selected from nitrogen, oxygen or sulfur, preferably nitrogen or oxygen.
The wavy line in the general formula [2] indicates the bonding site with the benzene ring.
m is an integer of 1 or 2 that satisfies the valence of V, and when m is 2, each R ^c may be the same or different.
each R ^c is independently a hydrogen atom, the hydrocarbon group having 1 to 40 carbon atoms (G2), the silicon-containing group (Si2), an ether bond-containing hydrocarbon group or a tertiary amino group-containing hydrocarbon group; A hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms is preferred.

Among the hydrocarbon groups (G2) having 1 to 40 carbon atoms, preferably methyl group, ethyl group, 1-propyl group, 1-butyl group, 1-pentyl group, 1-hexyl group and 1-heptyl group , 1-octyl group, iso-propyl group, sec-butyl (butan-2-yl) group, tert-butyl (2-methylpropan-2-yl) group, iso-butyl (2-methylpropyl) group, iso -pentyl (3-methylbutyl) group, neopentyl (2,2-dimethylpropyl) group, tert-pentyl (1,1-dimethylpropyl) group, allyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cyclo Heptyl group, cyclooctyl group, cyclooctenyl group, norbornyl group, bicyclo[2.2.2]octan-1-yl group, 1-adamantyl group, 2-adamantyl group, benzyl group, benzhydryl (diphenylmethyl) group, cumyl ( 2-phenylpropan-2-yl) group, 1,1-diphenylethyl group, trityl (triphenylmethyl) group, 2-phenylethyl group, 3-phenylpropyl group, 2-cinnamyl (3-phenylallyl) group, phenyl group, tolyl (methylphenyl) group, xylyl (dimethylphenyl) group, mesityl (2,4,6-trimethylphenyl) group, cumenyl (iso-propylphenyl) group, 2,6-di-iso-propylphenyl group , 2,4,6-tri-iso-propylphenyl group, 4-tert-butylphenyl group, 3,5-di-tert-butylphenyl group, 4-adamantylphenyl group, naphthyl group, biphenyl group, ter-phenyl group, binaphthyl group, phenanthryl group, anthracenyl group and ferrocenyl group, more preferably methyl group, ethyl group, 1-propyl group, 1-butyl group, iso-propyl group, sec-butyl (butan-2-yl ) group, tert-butyl (2-methylpropan-2-yl) group, iso-butyl (2-methylpropyl) group, allyl group, cyclopentyl group, cyclohexyl group, 1-adamantyl group, benzyl group, phenyl group, tolyl (methylphenyl) group, xylyl (dimethylphenyl) group, mesityl (2,4,6-trimethylphenyl) group, naphthyl group, biphenyl group and ter-phenyl group.

The ether bond-containing hydrocarbon group is not particularly limited as long as the effect of the present invention is exhibited, and examples thereof include methoxymethyl group, methoxyethyl group, tetrahydrofuryl group, tetrahydropyranyl group and methoxyphenyl group.

The tertiary amino group-containing hydrocarbon group is not particularly limited as long as the effect of the present invention is exhibited, but examples include N-dimethylamino group, N-diethylamino group, N-diallylamino group, N-dibenzylamino group, N-methylethylamino group, N-pyrrolidinyl group, N-piperidinyl group, N-morpholyl group, N-methyl-N-piperazinyl group, N-pyrrolyl group, N-indolinyl group, N-indolyl group, N-carbazolyl group , N-di-tert-butylcarbazolyl group, N-imidazolyl group, N-dimethylimidazolidinyl group, N-benzimidazolyl group, N-oxazolyl group, N-oxazolidinyl group, N-benzoxazolyl and the like.

R ^c forming R ^b1 and at least one selected from R ^a1 and R ^a2 and R ^c forming R ^b2 and at least one selected from R ^a3 and R ^a4 are bonded to each other to have a substituent may form an optional ring. The ring formed in this case may form a ring as a 5- to 8-membered saturated or unsaturated hydrocarbon group which may have a substituent condensed to the aromatic ring portion. R ^c forming R ^b1 and at least one selected from R ^a1 and R ^a2 and R ^c forming R ^b2 and at least one selected from R ^a3 and R ^a4 bind to each other to form a ring structure If so, it is preferably a saturated ring. In addition, when a plurality of rings exist, they may be the same or different. Although it is not particularly limited as long as the effect of the present invention is exhibited, it is preferably a 5- or 6-membered ring. , 2,2,7-trimethyl-2,3-dihydrobenzofuran-5-yl group, 4-methyldibenzo[b,d]furan-2-yl group, 2,7-dimethylbenzo[b]thiophene-5- yl group, 4-methyldibenzo[b,d]thiophen-2-yl group, 1,7-dimethylindol-5-yl group, 1,7-dimethylindolin-5-yl group, 1,9-dimethylcarbazole- 3-yl group, 9-julolidinyl (2,3,6,7-tetrahydro-1H,5H-benzo[ij]quinolidin-9-yl) group and the like, preferably 1,7-dimethylindoline-5 -yl group, 9-julolidinyl (2,3,6,7-tetrahydro-1H,5H-benzo[ij]quinolidin-9-yl) group.

When V is a nitrogen atom and m is 2, R ^c are bonded together to form an optionally substituted ring, for example, a 5- to 8-membered saturated or unsaturated hydrocarbon group ^. may When R ^c are bonded together to form a ring structure, it is preferably a saturated ring. Although it is not particularly limited as long as the effect of the present invention is exhibited, it is preferably a 5- or 6-membered ring. -morpholyl group, N-methyl-N-piperazinyl group, N-pyrrolyl group, N-indolinyl group, N-indolyl group, N-carbazolyl group, N-di-tert-butylcarbazolyl group, N-imidazolyl group, N-dimethylimidazolidinyl group, N-benzimidazolyl group, N-oxazolyl group, N-oxazolidinyl group, N-benzoxazolyl group and the like, preferably N-pyrrolidinyl group, N-piperidinyl group , N-morpholyl group and N-methyl-N-piperazinyl group.

The optionally substituted heterocyclic aromatic group having a 5-membered ring in the mother skeleton containing at least one atom selected from nitrogen, oxygen, and sulfur includes, for example, the following general formula [4a] A group represented by ~[4h] can be mentioned.

前記一般式［４ａ］～［４ｈ］中、Ｃｈは酸素原子あるいは硫黄原子であり、Ｒ^dはそれぞれ独立に、水素原子または前記炭素数１～４０の炭化水素基（Ｇ２）のうち炭素数１～２０の炭化水素基であり、それぞれ同一でも異なっていてもよい。

In the general formulas [4a] to [4h], Ch is an oxygen atom or a sulfur atom, and each R ^d is independently a hydrogen atom or a hydrocarbon group having 1 to 40 carbon atoms (G2). ∼20 hydrocarbon groups, each of which may be the same or different.

The wavy lines in the general formulas [4a] to [4h] indicate the bonding sites with the benzene ring.
Among the hydrocarbon groups having 1 to 20 carbon atoms, preferably methyl group, ethyl group, 1-propyl group, 1-butyl group, 1-pentyl group, 1-hexyl group, 1-heptyl group, 1- Octyl group, iso-propyl group, sec-butyl (butan-2-yl) group, tert-butyl (2-methylpropan-2-yl) group, iso-butyl (2-methylpropyl) group, iso-pentyl ( 3-methylbutyl) group, neopentyl (2,2-dimethylpropyl) group, tert-pentyl (1,1-dimethylpropyl) group, allyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclooctenyl group, norbornyl group, bicyclo[2.2.2]octan-1-yl group, 1-adamantyl group, 2-adamantyl group, benzyl group, benzhydryl (diphenylmethyl) group, cumyl (2-phenyl propan-2-yl) group, 1,1-diphenylethyl group, trityl (triphenylmethyl) group, 2-phenylethyl group, 3-phenylpropyl group, 2-cinnamyl (3-phenylallyl) group, phenyl group, tolyl (methylphenyl) group, xylyl (dimethylphenyl) group, mesityl (2,4,6-trimethylphenyl) group, cumenyl (iso-propylphenyl) group, 2,6-di-iso-propylphenyl group, 2, 4,6-tri-iso-propylphenyl group, 4-tert-butylphenyl group, 3,5-di-tert-butylphenyl group, 4-adamantylphenyl group, naphthyl group, biphenyl group, ter-phenyl group, binaphthyl group, phenanthryl group, anthracenyl group, ferrocenyl group, more preferably methyl group, ethyl group, 1-propyl group, 1-butyl group, iso-propyl group, sec-butyl(butan-2-yl) group, tert-butyl (2-methylpropan-2-yl) group, iso-butyl (2-methylpropyl) group, allyl group, cyclopentyl group, cyclohexyl group, 1-adamantyl group, benzyl group, phenyl group, tolyl (methylphenyl ) group, xylyl (dimethylphenyl) group, mesityl (2,4,6-trimethylphenyl) group, naphthyl group, biphenyl group and ter-phenyl group.

R ^d is an optionally substituted 5- to 8-membered saturated or unsaturated hydrocarbon group in which adjacent R ^d' s are bonded to each other and independently condensed to form a 5-membered heterocyclic ring. is not particularly limited as long as the effect of the present invention is exhibited, but is preferably a 5- or 6-membered ring. thiophene ring, indole ring, carbazole ring, benzoxazole ring, benzothiazole ring, benzimidazole ring, benzopyrazole ring and the like.

Of the heterocyclic aromatic groups [4a] to [4h], [4a] is preferred.
Among the heterocyclic aromatic groups [4a], preferred are 2-furyl group, 5-methyl-2-furyl group, 2-thienyl group, 5-methyl-2-thienyl group and N-pyrrolyl group.
R ^b1 and R ^b2 are particularly preferably alkoxy groups, dialkylamino groups or pyrrolidinyl groups.

Among the alkoxy groups, preferred are methoxy, ethoxy, 1-propoxy, 1-butoxy, iso-propoxy, sec-butoxy, tert-butoxy, iso-butoxy, allyloxy, and cyclopentyloxy. cyclohexyloxy, 1-adamantyloxy and benzyloxy, and most preferably methoxy, ethoxy, 1-propoxy, iso-propoxy and tert-butoxy.

Z ¹ and Z ² are each independently a saturated or unsaturated ring having 3 or 4 carbon atoms which forms a condensed ring which may have the same substituents as R ¹ to R ⁴ with respect to the carbon atom to which they are attached. It is a hydrocarbon group, and in this case, the structure together with the cyclopentadienyl moiety of the mother nucleus is substituted cyclopentathiophene ring, substituted indene ring, substituted tetrahydroindene ring, substituted azulene ring, substituted dihydroazulene ring, substituted tetrahydroazulene rings, substituted hexahydroazulene rings, etc., preferably substituted indene rings.

The substituents on Z ¹ may be combined with R ¹¹ and R ¹² and the substituents on Z ² with R ¹³ and R ¹⁴ to form a ring, in which case the mother nucleus cyclopentadienyl Structures combined with moieties and aromatic ring moieties include, for example, 3,6-dihydrocyclopentafluorene ring, cyclopentaphenanthrene ring, and 6,7-dihydrocyclopentaphenanthrene ring. In addition, when a plurality of rings are present, they may be the same or different.

The transition metal compound [A] constituting the olefin polymerization catalyst of the present invention is preferably a compound represented by the general formula [3].
In general formula [3], M, X, n, Q, R ¹ to R ⁴ , R ¹¹ to R ¹⁴ , R ^a1 to R ^a4 , R ^b1 and R ^b2 are respectively M, X , n, Q, R ¹ to R ⁴ , R ¹¹ to R ¹⁴ , R ^a1 to R ^a4 , R ^b1 and R ^b2 .

R ⁵ to R ¹⁰ each independently represent a hydrogen atom, the hydrocarbon group having 1 to 40 carbon atoms (G2), the halogen-containing group (H2), the silicon-containing group (Si2), the oxygen-containing group (O2 ), the nitrogen-containing group (N2) or the sulfur-containing group (S2), which may be the same or different.

Illustrative and preferred examples of the hydrocarbon group (G2) having 1 to 40 carbon atoms are the same as those mentioned above for R ¹ to R ⁴ .
Illustrative and preferred examples of the halogen-containing group (H2) are the same as those mentioned above for R ¹ to R ⁴ .

Illustrative and preferred examples of the silicon-containing group (Si2) are the same as those listed above for R ¹ to R ⁴ .
Illustrative and preferred examples of the oxygen-containing group (O2) are the same as those listed above for R ¹ to R ⁴ .

Illustrative and preferred examples of the nitrogen-containing group (N2) are the same as those mentioned above for R ¹ to R ⁴ .
Illustrative and preferred examples of the sulfur-containing group (S2) are the same as those mentioned above for R ¹ to R ⁴ .

Adjacent substituents from R ⁵ to R ¹⁰ may be joined together to form a ring. The ring formed in this case preferably forms a ring as a 5- to 8-membered saturated or unsaturated hydrocarbon group which may have a substituent group condensed to the aromatic ring portion. In addition, when a plurality of rings are present, they may be the same or different. Although it is not particularly limited as long as the effect of the present invention is exhibited, it is preferably a 5- or 6-membered ring. , and substituted cyclopentatetrahydronaphthalene, and substituted fluorene rings, preferably substituted tetrahydroindacene rings, are examples of the condensed ring structures of the R ¹ to R ⁴ moieties. When R ⁵ and R ⁶ or R ⁸ and R ⁹ form a ring structure, it is preferably a saturated ring.

R ⁵ and R ¹¹ or R ¹² , R ⁸ and R ¹³ or R ¹⁴ may combine with each other to form a ring. The ring formed in this case preferably forms a ring as a 5- to 8-membered saturated or unsaturated hydrocarbon group which may have a substituent group condensed to the aromatic ring portion. In addition, when a plurality of rings exist, they may be the same or different. Although it is not particularly limited as long as the effect of the present invention is exhibited, it is preferably a 5- or 6-membered ring. A cyclopentafluorene ring, a cyclopentaphenanthrene ring, and a 6,7-dihydrocyclopentaphenanthrene ring can be mentioned.

R ⁵ to R ¹⁰ are each independently preferably a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms among the hydrocarbon groups having 1 to 40 carbon atoms (G2), or an oxygen-containing group (O2). .
Preferred examples of the hydrocarbon group having 1 to 20 carbon atoms are the same as those mentioned above for R ^a1 to R ^a4 .

Preferred examples of the oxygen-containing group (O2) include the same alkoxy groups as those described above for R ^b1 and R ^b2 .
It is more preferable that R ⁵ to R ¹⁰ each independently represent a hydrogen atom or the aforementioned hydrocarbon group having 1 to 20 carbon atoms.

Among the hydrocarbon groups having 1 to 20 carbon atoms, particularly preferred examples are methyl group, iso-propyl group and tert-butyl(2-methylpropan-2-yl) group.
All of R ⁵ to R ¹⁰ are particularly preferably hydrogen atoms.

[Method for producing transition metal compound [A]]
The transition metal compound [A] of the present invention can be produced by a known method, and an example of a representative synthetic route is shown below, but the production method is not particularly limited.

First, the starting material, a 3,4,5-substituted aromatic compound having a heteroatom-containing electron-donating substituent at the 4-position and having substituents introduced at the vicinal 3,5-positions, is prepared by a known method. It can be manufactured by, and the manufacturing method is not particularly limited. 2006, 128, 16486.”, “Eur.J.Org.Chem. 2008, 1767.”, “Angew.Chem.Int.Ed. 52, 4239.”, “Org. Process. Res. Dev. 2011, 15, 1178.”, “Eur. J. Org. Chem. .Soc. 2014, 136, 10166.”, “Eur.J.Org.Chem.

In addition, the aromatic-substituted cyclopentadiene compound can be produced by a known method such as cross-coupling reaction using the 3,4,5-substituted aromatic compound as a raw material, and the production method is particularly limited. isn't it. As known production methods, for example, "Organometallics 2004, 23, 3267." 7910783, JP 2011-500800, "Organometallics 2011, 30, 5744.", "Chem. Eur. J. 2012, 18, 4174.", "Organometallics 2012, 31, 4962." 201519, JP-A-7-286005 by the present applicant, WO2001/027124, WO2004/029062, WO2006/126608, and the like.

In addition, the precursor compound (ligand) of the transition metal compound [A] can be produced by a known method using the aromatic-substituted cyclopentadiene compound as a raw material, and the production method is not particularly limited. do not have. As well-known production methods, for example, in addition to the above-mentioned production methods of substituted cyclopentadiene compounds, "J. Organomet. Chem. 1997, 530, 75." and "J. Organomet. Chem. ”, JP-A-2001-11089, JP-A-2003-201259, JP-A-2011-144157, JP-A-2014-193846, and the like.

Moreover, the target transition metal compound [A] can be produced by a known method using the precursor compound (ligand), and the production method is not particularly limited. As known production methods, for example, in addition to those mentioned as the production method of the precursor compound (ligand), US Pat. , 297.”, JP-A-2002-88092, “Organometallics 2012, 31, 4340.”, and WO2004/029062 by the present applicant.

Moreover, in the transition metal compound [A] of the present invention, the cyclopentadienyl ring portion that bonds to the central metal across the bridging portion has two planes (front side and back side). Therefore, when the two cyclopentadienyl ring moieties that are bonded to the central metal across the bridging portion are the same, there are two types of structural isomers, a racemic form and a meso form, and two cyclopentadienyl ring moieties exist. When the dienyl ring moieties are different from each other, there are two types of structural isomers, pseudo-racemic and pseudo-meso. The transition metal compound [A] represented by the general formula [1] or [3] has cyclopentadienyl ring partial aromatic substituents located on different sides, and is a racemate or a pseudo-racemate. The meso isomer and pseudo-meso isomer have a structure represented by the following general formula [5a] or [5b], in which the aromatic substituents of the cyclopentadienyl ring portion are located on the same left and right sides.

これら構造異性体混合物の精製、ラセミ体および疑似ラセミ体の分取、あるいはラセミ体および疑似ラセミ体の選択的な製造は、公知の方法によって可能であり、特に製造法が限定されるわけではない。公知の製造方法としては、前記遷移金属化合物［Ａ］の製造方法として挙げたものである。

Purification of these structural isomer mixtures, fractionation of racemates and pseudoracemates, or selective production of racemates and pseudoracemates can be performed by known methods, and the production method is not particularly limited. . Known production methods are those mentioned as the production method of the transition metal compound [A].

Specific examples of the transition metal compound [A] of the present invention are shown below, but the scope of the present invention is not particularly limited by these. In the present invention, the transition metal compound [A] may be used singly or in combination of two or more. Racemates and pseudo-racemates may be used. may be used, or combinations of the above may be used.

For convenience, the ligand structure of the transition metal compound [A] of the present invention, excluding MX _n (metal moiety), is represented by a cyclopentadienyl ring moiety, a cyclopentadienyl ring moiety aromatic substituent (Ar), a cyclopentadienyl 3- and 5-position substituents (T) in the ring portion aromatic substituents, 4-position substituents (Y) in the cyclopentadienyl ring portion aromatic substituents, and substitutions adjacent to the cyclopentadienyl ring portion bridge portion It is divided into seven groups: the group (R), the cyclopentadienyl ring portion oxygen atom-bonded alkyl substituent (Alk), and the structure of the bridging portion. The abbreviation for the cyclopentadienyl ring portion is α, the abbreviation for the cyclopentadienyl ring portion aromatic substituent (Ar) is β, and the 3- and 5-position substituents (T) in the cyclopentadienyl ring portion aromatic substituent group. is abbreviated as γ, the abbreviation for the substituent (Y) at the 4-position in the cyclopentadienyl ring partial aromatic substituent is δ, the abbreviation for the substituent (R) adjacent to the cyclopentadienyl ring partial bridge portion is ε, The abbreviation for the cyclopentadienyl ring portion oxygen atom-bonded alkyl substituent (Alk) is ζ, the abbreviation for the structure of the bridging portion is η, and the abbreviations for each substituent are shown in [Table 1] to [Table 7].

Specific examples of the metal portion MX _n include TiF ₂ , TiCl ₂ , TiBr 2 , TiI ₂ , Ti(Me) ₂ , Ti(Bn) ₂ , Ti(Allyl) _{2 ,} Ti(CH ₂ -tBu) ₂ , Ti (η ⁴ -1,3-butadienyl), Ti (η ⁴ -1,3-pentadienyl), Ti (η ⁴ -2,4-hexadienyl), Ti (η ⁴ -1,4-diphenyl-1, 3-pentadienyl), Ti( _CH2 -Si(Me) ₃ ) ₂ , Ti(OMe) ₂ , Ti(OiPr) ₂ , Ti( _NMe2 ) ₂ , Ti(OMs) ₂ , Ti(OTs) ₂ , Ti (OTf) ₂ , _ZrF2 , _ZrCl2 , ZrBr2, _ZrI2 , Zr(Me) ₂ , Zr(Bn) _{2 ,} Zr(Allyl) ₂ , Zr(CH2 _- tBu) ₂ , Zr( ^η4-1 ,3-butadienyl), Zr (η ⁴ -1,3-pentadienyl), Zr (η ⁴ -2,4-hexadienyl), Zr (η ⁴ -1,4-diphenyl-1,3-pentadienyl), Zr ( _CH2 -Si(Me) ₃ ) ₂ , Zr(OMe) ₂ , Zr(OiPr) ₂ , Zr( _NMe2 ) ₂ , Zr(OMs) ₂ , Zr(OTs) ₂ , Zr(OTf) ₂ , _HfF2 , HfCl ₂ , HfBr ₂ , HfI ₂ , Hf(Me) ₂ , Hf(Bn) ₂ , Hf(Allyl) ₂ , Hf(CH ₂ -tBu) ₂ , Hf(η ⁴ -1,3-butadienyl), Hf (η ⁴ -1,3-pentadienyl), Hf (η ⁴ -2,4-hexadienyl), Hf (η ⁴ -1,4-diphenyl-1,3-pentadienyl), Hf (CH ₂ —Si(Me) ₃ ) ₂ , Hf(OMe) ₂ , Hf(OiPr) ₂ , Hf( _NMe2 ) ₂ , Hf(OMs) ₂ , Hf(OTs) ₂ , Hf(OTf) ₂ and the like. Me is a methyl group, Bn is a benzyl group, tBu is a tert-butyl group, Si(Me) ₃ is a trimethylsilyl group, OMe is a methoxy group, OiPr is an iso-propoxy group, _NMe2 is a dimethylamino group, and OMs is methanesulfonate. OTs is the p-toluenesulfonate group and OTf is the trifluoromethanesulfonate group.

According to the above notation, the cyclopentadienyl ring portion is α-1 in [Table 1], the cyclopentadienyl ring portion aromatic substituent (Ar) is β-1 in [Table 2], cyclopentadienyl The 3 and 5-position substituents (T) in the dienyl ring partial aromatic substituent are γ-4 in [Table 3], and the 4-position substituent (Y) in the cyclopentadienyl ring partial aromatic substituent is δ-20 in [Table 4], the substituent (R) adjacent to the cyclopentadienyl ring portion bridge portion is ε-1 in [Table 5], and the bridge portion is η-16 in [Table 7]. The following compound [6] is exemplified when it is composed of a combination and MX _n of the metal moiety is ZrCl ₂ .

また、シクロペンタジエニル環部分が［表１］中のα－２、シクロペンタジエニル環部分芳香族置換基（Ａｒ）が［表２］中のβ－８、シクロペンタジエニル環部分架橋部隣接位の置換基（Ｒ）が［表５］中のε－１３、架橋部分が［表７］中のη－３２の組み合わせで構成され、金属部分のＭＸ_nがＺｒ（ＮＭｅ₂）₂の場合は、下記化合物［７］を例示している。

In addition, the cyclopentadienyl ring portion is α-2 in [Table 1], the cyclopentadienyl ring portion aromatic substituent (Ar) is β-8 in [Table 2], and the cyclopentadienyl ring portion is crosslinked. The substituent (R) adjacent to the site is ε-13 in [Table 5], the cross-linking portion is η-32 in [Table 7], and MX _n of the metal portion is Zr(NMe ₂ ) ₂ In the case of, the following compound [7] is exemplified.

また、シクロペンタジエニル環部分が［表１］中のα－１１、シクロペンタジエニル環部分芳香族置換基（Ａｒ）が［表２］中のβ－１、シクロペンタジエニル環部分芳香族置換基中３，５位の置換基（Ｔ）が［表３］中のγ－１０、シクロペンタジエニル環部分芳香族置換基中４位の置換基（Ｙ）が［表４］中のδ－３３、シクロペンタジエニル環部分架橋部隣接位の置換基（Ｒ）が［表５］中のε－２、架橋部分が［表７］中のη－２６の組み合わせで構成され、金属部分のＭＸ_nがＨｆ（Ｍｅ）₂の場合は、下記化合物［８］を例示している。

Further, the cyclopentadienyl ring portion is α-11 in [Table 1], the cyclopentadienyl ring portion aromatic substituent (Ar) is β-1 in [Table 2], and the cyclopentadienyl ring portion aromatic The 3,5-position substituent (T) in the group substituent is γ-10 in [Table 3], and the 4-position substituent (Y) in the cyclopentadienyl ring partial aromatic substituent is [Table 4] δ-33 of , the substituent (R) adjacent to the bridge portion of the cyclopentadienyl ring portion is ε-2 in [Table 5], and the bridge portion is η-26 in [Table 7]. When MX _n of the metal moiety is Hf(Me) ₂ , the following compound [8] is exemplified.

また、金属部分ＭＸ_nと結合している２つの置換シクロペンタジエニル環部分が、共に同じではなく、異なる場合、一方のシクロペンタジエニル環部分が［表１］中のα－４、シクロペンタジエニル環部分芳香族置換基（Ａｒ）が［表２］中のβ－１、シクロペンタジエニル環部分芳香族置換基中３，５位の置換基（Ｔ）が［表３］中のγ－９とγ－１１、シクロペンタジエニル環部分芳香族置換基中４位の置換基（Ｙ）が［表４］中のδ－５、シクロペンタジエニル環部分架橋部隣接位の置換基（Ｒ）が［表５］中のε－８、かつ、もう一方のシクロペンタジエニル環部分が［表１］中のα－８、シクロペンタジエニル環部分芳香族置換基（Ａｒ）が［表２］中のβ－６、シクロペンタジエニル環部分架橋部隣接位の置換基（Ｒ）が［表５］中のε－１１、シクロペンタジエニル環部分酸素原子結合アルキル置換基（Ａｌｋ）が［表６］中のζ－１であり、架橋部分が［表７］中のη－１の組み合わせで構成され、金属部分のＭＸ_nがＴｉ（η⁴－１，３－ペンタジエニル）の場合は、下記化合物［９］を例示している。

In addition, when the two substituted cyclopentadienyl ring moieties bonded to the metal moiety MX _n are not the same and are different, one of the cyclopentadienyl ring moieties is α-4 in [Table 1], cyclo The pentadienyl ring partial aromatic substituent (Ar) is β-1 in [Table 2], and the 3,5-position substituent (T) in the cyclopentadienyl ring partial aromatic substituent is [Table 3]. γ-9 and γ-11 of , the substituent (Y) at the 4-position in the cyclopentadienyl ring partial aromatic substituent is δ-5 in [Table 4], the position adjacent to the cyclopentadienyl ring partial cross-linking site The substituent (R) is ε-8 in [Table 5], and the other cyclopentadienyl ring portion is α-8 in [Table 1], the cyclopentadienyl ring portion aromatic substituent (Ar ) is β-6 in [Table 2], the substituent (R) adjacent to the cyclopentadienyl ring partial bridge portion is ε-11 in [Table 5], and the cyclopentadienyl ring partial oxygen atom-bonded alkyl substitution The group (Alk) is ζ-1 in [Table 6], the cross-linking portion is composed of a combination of η-1 in [Table 7], and the metal portion MX _n is Ti (η ⁴ -1,3- In the case of pentadienyl), the following compound [9] is exemplified.

上記の遷移金属化合物が特異な性能を示す理由は現時点では明らかではないが、本願発明者は下記の様に推測している。

Although the reason why the above transition metal compounds exhibit the unique performance is not clear at present, the inventor of the present application speculates as follows.

The transition metal compound of the present invention is the transition metal compound [A] represented by the general formula [1] or [3], characterized by having (i) a heteroatom-containing electron-donating substituent to a specific metallocene site. and This is thought to provide the potential for increased activity, which is thought to be due to the influx of electrons to the vicinity of the central metal via the conjugated system, and improved reactivity with α-olefins, especially higher α-olefins with a large number of carbon atoms. be done. In addition, the improvement in α-olefin reactivity suppresses chain transfer and reaction rate reduction (including dormant state) during the α-olefin reaction, and as a result, it is thought to lead to improvement in molecular weight and enhancement of molecular weight distribution. On the other hand, (ii) the substituent near the heteroatom is considered to reduce the interaction between the heteroatom and the Lewis acidic compound such as an organometallic compound described later, or the central metal of the transition metal compound. It is thought that only the performance improvement effect due to the introduction can be selectively expressed.

((B-1) organometallic compound)
As the organometallic compound (B-1) used in the present invention, specifically, 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 atom of:
R ^a _p Al (OR ^b ) _q H _r Y _s (B-1a)
(In the general formula (B-1a), R ^a and R ^b may be the same or different and represent a hydrocarbon group having 1 to 15, 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.) an organoaluminum compound;
M ³ AlR ^c1 ₄ (B-1b)
(In general formula (B-1b), M ³ represents Li, Na or K, and R ^c1 represents a hydrocarbon group having 1 to 15, preferably 1 to 4 carbon atoms.) A complex alkylate of an alkali metal of Group 1 of the Japanese alphabet 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 each represents a hydrocarbon group having 1 to 15, preferably 1 to 4 carbon atoms, and M ⁴ is Mg , Zn or Cd) with an alkaline earth metal of Group 2 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 ^a _p Al (OR ^b ) _3-p (B-1a-1)
(In the formula (B-1a-1), R ^a and R ^b may be the same or different and represent a hydrocarbon group having 1 to 15, preferably 1 to 4 carbon atoms, and p is preferably is a number of 1.5 ≤ p ≤ 3.) an organoaluminum compound represented by
R ^a _p AlY _3-p (B-1a-2)
(In the formula (B-1a-2), R ^a represents a hydrocarbon group having 1 to 15, preferably 1 to 4 carbon atoms, Y represents a halogen atom, and p is preferably 0<p<3 is the number of.) The organoaluminum compound represented by
R ^a _p AlH _3-p (B-1a-3)
(In the formula (B-1a-3), R ^a represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, and p is preferably a number satisfying 2≦p<3.) Organoaluminum compounds represented,
R ^a _p Al (OR ^b ) _q Y _s (B-1a-4)
(In the formula (B-1a-4), R ^a and R ^b may be the same or different and represent a hydrocarbon group having 1 to 15, preferably 1 to 4 carbon atoms, and Y is a halogen an atom, p is 0<p≤3, q is 0≤q<3, s is a number satisfying 0≤s<3, and p+q+s=3.).

More specific examples of organoaluminum compounds belonging to the general formula (B-1a) include trimethylaluminum, triethylaluminum, tri-n-butylaluminum, tripropylaluminum, tripentylaluminum, trihexylaluminum, trioctylaluminum, and tridecylaluminum. tri-n-alkylaluminum such as;
triisopropylaluminum, triisobutylaluminum, trisec-butylaluminum, tritert-butylaluminum, tri-2-methylbutylaluminum, tri-3-methylbutylaluminum, tri-2-methylpentylaluminum, tri-3-methylpentylaluminum, tri-4 - tri-branched alkyl aluminum such as methylpentylaluminum, tri-2-methylhexylaluminum, tri-3-methylhexylaluminum, tri-2-ethylhexylaluminum;
tricycloalkylaluminum such as tricyclohexylaluminum, tricyclooctylaluminum;
triarylaluminum such as triphenylaluminum, tritolylaluminum;
dialkylaluminum hydride such as diisobutylaluminum hydride;
(iC ₄ H ₉ ) _{x Aly} (C ₅ H ₁₀ ) _z (wherein x, y and z are positive numbers and z≧2x), etc. Trialkenyl aluminum such as;
alkylaluminum alkoxides such as isobutylaluminum methoxide, isobutylaluminum ethoxide, isobutylaluminum isopropoxide;
dialkylaluminum alkoxides such as dimethylaluminum methoxide, diethylaluminum ethoxide, dibutylaluminum butoxide;
alkylaluminum sesquialkoxides such as ethylaluminum sesquiethoxide, butylaluminum sesquibutoxide;
A partially alkoxylated aluminum alkyl having an average composition represented by R ^a _2.5 Al(OR ^b ) _0.5 , wherein R ^a and R ^b can be the same or different and have the number of carbon atoms 1 to 15, preferably 1 to 4 hydrocarbon groups);
diethylaluminum phenoxide, diethylaluminum (2,6-di-t-butyl-4-methylphenoxide), ethylaluminum bis(2,6-di-t-butyl-4-methylphenoxide), diisobutylaluminum (2,6- dialkylaluminum aryloxides such as di-t-butyl-4-methylphenoxide), isobutylaluminum bis(2,6-di-t-butyl-4-methylphenoxide);
dialkylaluminum halides such as dimethylaluminum chloride, diethylaluminum chloride, dibutylaluminum chloride, diethylaluminum bromide, diisobutylaluminum chloride;
alkylaluminum sesquihalides such as ethylaluminum sesquichloride, butylaluminum sesquichloride, ethylaluminum sesquibromide;
partially halogenated aluminum alkyls such as alkylaluminum dihalides such as ethylaluminum dichloride, propylaluminum dichloride, butylaluminum dibromide;
dialkylaluminum hydride such as diethylaluminum hydride, dibutylaluminum hydride;
Other partially hydrogenated aluminum alkyls such as alkylaluminum dihydrides such as ethylaluminum dihydride, propylaluminum dihydride;
Partially alkoxylated and halogenated alkylaluminums such as ethylaluminum ethoxychloride, butylaluminum butoxychloride, ethylaluminum ethoxybromide and the like can be mentioned.

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

In addition, the organometallic compound (B-1) includes methyllithium, ethyllithium, propyllithium, butyllithium, methylmagnesium bromide, methylmagnesium chloride, ethylmagnesium bromide, ethylmagnesium chloride, propylmagnesium bromide, and propylmagnesium. Chloride, butylmagnesium bromide, butylmagnesium chloride, and the like can also be used.

Further, a compound capable of forming the above organoaluminum compound in the polymerization system, such as a combination of an aluminum halide and an alkyllithium, or a combination of an aluminum halide and an alkylmagnesium, may be used as the organometallic compound (B-1). can also be used as

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

((B-2) Organic aluminum oxy compound)
The organoaluminumoxy compound (B-2) used in the present invention may be a conventionally known aluminoxane, or a benzene-insoluble organoaluminumoxy compound as exemplified in JP-A-2-78687. may
Conventionally known aluminoxanes can be produced, for example, by the method described below, and are usually obtained as a solution in a hydrocarbon solvent.

(1) Compounds containing adsorbed water or salts containing water of crystallization, such as magnesium chloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate, cerous chloride hydrate, etc. A method of adding an organoaluminum compound such as trialkylaluminum to the hydrocarbon medium suspension of (1) and reacting the adsorbed water or water of crystallization with the organoaluminum compound.

(2) A method in which water, ice or steam is directly acted on an organoaluminum compound such as trialkylaluminum in a medium such as benzene, toluene, ethyl ether or tetrahydrofuran.

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

The aluminoxane may contain a small amount of organometallic components. After removing the solvent or unreacted organoaluminum compound from the recovered aluminoxane solution by distillation, the obtained aluminoxane may be redissolved in the solvent or suspended in a poor solvent for the aluminoxane.

Specific examples of the organoaluminum compound used for preparing the 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 singly or in combination of two or more.

Solvents used in the preparation of aluminoxanes include aromatic hydrocarbons such as benzene, toluene, xylene, cumene, and cymene; aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, hexadecane, and octadecane; , cyclohexane, cyclooctane, methylcyclopentane and other alicyclic hydrocarbons, petroleum fractions such as gasoline, kerosene and light oil, or the above aromatic hydrocarbons, aliphatic hydrocarbons and alicyclic hydrocarbon halides. and hydrocarbon solvents such as sulfides and bromides. 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 singly or in combination.

The organoaluminumoxy compound (B-2) according to the present invention includes an aluminoxane having a structure represented by the following general formula (B-2a) or (B-2b), and a general formula (B-2c) below. and a repeating unit represented by the following general formula (B-2d) as a structure.

一般式中、Ｒ^e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^e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。（Ｂ－２ｃ）および（Ｂ－２ｄ）中の、片方が原子と繋がっていない直線は、図示していない別の原子との結合を示す。

In the general formula, each R ^e is independently a hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms, specifically a methyl group, an ethyl group, a propyl group, an isopropyl group, an isopropenyl group. , n-butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, octyl group, decyl group, dodecyl group, tridecyl group, tetradecyl group, hexadecyl group, octadecyl group, eicosyl group, cyclohexyl group, cyclo Hydrocarbon groups such as octyl group, phenyl group, tolyl group and ethylphenyl group can be exemplified. Among these exemplified groups, a methyl group, an ethyl group, and an isobutyl group are preferable, and a methyl group is particularly preferable ^. A portion may be substituted with a halogen atom such as chlorine or bromine, and the halogen content may be 40% by weight or less. A straight line in (B-2c) and (B-2d), one of which is not connected to an atom, indicates a bond with another atom (not shown).

In the general formulas (B-2a) and (B-2b), r represents an integer of 2-500, preferably 6-300, particularly preferably 10-100.
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 freezing point depression method of benzene. preferably within.

In the benzene-insoluble organoaluminumoxy compound used in the present invention, the Al component dissolved in benzene at 60° C. is usually 10% or less, preferably 5% or less, and particularly preferably 2% or less in terms of Al atoms. That is, it is preferably insoluble or sparingly soluble in benzene. )

Examples of the organoaluminumoxy compound (B-2) used in the present invention include 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 the general formula (B-2e), R ¹⁵ represents a hydrocarbon group having 1 to 10 carbon atoms, and the four R ¹⁶ may be the same or different and each independently represents a hydrogen atom, a halogen represents a hydrocarbon group having 1 to 10 atoms or carbon atoms.)

The organoaluminumoxy compound containing boron represented by the general formula (B-2e) is obtained by reacting an alkylboronic acid represented by the following general formula (B-2f) and an organoaluminum compound in an inert gas atmosphere. 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).)

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- Hexylboronic acid, cyclohexylboronic acid, phenylboronic acid, 3,5-difluoroboronic acid, pentafluorophenylboronic acid, 3,5-bis(trifluoromethyl)phenylboronic acid and the like. Among these, methylboronic acid, n-butylboronic acid, isobutylboronic acid, 3,5-difluorophenylboronic acid and pentafluorophenylboronic acid are preferred. These are used individually by 1 type or in combination of 2 or more types.

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

As the organoaluminum compound, trialkylaluminum and tricycloalkylaluminum are preferable, and trimethylaluminum, triethylaluminum and triisobutylaluminum are particularly preferable. These are used individually by 1 type or in combination of 2 or more types.

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

((B-3) a compound that forms an ion pair by reacting with the transition metal compound [A])
The compound (B-3) (hereinafter referred to as "ionizable ionic compound") that reacts with the transition metal compound [A] to form an ion pair used in the present invention includes JP-A-1-501950, Lewis described in JP-A-1-502036, JP-A-3-179005, JP-A-3-179006, JP-A-3-207703, JP-A-3-207704, US-5321106, etc. Examples include acids, ionic compounds, borane compounds and carborane compounds. In addition, heteropolycompounds and isopolycompounds may also be mentioned.

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

Examples of the ionic compound 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 ⁺ , carbonium cation, oxonium cation, ammonium cation, phosphonium cation, cycloheptyltrienyl cation or ferrocenium cation having a transition metal, and R ¹⁸ to R ²¹ , which may be the same or different, is an organic group, preferably an aryl group or a substituted aryl group).

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

Specific examples of the ammonium cation include lower alkyl to higher alkyl such as trimethylammonium cation, triethylammonium cation, tripropylammonium cation, tributylammonium cation, tri(n-butyl)ammonium cation, and di(n-octadecyl)methylammonium cation. Trialkylammonium cations of alkyl; N,N-dialkylanilinium cations such as N,N-dimethylanilinium cations, N,N-diethylanilinium cations, N,N-2,4,6-pentamethylanilinium cations di(isopropyl)ammonium cation, dialkylammonium cation such as dicyclohexylammonium cation, and the like.

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.

Specific examples of the trialkyl-substituted ammonium salts include triethylammoniumtetra(phenyl)boron, tripropylammoniumtetra(phenyl)boron, tri(n-butyl)ammoniumtetra(phenyl)boron, trimethylammoniumtetra(p-tolyl ) boron, trimethylammonium tetra(o-tolyl) boron, tri(n-butyl) ammonium tetra(pentafluorophenyl) boron, tripropylammonium tetra(o,p-dimethylphenyl) boron, tri(n-butyl) ammonium tetra (m,m-dimethylphenyl) boron, tri(n-butyl) ammonium tetra(p-trifluoromethylphenyl) boron, tri(n-butyl) ammonium tetra(3,5-ditrifluoromethylphenyl) boron, tri( n-butyl)ammonium tetra(o-tolyl)boron, di(octadecyl)methylammoniumtetraphenylboron, di(octadecyl)methylammoniumtetrakis(p-tolyl)boron, di(octadecyl)methylammoniumtetrakis(o-tolyl)boron , di(octadecyl)methylammoniumtetrakis(pentafluorophenyl)boron, di(octadecyl)methylammoniumtetrakis(2,4-dimethylphenyl)boron, di(octadecyl)methylammoniumtetrakis(3,5-dimethylphenyl)boron, di (octadecyl)methylammoniumtetrakis(4-trifluoromethylphenyl)boron, di(octadecyl)methylammoniumtetrakis(3,5-ditrifluoromethylphenyl)boron and other di(octadecyl)methylammonium lower to higher alkyls However, alkylammonium salts can be exemplified.

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

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

Furthermore, as ionic compounds, triphenylcarbeniumtetrakis(pentafluorophenyl)borate, N,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate, ferroceniumtetra(pentafluorophenyl)borate, triphenylcarbeniumpentaphenyl Cyclopentadienyl complexes, N,N-diethylanilinium pentaphenylcyclopentadienyl complexes, boron compounds represented by the following formula (B-3b) or (B-3c), and the like can also be mentioned.

（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.)

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

Specific carborane compounds that are examples of ionizable ionic compounds include, for example, 4-carbanonaborane, 1,3-dicarbanonaborane, 6,9-dicarbadecaborane, dodecahydride-1-phenyl-1,3- dicarbanonaborane, dodecahydride-1-methyl-1,3-dicarbanonaborane, undecahydrite-1,3-dimethyl-1,3-dicarbanonaborane, 7,8-dicarbaundecaborane, 2 ,7-dicarboundecaborane, undecahydride-7,8-dimethyl-7,8-dicarboundecaborane, dodecahydride-11-methyl-2,7-dicarboundecaborane, tri(n-butyl)ammonium 1-carbadecaborate, tri(n-butyl)ammonium 1-carbaundecaborate, tri(n-butyl)ammonium 1-carbadodecaborate, tri(n-butyl)ammonium 1-trimethylsilyl-1-carbadecaborate, tri(n-butyl)ammonium bromo-1-carbadodecaborate, tri(n-butyl)ammonium 6-carbadecaborate, tri(n-butyl)ammonium 6-carbadecaborate, tri(n-butyl)ammonium 7- carbaundecaborate, tri(n-butyl)ammonium 7,8-dicarbaundecaborate, tri(n-butyl)ammonium 2,9-dicarbaundecaborate, tri(n-butyl)ammonium dodecahydride-8-methyl -7,9-dicarbaundecaborate, tri(n-butyl)ammonium undecahydride -8-ethyl-7,9-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 dicarboundecaborate, tri(n-butyl)ammonium undecahydride-4,6-dibromo-7-carboundecaborate;
Tri(n-butyl)ammonium bis(nonahydride-1,3-dicarbanonaborate) cobaltate (III), tri(n-butyl)ammonium bis(undecahydride-7,8-dicarbaundecaborate) Ferrate (III), tri(n-butyl)ammonium bis(undecahydride-7,8-dicarboundecaborate) cobaltate (III), tri(n-butyl)ammonium bis(undecahydride-7 ,8-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-carboundecaborate) manganate (IV), bis[tri(n-butyl)ammonium]bis(undecahydride-7-carbohydrate) boundecaborate) cobaltate (III), bis[tri(n-butyl)ammonium]bis(undecahydride-7-carboundecaborate)nickelate (IV), and the like. be done.

Heteropolycompounds, which are examples of ionizable ionic compounds, contain atoms selected from silicon, phosphorus, titanium, germanium, arsenic and tin and one or more atoms selected from vanadium, niobium, molybdenum and tungsten. is a compound. Specifically, phosphovanadic acid, germanovanadic acid, arsenic vanadic acid, phosphoniobic acid, germanoniobic acid, siliconomolybdic acid, phosphomolybdic acid, titanium molybdic acid, germanomolybdic acid, arsenic molybdic acid, tin molybdic acid, phosphorus tungstic acid, germanotungstic acid, stannotungstic acid, phosphomolybdovanadate, phosphotungstovanadate, germanotungstovanadate, phosphomolybdotungstovanadate, germanomolybdotungstovanadate, phosphomolybdotungstic acid , phosphomolybdoniobic acid, and salts of these acids. The salt of the acid includes, for example, an alkali metal of Group 1 or an alkaline earth metal of Group 2 of the periodic table, specifically lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, and calcium. , strontium, barium and the like, and organic salts such as triphenylethyl salts.

Isopolycompounds, examples of ionized ionic compounds, are compounds composed of metal ions of one atom selected from vanadium, niobium, molybdenum and tungsten, and are considered molecular ionic species of metal oxides. can be done. Specific examples include, but are not limited to, vanadic acid, niobic acid, molybdic acid, tungstic acid, and salts of these acids. Further, as the salt, for example, a metal of Group 1 or Group 2 of the periodic table, specifically lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium, etc., of the acid. and organic salts such as triphenylethyl salts.

The ionized ionic compound (the compound (B-3) that forms an ion pair by reacting with the transition metal compound [A]) as described above may be used alone or in combination of two or more.
Further, the olefin polymerization catalyst according to the present invention comprises the transition metal compound [A], the organometallic compound (B-1), the organoaluminumoxy compound (B-2), and the ionized ionic compound (B-3). At least one compound [B] selected from the group consisting of and, if necessary, 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 the 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, a clay, a clay mineral, or an ion-exchange layered compound.
Specific examples of the porous oxide include SiO ₂ , Al ₂ O ₃ , MgO, ZrO, TiO ₂ , B ₂ O ₃ , CaO, ZnO, BaO, ThO ₂ and the like, or composites or mixtures containing these. can also be used, for _{example natural or synthetic zeolites, SiO2-MgO, SiO2-Al2O3 , SiO2 - TiO2 , SiO2 - V2O5} , _SiO2 - _{Cr2O3 ,} SiO ₂ -TiO2 _- MgO and the like can be used. Among these, the porous oxide is preferably composed mainly of SiO ₂ and/or Al ₂ O ₃ .

The above porous oxides contain a small amount of _{Na2CO3 , K2CO3 , CaCO3} , _MgCO3 , _{Na2SO4 , Al2} ( _SO4 ) ₃ , _BaSO4 , _KNO3 , Mg( _NO3 ) ₂ , Al(NO ₃ ) ₃ , Na ₂ O, K ₂ O, Li ₂ O and other carbonates, sulfates, nitrates, and oxide components.

Such porous oxides have different properties depending on the type and manufacturing method. Desirably, the pore volume is in the range of 50 to 1000 m ² /g, preferably 100 to 700 m ² /g, and the pore volume is in the range of 0.3 to 3.0 cm ³ /g. Such porous oxides are calcined at 100 to 1000° C., preferably 150 to 700° C., if necessary.

Examples of the solid aluminoxane compound include an aluminoxane selected from at least one of the aluminoxanes shown in (B-2a) to (B-2d) above.
The solid aluminoxane used in the present invention does not contain inorganic solid components such as silica and alumina, or organic polymer components such as polyethylene and polystyrene, unlike conventionally known carriers for olefin polymerization catalysts, and the main component is an alkyl aluminum compound. The solidified one is shown as The term "solid state" used in the present invention means that the aluminoxane component (B-2) maintains a substantially solid state under the reaction environment in which it is used. More specifically, for example, when the component [A] and the component [B] are brought into contact with each other as described below to prepare a solid catalyst component for olefin polymerization, an inert hydrocarbon solvent such as hexane or toluene used in the reaction Medium indicates that component [B] is in a solid state under a specific temperature and pressure environment. Further, for example, when suspension polymerization is carried out using a solid catalyst component for olefin polymerization prepared using component [B] as described later, it can be carried out in a hydrocarbon solvent such as hexane, heptane, or toluene at a specific temperature and pressure. It is also a necessary requirement that the component [B] contained in the catalyst component be in a solid state under 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 a monomer gas.

Visual confirmation is the easiest way to confirm whether component [B] is in a solid state under the above environment. However, visual confirmation is often difficult, for example, during polymerization. In that case, it is possible to determine, for example, from the properties of the polymer powder obtained after polymerization, the state of adhesion to the reactor, and the like. Conversely, if the properties of the polymer powder are good and there is little adhesion to the reactor, even if some of the component [B] is eluted under the polymerization environment, it does not deviate from the gist of the present invention. Indices for judging the properties of the polymer powder include bulk density, particle shape, surface shape, and the degree of presence of amorphous polymer. Polymer bulk density is preferable from the viewpoint of quantification. The bulk density in the present invention is generally 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 kept 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 ratio of the solid aluminoxane used in the present invention in n-hexane was obtained by adding 2 g of the solid aluminoxane carrier to 50 ml of n-hexane maintained at 25° C., stirring for 2 hours, and then adding the mixture to G-4 glass. It was obtained by separating the solution portion using a filter and measuring the aluminum concentration in this filtrate. Therefore, the dissolution ratio is determined as the ratio of aluminum atoms present in the filtrate to the amount of aluminum atoms corresponding to 2 g of aluminoxane used.

As the solid aluminoxane according to the present invention, known solid aluminoxanes can be used without limitation. As known production methods, for example, JP-B-7-42301, JP-A-6-220126, JP-A-6-220128, JP-A-11-140113, JP-A-11-310607, JP-A-2000 -38410, JP-A-2000-95810, WO201055652 and the like.

The average particle size of the solid aluminoxane according to the invention is generally in the range of 0.01-50000 μm, preferably 1-1000 μm, particularly preferably 1-200 μm.
The average particle size of the solid aluminoxane is obtained by observing particles with a scanning electron microscope, measuring the particle size of 100 or more particles, and averaging the weight average. The particle size of the solid aluminoxane was measured from the particle image of the maximum length by the Pythagoras method. That is, the length of the particle image sandwiched between two parallel lines is measured in each of the horizontal and vertical directions, and it is obtained by calculation using the following formula.
Particle size = ((horizontal length) ² + (vertical length) ² ) ^0.5
The weight average particle size of the solid aluminoxane is determined by the following formula using the particle size determined above.
Average particle size = Σnd ⁴ /Σnd ³ (here, 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, MgCl ₂ , MgBr ₂ , MnCl ₂ , MnBr ₂ and the like are used. The inorganic halide may be used as it is, or may be used after pulverizing with a ball mill or vibration mill. Moreover, after dissolving an inorganic halide in a solvent such as alcohol, it is possible to use a product obtained by depositing 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 planes formed by ionic bonds or the like are stacked in parallel with weak bonding force, and the ions contained therein are exchangeable. Most clay minerals are ion exchange layered compounds. Moreover, as these clays, clay minerals, and ion-exchangeable layered compounds, not only naturally occurring ones but also artificially synthesized ones can be used.

Examples of clays, clay minerals, or ion-exchangeable layered compounds include ionic crystalline compounds having layered crystal structures such as hexagonal close-packing type, antimony type, _CdCl2 type, and _CdI2 type.

Furthermore, clays and clay minerals include kaolin, bentonite, kibushi clay, gyrome clay, allophane, hisingerite, pyrophyllite, ummo group, montmorillonite group, vermiculite, ryokudite group, palygorskite, kaolinite, nacrite, dickite, halloy sites, etc.
Examples of ion-exchangeable layered compounds include α-Zr(HAsO ₄ ) _{2.H 2} O, α-Zr(HPO ₄ ) ₂ , α-Zr(KPO ₄ ) _{2.3H 2} O, α-Ti(HPO ₄ ). ₂ , α-Ti(HAsO ₄ ) ₂ H ₂ O, α-Sn(HPO ₄ ) ₂ H ₂ O, γ-Zr (HPO ₄ ) ₂ , γ-Ti (HPO ₄ ) ₂ , γ-Ti( Crystalline acid salts of polyvalent metals such as NH ₄ PO ₄ ) ₂ ·H ₂ O and the like can be mentioned.

Such a clay, clay mineral, or ion-exchangeable layered compound preferably has a pore volume of 0.1 cc/g or more, more preferably 0.3 to 5 cc/g, with a radius of 20 Å or more measured by mercury porosimetry. is particularly preferred. Here, the pore volume is measured in the pore radius range of 20 to 30000 Å by mercury porosimetry using a mercury porosimeter.
When a carrier having a pore volume of less than 0.1 cc/g with a radius of 20 Å or more is used, 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. Any chemical treatment can be used, such as a surface treatment for removing impurities adhering to the surface, a treatment for affecting the crystal structure of clay, and the like. Specific examples of chemical treatment include acid treatment, alkali treatment, salt treatment, and organic treatment. The acid treatment removes surface impurities and also elutes cations such as Al, Fe and Mg in the crystal structure to increase the surface area. Alkaline treatment destroys the crystalline structure of the clay, resulting in changes in the clay structure. Also, in salt treatment and organic matter treatment, ionic complexes, molecular complexes, organic derivatives, etc. are formed, and the surface area and interlayer distance can be changed.

The ion-exchangeable layered compound used in the present invention may be a layered compound in which the interlayer spacing is expanded by exchanging the exchangeable ions between the layers with other large bulky ions by utilizing the ion-exchangeability. . Such bulky ions play a pillar-like role supporting the layered structure and are usually called pillars. Also, the introduction of another substance between the layers of a layered compound is called intercalation. Guest compounds for intercalation include cationic inorganic compounds such as TiCl ₄ and ZrCl ₄ , metal alkoxides such as Ti(OR) ₄ , Zr(OR) ₄ , PO(OR) ₃ and B(OR) ₃ ( R is a hydrocarbon group, etc.), metal hydroxide ions such as [Al ₁₃ O ₄ (OH) ₂₄ ] ⁷⁺ , [Zr ₄ (OH) ₁₄ ] ²⁺ , [Fe ₃ O (OCOCH ₃ ) ₆ ] ⁺ etc. These compounds are used alone or in combination of two or more. In addition, when intercalating these compounds, hydrolyzing metal alkoxides (R represents a hydrocarbon group, etc.) such as Si(OR) ₄ , Al(OR) ₃ , Ge(OR) ₄ , etc. The obtained polymer, a colloidal inorganic compound such as SiO ₂ , etc. can be coexistent. Examples of pillars include oxides produced by intercalating the above metal hydroxide ions between layers and then dehydrating them by heating.

The clay, clay mineral, and ion-exchangeable layered compound used in the present invention may be used as they are, or may be used after being subjected to treatments such as ball milling and sieving. Alternatively, water may be newly added and adsorbed, or may be used after heat dehydration treatment. Furthermore, it 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 described above, the carrier [C] is an inorganic or organic compound, and examples of organic compounds include granular or particulate solids having a particle size in the range of 10 to 300 μm. Specifically, polymers produced mainly from α-olefins having 2 to 14 carbon atoms such as ethylene, propylene, 1-butene and 4-methyl-1-pentene, or vinylcyclohexane and styrene as main components. Polymers produced as and modified products thereof can be exemplified.

The olefin polymerization catalyst according to the present invention comprises the transition metal compound [A], the compound [B], and optionally the carrier [C], and optionally the following specific organic compound component [D]. can also contain

[[D] Organic compound component]
In the present invention, the organic compound component [D] optionally 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). used for the purpose of Examples of such organic compounds include, but are not limited to, alcohols, phenolic compounds, carboxylic acids, phosphorus compounds and sulfonates.

As the alcohols and 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, carbon atoms 6 to 50) or a halogenated hydrocarbon group having 1 to 50 carbon atoms (6 to 50 carbon atoms in the case of phenols).

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

As the carboxylic acid, those represented by R ²³ —COOH 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.

Phosphoric acids having P—O—H bonds, phosphates having P—OR and P═O bonds, and phosphine oxide compounds are preferably used as the phosphorus compound.
Examples of the sulfonate include those represented by the following general formula (Da).

（一般式（Ｄ－ａ）中、Ｍ⁵は周期律表第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 general formula (Da), M ⁵ is an atom of groups 1 to 14 of the periodic table, R ²⁴ is hydrogen, a hydrocarbon group having 1 to 20 carbon atoms, or a halogen 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 t−u≧1.)

<Method for producing polyolefin>
In the method for producing a polyolefin according to the present invention, a polyolefin is obtained by including a step of polymerizing (homopolymerizing or copolymerizing) an olefin in the presence of an olefin polymerization catalyst as described above. As described above, the term olefin as used herein 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 are arbitrarily selected, but the following methods are exemplified.
(1) A method of adding the transition metal compound [A] alone to the polymerization vessel.
(2) A method of adding the transition metal compound [A] and the compound [B] in any order to the polymerization vessel.
(3) A method of adding a catalyst component in which a transition metal compound [A] is supported on a carrier [C] and a compound [B] in an arbitrary order to a polymerization vessel.
(4) A method of adding the catalyst component in which the compound [B] is supported on the carrier [C] and the transition metal compound [A] to the polymerization vessel in any order.
(5) A method of adding a catalyst component in which a transition metal compound [A] and a compound [B] are supported on a carrier [C] to a polymerization vessel.
(6) A method of adding the catalyst component in which the transition metal compound [A] and the compound [B] are supported on the carrier [C] and the compound [B] in an arbitrary order to the polymerization vessel. 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 of adding the catalyst component in which the compound [B] is supported on the carrier [C] and the transition metal compound [A] in any order to the polymerization vessel.
(8) A method of adding the catalyst component in which the compound [B] is supported on the carrier [C], the transition metal compound [A], and the compound [B] to the 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 of adding a component in which a transition metal compound [A] is supported on a carrier [C] and a component in which a compound [B] is supported on a carrier [C] in an arbitrary order to a polymerization vessel.
(10) A method of adding 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] to an arbitrary sequential polymerization vessel. 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 of adding the transition metal compound [A], the compound [B], and the organic compound component [D] to the polymerization vessel in any order.
(12) A method in which the component obtained by contacting the compound [B] and the organic compound component [D] in advance, and the transition metal compound [A] are added in any order to the polymerization reactor.
(13) A method in which the compound [B] and the organic compound component [D] supported on the carrier [C], and the transition metal compound [A] are added in any order to the polymerization vessel.
(14) A method of adding the catalyst component obtained by contacting the transition metal compound [A] and the compound [B] in advance, and the organic compound component [D] in any order to the polymerization vessel.
(15) A method of adding the catalyst component obtained by contacting the transition metal compound [A] and the compound [B] in advance, the compound [B], and the organic compound component [D] to a polymerization reactor 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 are added in an arbitrary order to the polymerization reactor. 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 of adding a component in which a transition metal compound [A] is supported on a carrier [C], a compound [B], and an organic compound component [D] to a polymerization vessel in any order.
(18) A method in which the component in which the transition metal compound [A] is supported on the carrier [C] and the component in which the compound [B] and the organic compound component [D] are brought into contact in advance are added to the polymerization vessel in any order.
(19) A method in which the transition metal compound [A], the compound [B] and the organic compound component [D] are brought into contact in advance in any order and added to the polymerization reactor.
(20) A method in which the catalyst component obtained by contacting the transition metal compound [A], the compound [B] and the organic compound component [D] in advance, and the compound [B] are added in any order to the polymerization vessel. In this case, the compound [B] brought into contact with the transition metal compound [A] and the organic compound component [D] and the compound [B] added alone may be the same or different.
(21) A method of adding 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 of adding a catalyst component in which a transition metal compound [A], a compound [B] and an organic compound component [D] are supported on a carrier [C], and the component [B] in an arbitrary order to a polymerization vessel. 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] are prepared with an olefin. It may be polymerized, and a catalyst component may be further supported on the prepolymerized solid catalyst component.

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

When olefin polymerization is carried out using the olefin polymerization catalyst as described above, the transition metal compound [A] is generally 10 ^-12 to 10 ^-2 mol, preferably 10 ^-10 to 10 mol per liter of reaction volume. It is used in such an amount that it becomes ^-3 moles.

In the organometallic compound (B-1), the molar ratio [(B-1)/M] between the organometallic compound (B-1) and all the transition metal atoms (M) in the transition metal compound [A] is usually It is used in an amount of 0.01 to 100,000, preferably 0.05 to 50,000. The organoaluminum oxy compound (B-2) is the molar ratio of the aluminum atoms in the organoaluminum oxy compound (B-2) to the total transition metal (M) in the transition metal compound [A] [(B-2) /M] is generally 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 the atom (M) is generally 1-10, preferably 1-5.

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

The temperature for olefin polymerization using such an olefin polymerization catalyst is usually -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. 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 polyolefin can be adjusted by allowing hydrogen to be present in the polymerization system or by changing the polymerization temperature. Furthermore, it can also be adjusted by the amount of the 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. is 2 to 10 linear or branched α-olefins 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 carbon atoms, 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.

The catalyst for olefin polymerization of the present invention is used for homopolymerization of ethylene or copolymerization of ethylene with an α-olefin having 3 to 20 carbon atoms, preferably a linear or branched α-olefin having 3 to 10 carbon atoms. It is more preferable to use The α-olefins may be used singly or in combination of two or more.

In the case of copolymerization of ethylene with an α-olefin having 3 to 20 carbon atoms, preferably 3 to 10 carbon atoms, the α-olefin (hereinafter also referred to as olefin A) is not particularly limited as long as the effect of the present invention is exhibited. but, 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 preferable.

When ethylene is used and the above olefin A is used, the ratio of the amount of ethylene and the above olefin A used is ethylene:the above olefin A (molar ratio), usually 1:10 to 5000:1, preferably 1:5 to 1000:1.

The olefin polymerization catalyst of the present invention is the homopolymerization of propylene, or propylene and an α-olefin having 2 to 20 carbon atoms (excluding propylene), preferably a linear or branched α having 2 to 10 carbon atoms. - It is also preferably used for copolymerization with olefins. The α-olefins may be used singly or in combination of two or more.

In the production method of the present invention, when homopolymerization of propylene or copolymerization of propylene with an α-olefin having 2 to 20 carbon atoms (excluding propylene) is performed, the activity of the catalyst is high, and the resulting polymer is It is possible to obtain a polymer having a high molecular weight and high stereoregularity.

In the case of copolymerization of propylene and an α-olefin having 2 to 20 carbon atoms, preferably 2 to 10 carbon atoms (excluding propylene), the α-olefin (hereinafter also referred to as olefin B) may be Although not particularly limited as long as the effect is exhibited, for example, ethylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1 -octene, 1-decene are preferred. 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 preferable.

When propylene is used and the olefin B is used, the ratio of the amount of propylene and the olefin B used is propylene:the olefin B (molar ratio), usually 1:10 to 5000:1, preferably 1:5 to 1000:1.

The olefin polymerization catalyst of the present invention is a homopolymerization of 1-butene, or 1-butene and an α-olefin having 2 to 20 carbon atoms (excluding 1-butene), preferably a linear chain having 2 to 10 carbon atoms. It is also preferably used for copolymerization with linear or branched α-olefins. The α-olefins may be used singly or in combination of two or more.

In the production method of the present invention, when homopolymerization of 1-butene or copolymerization of 1-butene and an α-olefin having 2 to 20 carbon atoms (excluding 1-butene) is performed, the activity of the catalyst is high. , the molecular weight of the resulting polymer can be increased, and a polymer having high stereoregularity can be obtained.

In the case of copolymerization of 1-butene with an α-olefin having 2 to 20 carbon atoms, preferably 2 to 10 carbon atoms (excluding 1-butene), the α-olefin (hereinafter also referred to as olefin C) is , but not particularly limited as long as the effects of the present invention are exhibited, but examples include ethylene, propylene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene , 1-octene and 1-decene are preferred. These α-olefins may be used alone or in combination of two or more. Among these, at least one selected from propylene, 1-hexene, 4-methyl-1-pentene and 1-octene is more preferable.

When 1-butene is used and the above olefin C is used, the ratio of the amount of 1-butene and the above olefin C used is 1-butene:the above olefin C (molar ratio), usually 1:10 to 5000:1, It is preferably 1:5 to 1000:1.

The olefin polymerization catalyst of the present invention is also preferably used for copolymerization of ethylene, a cyclic olefin and an aromatic vinyl compound. A cyclic olefin and an aromatic vinyl compound may be used individually by 1 type, respectively, and may use 2 or more types together.

In the production method of the present invention, when ethylene, a cyclic olefin, and an aromatic vinyl compound are copolymerized, a polymer having high catalytic activity and having many structural units derived from the aromatic vinyl compound can be obtained. In addition, having many structural units derived from an aromatic vinyl compound means that the aromatic vinyl compound in the present invention is more aromatic than when ethylene, a cyclic olefin, and an aromatic vinyl compound are copolymerized using another catalyst. It means that the conversion rate of the vinyl compound (the rate at which the aromatic vinyl compound reacts) is high, and the polymer contains many structural units derived from the aromatic vinyl compound.

Cyclic olefins include cyclic olefins having 3 to 30 carbon atoms, preferably 3 to 20 carbon atoms, and more preferably 3 to 10 carbon atoms. Specific examples of cyclic olefins include cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene (tetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ]-3-dodecene) , 2-methyl-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene.

The aromatic vinyl compound includes an aromatic vinyl compound having 8 to 20 carbon atoms, preferably 8 to 18 carbon atoms, more preferably 8 to 16 carbon atoms. Specific examples of aromatic vinyl compounds include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, o,p-dimethylstyrene, 3,5-dimethylstyrene, o-ethylstyrene, m-ethylstyrene, p-ethylstyrene, o-iso-propylstyrene, m-iso-propylstyrene, p-iso-propylstyrene, 3,5-iso-propylstyrene, o-tert-butylstyrene, m-tert-butylstyrene, p mono- or polyalkylstyrenes such as -tert-butylstyrene, 3,5-tert-butylstyrene, and the like.

When ethylene, a cyclic olefin, and an aromatic vinyl compound are copolymerized, the ratio (molar ratio) of the amount of each monomer used is usually 0.0002 to 10 for the cyclic olefin when ethylene is 1, and the aromatic vinyl compound is used. 0.0002 to 10 for the group vinyl compound, preferably 0.001 to 5 for the cyclic olefin, and 0.001 to 5 for the aromatic vinyl compound.

The olefin polymerization catalyst of the present invention may polymerize a linear unsaturated hydrocarbon having a polar group (for example, a carbonyl group, a hydroxyl group, an ether bond group, etc.). , for example acrylic acid, 3-butenoic acid, 4-pentenoic acid, 5-hexenoic acid, 6-heptenoic acid, 7-octenoic acid, 8-nonenoic acid, 9-decenoic acid, 10-undecenoic acid, 11-dodecenoic acid, 12-tridecenoic acid, 13-tetradecenoic acid, 14-pentadecenoic acid, 15-hexadecenoic acid, 16-heptadecenoic acid, 17-octadecenoic acid, 18-nonadecenoic acid, 19-eicosenoic acid, 20-henicosenoic acid, 21-docosenoic acid, 22-tricosenoic acid, methacrylic acid, 2-methylpentenoic acid, 2,2-dimethyl-3-butenoic acid, 2,2-dimethyl-4-pentenoic acid, 3-vinylbenzoic acid, 4-vinylbenzoic acid, 2, 6-heptadienoic acid, 2-(4-isopropylbenzylidene)-4-pentenoic acid, allylmalonic acid, 2-(10-undecenyl)malonic acid, fumaric acid, itaconic acid, bicyclo[2.2.1]-5-heptene -2-carboxylic acid, unsaturated carboxylic acids such as bicyclo[2.2.1]-5-heptene-2,3-dicarboxylic acid, and sodium salts, potassium salts, lithium salts, zinc salts, magnesium salts thereof, Metal salts such as calcium salts, and unsaturated carboxylic acids such as methyl esters, ethyl esters, n-propyl esters, isopropyl esters, n-butyl esters, isobutyl esters, (5-norbornen-2-yl) esters, etc. Carboxylic acid esters (when the unsaturated carboxylic acid is a dicarboxylic acid, it may be a monoester or a diester), and unsaturated carboxylic acid amides of these unsaturated carboxylic acids, such as N,N-dimethylamide. saturated carboxylic acid amides (which may be monoamides or diamides when the unsaturated carboxylic acid is a dicarboxylic acid);
maleic anhydride, itaconic anhydride, allylsuccinic anhydride, isobutenylsuccinic anhydride, (2,7-octadien-1-yl)succinic anhydride, tetrahydrophthalic anhydride, bicyclo[2.2.1 ]-Unsaturated carboxylic anhydrides such as 5-heptene-2,3-dicarboxylic anhydride;
Vinyl esters such as vinyl acetate, vinyl propionate, vinyl caproate, vinyl caprate, vinyl laurate, vinyl stearate;
allyl esters such as allyl acetate, allyl propionate, allyl caproate, allyl caprate, allyl laurate, and allyl stearate;
halogenated olefins such as vinyl chloride, vinyl fluoride, vinyl bromide, vinyl iodide, allyl bromide, allyl chloride, allyl fluoride, allyl bromide;
Halogenated styrenes such as o-chlorostyrene and p-chlorostyrene;
silyl group-containing styrenes such as p-trimethylsilylstyrene;
polar group-containing styrenes such as p-methoxystyrene, p-methylthiostyrene, p-trimethylsiloxystyrene;
Silylated olefins such as allyltrimethylsilane, diallyldimethylsilane, 3-butenyltrimethylsilane, allyltriisopropylsilane, allyltriphenylsilane;
Unsaturated nitriles such as acrylonitrile, 2-cyanobicyclo[2.2.1]-5-heptene, 2,3-dicyanobicyclo[2.2.1]-5-heptene;
Unsaturated alcohol compounds such as allyl alcohol, 3-butenol, 4-pentenol, 5-hexenol, 6-hebutenol, 7-octenol, 8-nonenol, 9-decenol, 10-undecenol, 11-dodecenol, and 12-tridecenol , and unsaturated esters such as these acetates, benzoates, propionates, caproates, caprates, laurates, and stearates;
substituted phenols such as vinylphenol and allylphenol, and unsaturated esters thereof such as acetate, benzoate, propionate, caproate, caprate, laurate and stearate;
substituted benzyl alcohols such as vinyl benzyl alcohol and allyl benzyl alcohol; and unsaturated esters thereof such as acetates, benzoates, propionates, caproates, caprates, laurates and stearates;
Unsaturated ethers such as methyl vinyl ether, ethyl vinyl ether, allyl methyl ether, allyl propyl ether, allyl butyl ether, allylmethallyl ether, methoxystyrene, ethoxystyrene, allylanisole;
unsaturated epoxides such as butadiene monoxide, 1,2-epoxy-7-octene, 3-vinyl 7-oxabicyclo[4.1.0]heptane;
Unsaturated aldehydes such as acrolein and undecenal, and unsaturated acetals thereof such as dimethylacetal and diethylacetal;
Unsaturated ketones such as methyl vinyl ketone, ethyl vinyl ketone, allyl methyl ketone, allyl ethyl ketone, allyl propyl ketone, allyl butyl ketone, allyl benzyl ketone, and unsaturated acetals thereof such as dimethyl acetal and diethyl acetal;
Unsaturated thioethers such as allylmethylsulfide, allylphenylsulfide, allylisopropylsulfide, allyl n-propylsulfide, 4-pentenylphenylsulfide;
Unsaturated sulfoxides such as allylphenyl sulfoxide;
Unsaturated sulfones such as allylphenyl sulfone;
Unsaturated phosphines such as allyldiphenylphosphine;
and unsaturated phosphine oxides such as allyldiphenylphosphine oxide.

Furthermore, unsaturated hydrocarbons having two or more of the polar groups listed above, such as vinyl trifluoroacetate, allyl trifluoroacetate, methyl 4-(3-butenyloxy)benzoate, glycidyl acrylate, allyl glycidyl ether, (2H-perfluoropropyl)-2-propenyl ether, linalool oxide, 3-allyloxy-1,2-propanediol, 2-(allyloxy)ethanol, N-allylmorpholine, allylglycine, N-vinylpyrrolidone, allyltrichlorosilane, Acryltrimethylsilane, allyldimethyl(diisopropylamino)silane, 7-octenyltrimethoxysilane, allyloxytrimethylsilane, allyloxytriphenylsilane, etc. may also be polymerized by the olefin polymerization catalyst of the present invention.

Further, the olefin polymerization catalyst of the present invention may polymerize vinylcyclohexane, dienes, polyenes, and 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 styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, o,p-dimethylstyrene, o-ethylstyrene, m-ethylstyrene, p-ethylstyrene and the like mono- or poly- alkyl styrene;
functional group-containing styrene derivatives 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.

The transition metal compound [A] of the present invention has a novel structure in which a specific substituent is introduced at a specific position of the metallocene skeleton as described above, and the olefin polymerization of the present invention containing the compound [A]. These catalysts have particularly superior α-olefin copolymerization properties and good olefin polymerization activity compared to transition metal compounds with conventional metallocene skeletons (which do not have specific substituents at specific positions). Low density ethylene-based copolymers of sufficient molecular weight can be produced.

The effect is due to (i) the effect of introducing a heteroatom-containing electron-donating substituent to the metallocene specific site in the transition metal compound [A] represented by the general formula [1] or [3], which is remarkable for α-olefin It is believed that this is due to the improvement of copolymerizability and (ii) the effect of inhibiting the phenomenon of lowering activity due to the introduction of a heteroatom by the effect of introducing substituents into the vicinity.

[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 specific structure described above, one or more α-olefins having 2 to 30 carbon atoms Preferably, an olefin polymer can be efficiently produced by homopolymerizing ethylene or copolymerizing ethylene with an α-olefin having 3 to 20 carbon atoms (olefin A). .

Further, in the present invention, homopolymerization of propylene, or propylene and α- An olefin polymer can also be efficiently produced by copolymerizing an olefin (excluding propylene) (olefin B), and ethylene, a cyclic olefin, and an aromatic vinyl compound are copolymerized. It is also possible to efficiently produce olefin polymers by homopolymerization of 1-butene, or 1-butene and α-olefins having 2 to 20 carbon atoms (excluding 1-butene) (olefin It is also possible to efficiently produce an olefin polymer by copolymerizing C).

As one aspect of the olefin polymer of the present invention, an ethylene-based polymer containing ethylene-derived structural units in an amount of preferably 90 to 100 mol%, more preferably 92 to 100 mol%, and still more preferably 95 to 100 mol% coalescence is mentioned. The ethylene-based polymer preferably contains 0 to 10 mol %, more preferably 0 to 8 mol %, and still more preferably 0 to 5 mol % of structural units derived from olefin A. However, the sum of the content of the structural unit derived from ethylene and the content of the structural unit derived from olefin A is 100 mol %. The ethylene-based polymer in which the structural unit derived from olefin A falls within the above range is excellent in moldability. In addition, other structural units may be included within the scope of the present invention. These contents can be measured by nuclear magnetic resonance spectroscopy, or by infrared spectroscopy when there is a standard substance.

Among these polymers, ethylene homopolymers, ethylene/propylene copolymers, ethylene/1-butene copolymers, ethylene/propylene/1-butene copolymers, ethylene/1-octene polymers, 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. It may also be a so-called block copolymer (impact copolymer) obtained by mixing or continuously producing two or more selected from these polymers.

The ethylene-based polymer of the present invention is preferably an α-olefin polymer consisting essentially of α-olefin-derived structural units having 2 to 20 carbon atoms, among the polymers having the above-described structural units. The term “substantially” means that the ratio of structural units derived from α-olefins having 2 to 20 carbon atoms is 95% by weight or more with respect to all structural units.

As another aspect of the olefin polymer of the present invention, the propylene-derived structural unit is preferably 50 to 100 mol%, more preferably 55 to 100 mol%, still more preferably 80 to 100 mol%, particularly preferably 90 A propylene-based polymer containing in the range of up to 100 mol % is mentioned. The propylene-based polymer preferably contains 0 to 50 mol%, more preferably 0 to 45 mol%, still more preferably 0 to 20 mol%, and particularly preferably 0 to 10 mol% of the constituent units derived from the olefin B. Including in the range of However, the sum of the content of the structural unit derived from propylene and the content of the structural unit derived from olefin B is 100 mol %. A propylene-based polymer having the structural unit derived from the olefin B within the above range is excellent in moldability and strength. In addition, other structural units may be included within the scope of the present invention. These contents can be measured by nuclear magnetic resonance spectroscopy, or by infrared spectroscopy when there is a standard substance.

Among these polymers, propylene homopolymers, propylene/ethylene copolymers, propylene/1-butene copolymers, propylene/ethylene/1-butene copolymers, propylene/1-octene polymers, propylene/1 -hexene polymer, propylene/4-methyl-1-pentene polymer, propylene/ethylene/1-octene polymer, propylene/ethylene/1-hexene polymer, propylene/ethylene/4-methyl-1-pentene polymer is particularly preferred. It may also be a so-called block copolymer (impact copolymer) obtained by mixing or continuously producing two or more selected from these polymers.

The propylene-based polymer of the present invention is preferably an α-olefin polymer consisting essentially of α-olefin-derived structural units having 2 to 20 carbon atoms among the polymers having the above-described structural units. The term “substantially” means that the ratio of structural units derived from α-olefins having 2 to 20 carbon atoms is 95% by weight or more with respect to all structural units.

Another aspect of the olefin polymer of the present invention is an ethylene/cyclic olefin/aromatic vinyl compound copolymer obtained by copolymerizing ethylene, a cyclic olefin, and an aromatic vinyl compound. The ethylene/cyclic olefin/aromatic vinyl compound copolymer contains ethylene-derived structural units in an amount of preferably 30 to 70 mol%, more preferably 35 to 70 mol%, still more preferably 40 to 65 mol%, It contains preferably 10 to 70 mol %, more preferably 20 to 60 mol %, and still more preferably 20 to 45 mol % of structural units derived from cyclic olefins, and preferably contains 0.5 mol % of structural units derived from aromatic vinyl compounds. It is contained in the range of 1 to 20 mol %, more preferably 1 to 20 mol %, still more preferably 5 to 20 mol %. However, the sum of the content of structural units derived from ethylene, the content of structural units derived from cyclic olefins, and the content of structural units derived from aromatic vinyl compounds is 100 mol %. An ethylene/cyclic olefin/aromatic vinyl compound copolymer having a structural unit derived from each monomer within the above range is excellent in optical properties such as heat resistance, transparency, and refractive index. In addition, other structural units may be included within the scope of the present invention. These contents can be measured by nuclear magnetic resonance spectroscopy, or by infrared spectroscopy when there is a standard substance.

Among these polymers, ethylene/tetracyclododecene/styrene copolymers,
Ethylene/norbornene/styrene copolymers are preferred. It may also be a so-called block copolymer (impact copolymer) obtained by mixing or continuously producing two or more selected from these polymers.

The ethylene/cyclic olefin/aromatic vinyl compound copolymer of the present invention is, among the polymers having the above-described structural units, substantially ethylene-derived structural units, cyclic olefin-derived structural units, and aromatic vinyl A copolymer consisting only of structural units derived from a compound is preferred. The term "substantially" means that the ratio of structural units derived from the monomer is 95% by weight or more with respect to all structural units.

As another aspect of the olefin polymer of the present invention, the constituent unit derived from 1-butene is preferably 50 to 100 mol%, more preferably 55 to 100 mol%, still more preferably 80 to 100 mol%, particularly preferably is a 1-butene polymer containing in the range of 90 to 100 mol %. The 1-butene polymer preferably contains a total of 0 to 50 mol%, more preferably 0 to 45 mol%, still more preferably 0 to 20 mol%, and particularly preferably 0 to 10 Included in the range of mol %. However, the sum of the content of the structural unit derived from 1-butene and the content of the structural unit derived from olefin C is 100 mol %. The 1-butene polymer having the olefin C-derived structural unit within the above range is excellent in moldability and strength. In addition, other structural units may be included within the scope of the present invention. These contents can be measured by nuclear magnetic resonance spectroscopy, or by infrared spectroscopy when there is a standard substance.

Among these polymers, 1-butene homopolymer, 1-butene/ethylene copolymer, 1-butene/propylene copolymer, 1-butene/ethylene/propylene copolymer, 1-butene/1-octene Polymer, 1-butene/1-hexene polymer, 1-butene/4-methyl-1-pentene polymer, 1-butene/ethylene/1-octene polymer, 1-butene/ethylene/1-hexene polymer , 1-butene/ethylene/4-methyl-1-pentene polymers are particularly preferred. It may also be a so-called block copolymer (impact copolymer) obtained by mixing or continuously producing two or more selected from these polymers.

The 1-butene polymer of the present invention is preferably an α-olefin polymer composed substantially only of α-olefin-derived structural units having 2 to 20 carbon atoms among the polymers having the above-described structural units. . The term “substantially” means that the ratio of structural units derived from α-olefins having 2 to 20 carbon atoms is 95% by weight or more with respect to all structural units.

In the ethylene-based polymer of the present invention, the weight average molecular weight measured by gel permeation chromatography (GPC) is not particularly limited, but is preferably 10,000 to 5,000,000, more preferably 10,000. 000 to 2,000,000, particularly preferably 20,000 to 1,000,000. The molecular weight distribution (Mw/Mn), which is the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn), is not particularly limited, but is preferably 1 to 10, more preferably 1 to 7, particularly preferably 1 to 5. The molecular weight distribution can also be adjusted by producing polymers with different molecular weights using a multistage polymerization method or the like, or by a method such as solvent fractionation.

The ethylene polymer of the present application has a relatively narrow molecular weight distribution when obtained by single-stage polymerization, and tends to narrow the molecular weight distribution as the density decreases due to copolymerization with (higher) α-olefins. The reason why such a phenomenon occurs can be presumed as described above.

Although the density of the ethylene polymer of the present invention is not particularly limited, it is preferably 875 kg/m ³ or more and 975 kg/m ³ or less.
In the ethylene polymer of the present invention, the intrinsic viscosity [η] in decalin at 135° C. is not particularly limited, but is preferably 0.1 to 40 dl/g, more preferably 0.5 to 15 dl/g, and particularly preferably 1 to 10 dl/g.

In the ethylene polymer of the present invention, the melt mass flow rate (MFR; unit is g/10 min) measured under the conditions of 190° C. and 2.16 kg load according to ASTM D1238-89 is not particularly limited, but preferably It is 0.001 g/10 min or more and 300 g/10 min or less, more preferably 0.001 g/10 min or more and 200 g/10 min 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 10kg load by the MFR value measured under the conditions of 190°C and 2.16kg load is 5. It is preferably 0 or more and less than 300.

The details of the measurement conditions for the above physical property values are as described in Examples.

The following examples further illustrate the present invention. It should be noted that the present invention is not limited to the description of the following examples.
The compounds described in the synthesis examples are 270 MHz, ¹ H-NMR (JEOL; GSH-270), gas chromatograph mass spectrometer (GC-MS) (Shimadzu Corporation; GCMS-QP5050A and Shimadzu Corporation; GCMS-QP2010Ultra), It was identified using FD-mass spectrometry (JEOL SX-102A).
Also, a method for measuring physical properties and properties of a polymer obtained by polymerization of an olefin in the presence of a catalyst containing the transition metal compound of the present invention is described below.

・Density (kg/m ³ )
Using a hydraulic ^heat press machine manufactured by Shindo Metal Industry Co., Ltd. set at 190 ° C., a 0.5 mm thick sheet was formed at a pressure of 100 kg / cm (spacer shape: 240 × 240 × 0.5 (mm) thick plate 45 × 45 × 0.5 (mm), 9 pieces), and cooled by compressing at a pressure of 100 kg / cm ² using another hydraulic heat press manufactured by Shindo Metal Industry Co., Ltd. set at 20 ° C. A sample for measurement was prepared. A 5 mm thick SUS plate was used as the hot plate.
This pressed sheet was heat-treated at 120° C. for 1 hour, linearly cooled to room temperature over 1 hour, and then measured with a density gradient tube.

・Weight average molecular weight (Mw), number average molecular weight (Mn)
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 Waters "Alliance GPC 2000" gel permeation chromatograph (high temperature size exclusion chromatograph), the operating conditions are as follows:

[Equipment and conditions used]
-Molecular weight distribution and various average molecular weight measuring devices; gel permeation chromatograph alliance GPC2000 type (Waters)
Analysis software; chromatography data system Empower (trademark, Waters)
Column; TSKgel GMH6-HT × 2 + TSKgel GMH6-HT × 2
(Inner diameter 7.5 mm x length 30 cm, Tosoh Corporation)
Mobile phase; o-dichlorobenzene [= ODCB] (Wako Pure Chemical special grade reagent)
Detector: Differential refractometer (built-in)
Column temperature; 140°C
Flow rate; 1.0 mL/min
Injection volume: 500 μL
Sampling time interval; 1 second Sample concentration; 0.15% (w/v)
Molecular weight calibration Monodisperse polystyrene (Tosoh Corporation)/molecular weight 495 to 20.6 million Polym. Sci. , B5, 753. (1967) and calculated as polyethylene molecular weight equivalents according to the universal calibration procedure.

・Melting point (Tm; °C)
Using an RDC220 differential scanning calorimeter manufactured by SII, about 10 mg of a sample was heated to 30 to 200° C. at a heating rate of 50° C./min under a nitrogen atmosphere, and held at that temperature for 10 minutes. Furthermore, it was cooled to 30°C at a temperature decrease rate of 10°C/min, held at that temperature for 5 minutes, and then heated to 200°C at a temperature increase rate of 10°C/min. The endothermic peak observed during the second temperature rise was defined as the melting peak, and the temperature at which the melting peak appeared was determined as the melting point (Tm).

- Melting point (Tm; °C) and crystallization temperature (Tc; °C) of olefin (co)polymer containing structural units derived from 1-butene
The melting point (Tm) or crystallization temperature (Tc) of the olefin (co)polymer containing a structural unit derived from 1-butene was measured using a differential scanning calorimeter (DSC), DSC7020 manufactured by SII, as follows. It was measured.

Under a nitrogen atmosphere (20 mL/min), the sample (about 5 mg) was (1) heated to 230°C and held at 230°C for 10 minutes, (2) cooled to 30°C at 10°C/min and heated at 30°C. After holding for 1 minute, (3) the temperature was raised to 230°C at 10°C/min.

The melting point (Tm) was calculated from the peak apex of the crystalline melting peak in the temperature rising process (3) above, and the crystallization temperature (Tc) was calculated from the peak apex of the crystallization peak in the temperature lowering process (2) above. In addition, in the olefin (co)polymers containing 1-butene-derived structural units described in Examples and Comparative Examples, when a plurality of crystal melting peaks are observed (for example, low temperature side peak Tm1, high temperature side peak Tm2) , the peak on the high temperature side was defined as the melting point (Tm) of an olefin (co)polymer containing a structural unit derived from 1-butene. The heat of fusion (ΔH) was calculated by measuring the area of the crystal melting peak and the melting curve.

In addition, the data described as "after crystal stabilization" is obtained by heating the sample (about 5 mg) to 220 ° C. under a nitrogen atmosphere (20 mL / min), holding it at 220 ° C. for 10 minutes, cooling it to room temperature, After 10 days or longer at room temperature, the melting point (Tm) and heat of fusion (ΔH) were measured as follows.

Under a nitrogen atmosphere (20 mL/min), the sample (approximately 5 mg) was (1) cooled from room temperature to −20° C. at 20° C./min and held at −20° C. for 10 minutes, and (2) 200 at 20° C./min. The temperature was raised to °C. The melting point (Tm) was calculated from the apex of the crystal melting peak in the temperature rising process of (2), and the heat of fusion (ΔH) was calculated by measuring the area of the melting curve.

・Glass transition temperature (Tg; ° C.)
Using an RDC220 differential scanning calorimeter manufactured by SII, about 10 mg of a sample was heated to 30 to 200° C. at a heating rate of 50° C./min under a nitrogen atmosphere, and held at that temperature for 10 minutes. Further, it was cooled to −100° C. at a temperature decrease rate of 10° C./min, held at that temperature for 5 minutes, and then heated to 200° C. at a temperature increase rate of 10° C./min. The glass transition temperature (Tg) is sensed in the form that the DSC curve bends and the baseline shifts in parallel due to the change in specific heat during this second temperature rise. The glass transition temperature (Tg) was obtained as the temperature at the intersection of the contact point of the base line, which is lower than the bending temperature, and the point of contact at which the inclination at the bending portion becomes maximum.

・Intrinsic viscosity [η] (dL/g)
The intrinsic viscosity [η] of the olefin polymer is a value measured at 135°C using decalin solvent.

That is, about 20 mg of polymerized powder or resin mass is dissolved in 15 ml of decalin, and the specific viscosity η _sp is measured in an oil bath at 135°C. 5 ml of decalin solvent is added to this decalin solution to dilute it, and then the specific viscosity η _sp is measured in the same manner. This dilution operation is repeated twice, and the value of η _sp /C when the concentration (C) is extrapolated to 0 is determined as the intrinsic viscosity [η] (see the following formula).
[η]=lim(η _sp /C) (C→0)

・Comonomer content (ethylene/1-hexene copolymer)
The comonomer content of the copolymer was measured by FT-IR (FT-IR410 infrared spectrophotometer manufactured by JASCO Corporation). FT-IR uses a film obtained by melting and stretching the copolymer-generated polymer obtained in the example in a hot press heated to 135 ° C. and then pressurizing and cooling at room temperature as a measurement sample. Measured at wavelengths between 5000 cm ^-1 and 400 cm ^-1 . The hexene content was measured using the C—CH ₂ CH ₂ CH ₂ CH ₃ skeleton vibration (1378 cm ⁻¹ ) based on hexene as a key band, and the absorbance (D1378) of the key band and the internal standard band (4321 cm ⁻¹ : CH stretching vibration and the combination tone of methylene and methyl bending vibrations) to the absorbance (D4321) [D1378/D4321].

A calibration curve specifying the relationship between the comonomer content and [D1378/D4321] is used to determine the comonomer content. The calibration curve is prepared in advance from the above [D1378/D4321] results obtained by FT-IR measurement of ethylene copolymers of various compositions, the comonomer contents of which are specified by 13C NMR, by the above method.

・Comonomer content (ethylene/tetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ]-3-dodecene/styrene copolymer)
Ethylene/tetracyclo[4.4.0.1 ^2,5 . 1 ^7,10 ]-3-dodecene (TD) / styrene (ST) content ratio of each component in the copolymer (hereinafter expressed as E / TD / ST; mol%) It was obtained under the following measurement conditions using a resonator.

〔Measurement condition〕
Measurement nucleus; ¹ H (400 MHz)
Measurement mode; Single pulse Pulse width; 45° (6.44 μs)
number of points; 32k
Measurement range; 20 ppm (-4 to 16 ppm)
Repeat time; 7.0 seconds Accumulation times; 128 times Measurement solvent; 1,1,2,2-tetrachloroethane-d2
sample concentration; ca. 20 mg/0.6 mL
Measurement temperature; 120°C
Window function; exponential (BF; 0.12 Hz)
Chemical shift standard; 1,1,2,2-tetrachloroethane (5.91 ppm)
The TD content, ST content and ethylene content were calculated from the peak intensity derived from protons directly bonded to double-bonded carbons, the peak intensity derived from phenyl group protons, and the peak intensities of other protons.

<(1) Synthesis of transition metal compound>
[Example 1]
[Example 1-1]
0.53 g (21.8 mmol) of magnesium pieces were introduced into a 200 mL reactor that was sufficiently dried and replaced with argon, and vigorously stirred for 30 minutes while heating under reduced pressure. After cooling to room temperature, one piece of iodine and 22 mL of tetrahydrofuran were charged and stirred. To this solution, Eur. J. Org. Chem. 2006, 2727. and a diluted solution of 5.69 g (20.0 mmol) of 4-bromo-2,6-di-iso-propyl-N,N-dimethylaniline synthesized by the method described in WO2007/034975 in 30 mL of tetrahydrofuran was slowly added, The mixture was heated to reflux in an oil bath at 80° C. for 1 hour. After cooling this reaction solution to −78° C., 2.50 mL (22.5 mmol) of trimethoxyborane was slowly added, and stirring was continued for 18 hours while the temperature was slowly returned to room temperature. To this reaction solution, 3.61 g (17.1 mmol) of 4-bromo-1-indanone, 8.48 g (40.0 mmol) of tripotassium phosphate, 0.04 g (0.18 mmol) of palladium acetate, 2-dicyclohexylphosphino 0.11 g (0.26 mmol) of -2',6'-dimethoxybiphenyl (S-Phos) and 10 mL of distilled water were charged and heated under reflux in an oil bath for 2 hours. After cooling the reaction solution to room temperature, 1.0 M hydrochloric acid aqueous solution was added, the soluble matter was extracted with ethyl acetate, the resulting fraction was washed with saturated brine and dried over anhydrous magnesium sulfate. After filtering magnesium sulfate, 20 mL of tetrahydrofuran and 10 mL of methanol were added to the residue obtained by distilling off the filtrate, and the mixture was stirred. The solution was cooled to 0° C., 1.32 g (35.0 mmol) of sodium hydroborate was slowly added little by little, and the mixture was stirred at room temperature for 1 hour. This solution was cooled to 0° C., 1.0 M hydrochloric acid aqueous solution was slowly added, the soluble matter was extracted with ethyl acetate, the resulting fraction was washed with saturated brine and dried over anhydrous magnesium sulfate. After filtering magnesium sulfate, 35 mL of toluene and 0.34 g (1.80 mmol) of p-toluenesulfonic acid monohydrate were added to the residue obtained by evaporating the filtrate, and the mixture was placed in an oil bath at 120°C. It was heated to reflux for 2 hours. After cooling the reaction solution to room temperature, saturated aqueous sodium hydrogencarbonate solution was added, soluble matter was extracted with hexane, and the obtained fraction was washed with saturated brine and dried over anhydrous magnesium sulfate. After filtering magnesium sulfate, the residue obtained by evaporating the filtrate was purified by silica gel column chromatography to obtain 3.62 g of the desired product represented by the following formula (1a) (hereinafter referred to as compound (1a)) ( Yield 66%) was obtained.
¹ H NMR (270 MHz, CDCl ₃ ) δ 7.43-7.31 (2H, m, Ar-H), 7.30-7.23 (3H, m, Ar-H), 6.94 (1H, dt, J = 5.6 and 1.9 Hz, Ar-CH=C), 6.59 (1H, dt, J = 5.6 and 1.9 Hz, -CH=CH-CH ₂ -), 3.51 (2H, t , J=1.9 Hz, Ar—CH ₂ —C), 3.40 (2H, sep, J=6.9 Hz, —CH(CH ₃ ) ₂ ), 2.89 (6H, s, —NC(CH ₃ ) ₂ ), 1.48 (12H, d, J = 6.9 Hz, -CH( _CH3 ) ₂ ) ppm

[Example 1-2]
A 300 mL reactor was charged with 3.61 g (11.3 mmol) of compound (1a) obtained in Example 1-1, 1.16 g (29.0 mmol) of sodium hydroxide, 8 mL of tetrahydrofuran, 0 of 15-crown 5-ether. A solution of 0.06 g (0.29 mmol) of tetrahydrofuran in 2 mL was charged, and heated under reflux in an oil bath at 80° C. for 2 hours. This solution was cooled to 0° C., 0.42 mL (5.70 mmol) of acetone was added to this solution, and after stirring at room temperature for 10 minutes, the mixture was heated under reflux in an oil bath at 80° C. for 3 hours. The solution was cooled to 0° C., 1.0 M hydrochloric acid aqueous solution was slowly added, the soluble matter was extracted with ethyl acetate, the resulting fraction was washed with saturated brine and dried over anhydrous magnesium sulfate. After filtering magnesium sulfate, hexane was added to the residue obtained by distilling off the filtrate to prepare a suspension, insoluble matter was filtered off, and the residue was dried under reduced pressure to give the following formula (1b ) (hereinafter referred to as compound (1b)) was obtained in an amount of 1.88 g (yield 49%).
¹ H NMR (270 MHz, CDCl ₃ ) δ 7.38 (2H, dd, J=6.5 and 2.2 Hz, Ar-H), 7.20, (4H, s, Ar-H), 7.17-7 .09 (4H, m, Ar—H), 6.56 (2H, s, —C═CH—CH ₂ —), 3.49 (4H, d, J=1.7 Hz, ═CH—CH ₂ — ), 3.39 (4H, sep, J=6.9 Hz, —CH(CH ₃ ) ₂ ), 2.89 (12H, s, —NC(CH ₃ ) ₂ ), 1.80 (6H, s, C—CH ₃ ), 1.24 (24H, d, J=6.9 Hz, —CH(CH ₃ ) ₂ ) ppm

[Example 1-3]
1.02 g (1.50 mmol) of the compound (1b) obtained in Example 1-2 and 15 mL of toluene were charged into a 100 mL reactor sufficiently dried and replaced with argon, and stirred. To this solution, 0.41 g (1.52 mmol) of tetrakis(dimethylamino)zirconium was added under ice-cooling, stirred at room temperature for 5 minutes, and then heated to reflux in an oil bath at 120° C. for 7 hours. After distilling off the solvent of the reaction solution, 10 mL of toluene and 0.40 mL (3.17 mmol) of chlorotrimethylsilane were added to the residue, and the mixture was stirred in an oil bath at 70° C. for 3 hours. After distilling off the solvent of the reaction solution, dichloromethane was added to the resulting solid to prepare a suspension, and insoluble matter was filtered off through a glass filter. The filtrate was concentrated under reduced pressure, and hexane was added to prepare a suspension. The insoluble matter was filtered off, and the residue was dried under reduced pressure to give an orange powdery isopropylidenebis(4-(3,5-di-iso-propyl-4-dimethylaminophenyl) compound represented by the following formula (1). )-1-indenyl)zirconium dichloride (hereinafter referred to as metallocene compound (1)) was obtained (yield 32%, racemic purity 100%).
¹ H NMR (270 MHz, CDCl ₃ ) δ 7.74 (2H, d, J = 8.9 Hz, Ar-H), 7.39 (4H, s, Ar-H), 7.33 (2H, d, J = 6.8 Hz, Ar-H), 7.13 (2H, dd, J = 8.9 and 6.9 Hz, Ar-H), 6.90 (2H, d, J = 3.3 Hz, Cp-H) , 6.24 (2H, d, J = 3.6 Hz, Cp-H), 3.34 (4H, sep, J = 6.8 Hz, -CH (CH ₃ ) ₂ ), 2.84 (12H, s , —NC(CH ₃ ) ₂ ), 2.42 (6H, s, C—CH ₃ ), 1.25 (12H, d, J=6.8 Hz, —CH(CH ₃ ) ₂ ), 1.15 (12H, d, J = 6.8 Hz, -CH( _CH3 ) ₂ ) ppm
FD-mass spectroscopy (M ⁺ ): 838

[Example 2]
[Example 2-1]
0.53 g (21.8 mmol) of magnesium pieces were introduced into a 200 mL reactor that was sufficiently dried and replaced with argon, and vigorously stirred for 30 minutes while heating under reduced pressure. After cooling to room temperature, one piece of iodine and 20 mL of tetrahydrofuran were charged and stirred. To this solution, J. Am. Chem. Soc. 2006, 128, 16486. A solution of 5.99 g (20.0 mmol) of 1-bromo-3,5-di-tert-butyl-4-methoxybenzene synthesized by the described method diluted in 30 mL of tetrahydrofuran was slowly added, and the mixture was stirred in an oil bath at 80°C. Heated to reflux for 1 hour. After cooling this reaction solution to −78° C., 2.50 mL (22.5 mmol) of trimethoxyborane was slowly added, and stirring was continued for 21 hours while the temperature was slowly returned to room temperature. A 1.0 M hydrochloric acid aqueous solution was added, the soluble matter was extracted with diethyl ether, the resulting fraction was washed with water and saturated brine, and dried over anhydrous magnesium sulfate. After filtering magnesium sulfate, the residue obtained by evaporating the filtrate was mixed with 3.67 g (17.4 mmol) of 4-bromo-1-indanone, 8.54 g (40.2 mmol) of tripotassium phosphate, and acetic acid. 0.04 g (0.18 mmol) of palladium, 0.11 g (0.26 mmol) of 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl (S-Phos), 45 mL of tetrahydrofuran, and 9 mL of distilled water were charged in an oil bath. was heated to reflux for 2 hours. After the reaction solution was cooled to room temperature, saturated aqueous ammonium chloride solution was added, the soluble matter was extracted with ethyl acetate, the resulting fraction was washed with saturated brine and dried over anhydrous magnesium sulfate. After filtering magnesium sulfate, the residue obtained by evaporating the filtrate was purified by silica gel column chromatography to obtain 5.86 g of the desired product represented by the following formula (2a) (hereinafter referred to as compound (2a)) ( Yield 96%) was obtained.
¹ H NMR (270 MHz, CDCl ₃ ) δ 7.75 (1H, dd, J = 7.6 and 1.1 Hz, Ar-H), 7.61 (1H, dd, J = 7.5 and 1.2 Hz, Ar-H ), 7.46 (1H, t, J = 7.5 Hz, Ar-H), 7.34 (2H, s, Ar-H), 3.76 (3H, s, -OCH ₃ ), 3.25 -3.15 (2H, m, Ar--CH ₂ --C), 2.73-2.68 (2H, m, Ar--CO--CH ₂ --), 1.48 (18H, s, --C(CH ₃ ) ₃ ) ppm

[Example 2-2]
A 500 mL reactor was charged with 5.85 g (16.7 mmol) of the compound (2a) obtained in Example 2-1, 20 mL of tetrahydrofuran, and 8 mL of methanol, and stirred. The solution was cooled to 0° C., 1.27 g (33.7 mmol) of sodium hydroborate was slowly added in portions, and the mixture was stirred at room temperature for 1 hour. This solution was cooled to 0° C., 1.0 M hydrochloric acid aqueous solution was slowly added, the soluble matter was extracted with ethyl acetate, the resulting fraction was washed with saturated brine and dried over anhydrous magnesium sulfate. After filtering magnesium sulfate, 30 mL of toluene and 0.07 g (0.36 mmol) of p-toluenesulfonic acid monohydrate were added to the residue obtained by distilling off the filtrate, and the mixture was placed in an oil bath at 120°C. It was heated to reflux for 2 hours. After cooling the reaction solution to room temperature, saturated aqueous sodium hydrogencarbonate solution was added, soluble matter was extracted with hexane, and the obtained fraction was washed with saturated brine and dried over anhydrous magnesium sulfate. After filtering magnesium sulfate, the residue obtained by evaporating the filtrate was purified by silica gel column chromatography to obtain 4.38 g of the desired product represented by the following formula (2b) (hereinafter referred to as compound (2b)) ( Yield 78%) was obtained.
¹ H NMR (270 MHz, CDCl ₃ ) δ 7.44 (2H, s, Ar—H), 7.42-7.30 (2H, m, Ar—H), 7.23 (1H, dd, J= 6.6 and 2.3 Hz, Ar-H), 6.98-6.91 (1H, m, Ar-CH=C), 6.63-6.54 (1H, m, -CH=CH-CH ₂ - ), 3.76 (3H, s, —OCH ₃ ), 3.50 (2H, t, J=1.9 Hz, Ar—CH ₂ —C), 1.48 (18H, s, —C (CH ₃ ) ₃ ) ppm

[Example 2-3]
A 100 mL reactor was charged with 4.36 g (13.0 mmol) of the compound (2b) obtained in Example 2-2, 7 mL of tetrahydrofuran, and a 1 mL solution of 0.07 g (0.33 mmol) of 15-crown 5-ether in tetrahydrofuran. 1.32 g (32.9 mmol) of sodium hydroxide and 0.48 mL (6.51 mmol) of acetone were charged and heated under reflux in an 80° C. oil bath for 3 hours. This solution was cooled to 0° C., 1.0 M hydrochloric acid aqueous solution was added slowly, the soluble matter was extracted with hexane, and the obtained fraction was washed with saturated brine and dried over anhydrous magnesium sulfate. After filtering magnesium sulfate, diethyl ether was added to the residue obtained by evaporating the filtrate to prepare a suspension, insoluble matter was filtered off, and the residue was dried under reduced pressure to obtain a compound of the following formula ( 1.87 g (yield 41%) of the desired product shown in 2c) (hereinafter referred to as compound (2c)) was obtained.
¹ H NMR (270 MHz, CDCl ₃ ) δ 7.43-6.34 (6H, m, Ar-H), 7.20-7.07 (4H, m, Ar-H), 6.57 (2H, s, -C=CH-CH ₂ -), 3.75 (6H, s, -OCH ₃ ), 3.51-3.47 (4H, m, =CH-CH ₂ -), 1.80 (6H , s, C—CH ₃ ), 1.47 (36H, s, —C(CH ₃ ) ₃ ) ppm

[Example 2-4]
0.67 g (2.52 mmol) of tetrakis(dimethylamino)zirconium and 5 mL of toluene were charged into a 100 mL reactor that had been sufficiently dried and replaced with argon, and the mixture was stirred. This suspension was cooled to −78° C., and a toluene 15 mL suspension of 1.77 g (2.50 mmol) of compound (2c) obtained in Example 2-3 was added. Stirring was continued at rt for 6 hours. After distilling off the solvent of the reaction solution, hexane is added to the residue to prepare a suspension, insoluble matter is filtered off with a glass filter, and the residue is dried under reduced pressure to give a pink-orange color represented by the following formula (2d). 1.36 g of powdery compound (hereinafter referred to as metallocene compound (2d)) was obtained (yield 61%, racemic purity 88%).
¹ H NMR (270 MHz, C ₆ D ₆ ) δ 7.80-7.70 (2H, m, Ar-H), 7.20-7.00 (10 H, m, Ar-Hand Cp-H), 6. 77 (meso-, d, J=3.3 Hz, Cp-H), 6.38 (2H, d, J=3.5 Hz, Cp-H), 5.84 (meso-, d, J=3. 4 Hz, Cp—H), 3.38 (6H, s, —OCH ₃ ), 2.68 (12H, s, —N(CH ₃ ) ₂ ), 2.11 (meso—, s, C—CH ₃ ), 2.08 (6H, s, C—CH ₃ ), 1.51 (36H, s, —C(CH ₃ ) ₃ ) ppm

[Example 2-5]
0.45 g (0.51 mmol) of the metallocene compound (2d) obtained in Example 2-4 and 6 mL of toluene were charged into a 100 mL reactor sufficiently dried and purged with argon, and stirred. After adding 0.15 mL (1.19 mmol) of chlorotrimethylsilane to this suspension at room temperature, stirring was continued for 3 hours in an oil bath at 70°C. After distilling off the solvent of the reaction solution, dichloromethane and hexane were added to the obtained solid to prepare a suspension, insoluble matter was filtered off through a glass filter, and the residue was dried under reduced pressure to give the following formula (2). The pink-orange powdery compound isopropylidenebis(4-(3,5-di-tert-butyl-4-methoxyphenyl)-1-indenyl)zirconium dichloride (hereinafter referred to as metallocene compound (2)) was added at 0.5%. 35 g (yield 78%, racemate purity 100%) was obtained.
¹ H NMR ( 270 MHz, CDCl ₃ ) δ 7.73 (2H, d, J = 8.9 Hz, Ar-H), 7.49 (4H, s, Ar-H), 7.30 (2H, d, J = 6.8 Hz, Ar-H), 7.13 (2H, dd, J = 8.9 and 6.9 Hz, Ar-H), 6.83 (2H, d, J = 3.6 Hz, Cp-H) , 6.23 (2H, d, J = 3.7 Hz, Cp-H), 3.69 (6H, s, _-OCH3 ), 2.42 (6H, s, C- _CH3 ), 1.41 _{(36H,s,-C(CH3)3 )} ppm
FD-mass spectroscopy (M ⁺ ): 868

[Comparative Example 1]
[Comparative Example 1-1]
In a 200 mL reactor were charged 2.53 g (12.0 mmol) of 4-bromo-1-indanone, 2.18 g (14.4 mmol) of 4-methoxyphenylboronic acid, 6.11 g (28.8 mmol) of tripotassium phosphate, 0.03 g (0.12 mmol) of palladium acetate, 0.07 g (0.18 mmol) of 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl (S-Phos), 30 mL of tetrahydrofuran, and 6 mL of distilled water were charged in an oil bath. The mixture was heated under reflux for 2 hours. After the reaction solution was cooled to room temperature, saturated aqueous ammonium chloride solution was added, the soluble matter was extracted with ethyl acetate, the resulting fraction was washed with saturated brine and dried over anhydrous magnesium sulfate. After filtering magnesium sulfate, the residue obtained by evaporating the filtrate was purified by silica gel column chromatography to obtain 2.60 g of the target compound represented by the following formula (3a) (hereinafter referred to as compound (3a)) ( Yield 91%) was obtained.
¹ H NMR (270 MHz, CDCl ₃ ) δ 7.75 (1H, d, J=7.5 Hz, Ar-H), 7.57 (1H, dd, J=7.4 and 1.2 Hz, Ar-H), 7.49-7.35 (3H, m, Ar—H), 7.05-6.97 (2H, m, Ar—H), 3.87 (3H, s, —OCH ₃ ), 3.21 -3.12 (2H, m, Ar- _CH2 -C), 2.73-2.65 (2H, m, Ar-CO- _CH2- ) ppm

[Comparative Example 1-2]
A 200 mL reactor was charged with 2.59 g (10.3 mmol) of the compound (3a) obtained in Comparative Example 1-1, 15 mL of tetrahydrofuran, and 5 mL of methanol, and stirred. The solution was cooled to 0° C., 0.84 g (22.1 mmol) of sodium hydroborate was slowly added in portions, and the mixture was stirred at room temperature for 2 hours. This solution was cooled to 0° C., 1.0 M hydrochloric acid aqueous solution was slowly added, the soluble matter was extracted with ethyl acetate, the resulting fraction was washed with saturated brine and dried over anhydrous magnesium sulfate. After filtering magnesium sulfate, 20 mL of toluene and 0.04 g (0.23 mmol) of p-toluenesulfonic acid monohydrate were added to the residue obtained by evaporating the filtrate, and the mixture was placed in an oil bath at 120°C. Heated to reflux for 2 hours. After cooling the reaction solution to room temperature, saturated aqueous sodium hydrogencarbonate solution was added, the soluble matter was extracted with ethyl acetate, the resulting fraction was washed with saturated brine and dried over anhydrous magnesium sulfate. After filtering magnesium sulfate, the residue obtained by evaporating the filtrate was purified by silica gel column chromatography to obtain 1.43 g of the target compound represented by the following formula (3b) (hereinafter referred to as compound (3b)) ( Yield 63%) was obtained.
¹ H NMR (270 MHz, CDCl ₃ ) δ 7.53-7.44 (2H, m, Ar-H), 7.43-7.30 (2H, m, Ar-H), 7.20 (1H, dd, J = 6.8 and 1.9 Hz, Ar-H), 6.96-6.91 (1H, m, Ar-CH=C), 6.61-6.54 (1H, m, -CH=CH —CH ₂ —), 3.86 (3H, s, —OCH ₃ ), 3.47 (2H, t, J=1.9 Hz, Ar—CH ₂ —C) ppm

[Comparative Example 1-3]
A 300 mL reactor was charged with 1.43 g (6.45 mmol) of the compound (3b) obtained in Comparative Example 1-2, 0.61 g (15.3 mmol) of sodium hydroxide, 5 mL of tetrahydrofuran, 15-crown 5-ether 0 A solution of 0.04 g (0.17 mmol) of tetrahydrofuran in 2 mL was charged and heated under reflux in an oil bath at 80° C. for 2 hours. This solution was cooled to 0° C., 0.25 mL (3.39 mmol) of acetone was added to this solution, and after stirring at room temperature for 10 minutes, the mixture was heated under reflux in an oil bath at 80° C. for 3 hours. This solution was cooled to 0° C., 1.0 M hydrochloric acid aqueous solution was slowly added, the soluble matter was extracted with ethyl acetate, the resulting fraction was washed with saturated brine and dried over anhydrous magnesium sulfate. After filtering magnesium sulfate, diethyl ether and hexane were added to the residue obtained by evaporating the filtrate to prepare a suspension, insoluble matter was filtered off, and the residue was dried under reduced pressure to give the following: 0.79 g (yield 51%) of the desired product represented by the formula (3c) (hereinafter referred to as compound (3c)) was obtained.
¹ H NMR (270 MHz, CDCl ₃ ) δ 7.49-7.39 (4H, m, Ar—H), 7.35, (2H, dd, J=7.4 and 1.2 Hz, Ar—H), 7 .17-7.03 (4H, m, Ar-H), 7.01-6.93 (4H, m, Ar-H), 6.56 (2H, t, J = 2.0 Hz, -C = CH—CH ₂ —), 3.86 (6H, s, —OCH ₃ ), 3.46 (4H, d, J=1.9 Hz, =CH—CH ₂ —), 1.79 (6H, s, C—CH ₃ ) ppm

[Comparative Example 1-4]
0.73 g (1.50 mmol) of the compound (3c) obtained in Comparative Example 1-3 and 15 mL of toluene were charged into a 100 mL reactor sufficiently dried and replaced with argon, and stirred. This solution was cooled to −78° C., 0.41 g (1.53 mmol) of tetrakis(dimethylamino)zirconium was added, stirred at room temperature for 10 minutes, and heated to reflux in an oil bath at 120° C. for 7 hours. After distilling off the solvent of the reaction solution, 8 mL of toluene and 0.40 mL (3.17 mmol) of chlorotrimethylsilane were added to the residue, and the mixture was stirred in an oil bath at 70° C. for 3 hours. After distilling off the solvent of the reaction solution, dichloromethane was added to the resulting solid to prepare a suspension, insoluble matter was filtered off through a glass filter, and the residue was dried under reduced pressure to obtain a product represented by the following formula (3). 0.54 g (yield 56%, racemic purity 93% )Obtained.
¹ H NMR (270 MHz, CDCl ₃ ) δ 7.81 (meso-, d, J = 8.9 Hz, Ar-H), 7.70 (2H, d, J = 8.9 Hz, Ar-H), 7 .57-7.47 (4H, m, Ar-H), 7.24 (2H, d, J = 7.2 Hz, Ar-H), 7.15-7.03 (2H, m, Ar-H ), 7.01-6.92 (4H, m, Ar-H), 6.79 (2H, dd, J = 3.6 and 0.7 Hz, Cp-H), 6.22 (2H, d, J = 3.6 Hz, Cp-H), 6.10 (meso-, d, J = 3.6 Hz, Cp-H), 3.82 (6H, s, -OCH ₃ ), 2.73 (meso-, s , C--CH ₃ ), 2.41 (6H, s, C--CH ₃ ), 2.22 (meso-, s, C--CH ₃ ) ppm
FD-Mass Spec (M ⁺ ): 644

[Comparative Example 2]
[Comparative Example 2-1]
680 mg (2.54 mmol) of tetrakis(dimethylamino)zirconium and 5 mL of toluene were charged into a 100 mL reactor that had been sufficiently dried and replaced with argon, and the mixture was stirred. This suspension was cooled to −78° C., and 1.06 g (2.50 mmol) of 2,2-bis(7-phenyl-3-indenyl)propane synthesized by the method described in Japanese Patent No. 5710035 was suspended in 10 mL of toluene. After adding the turbid liquid, stirring was continued for 2 hours in an oil bath at 120°C. After distilling off the solvent of the reaction solution, hexane was added to the residue to prepare a suspension, and insoluble matter was filtered off with a glass filter. The obtained solution is concentrated under reduced pressure to prepare a suspension, and the obtained solid is filtered and dried to give an orange powdery compound represented by the following formula (4a) (hereinafter referred to as a metallocene compound (4a )) was obtained (yield 53%, racemic purity 83%).
¹ H NMR (270 MHz, C ₆ D ₆ ) δ 8.25 (meso-, d, J = 8.9 Hz, Ar-H), 7.77-7.65 (6H, m, Ar-H), 7 .28-7.22 (4H, m, Ar-H), 7.16-6.93 (6H, m, Ar-H), 6.83 (2H, d, J = 3.5 Hz, Cp-H ), 6.63 (meso-, d, J = 3.3 Hz, Cp-H), 6.37 (2H, d, J = 3.5 Hz, Cp-H), 5.83 (meso-, d, J = 3.4 Hz, Cp-H), 2.49 (12H, s, -N( _CH3 ) ₂ ), 2.08 (6H, s, C- _CH3 ) ppm

[Comparative Example 2-2]
0.30 g (0.50 mmol) of the metallocene compound (4a) obtained in Comparative Example 2-1 and 2.5 mL of toluene were charged into a 30 mL reactor sufficiently dried and purged with argon, and stirred. After adding 0.13 mL (1.0 mmol) of chlorotrimethylsilane to this suspension at room temperature, stirring was continued for 3 hours in an oil bath at 70°C. After distilling off the solvent of the reaction solution, dichloromethane was added to the resulting solid to prepare a suspension, insoluble matter was filtered off through a glass filter, and the residue was dried under reduced pressure to obtain a residue represented by the following formula (4). 0.17 g (yield: 56%, racemic purity: 100%) of dark pink powdery compound isopropylidenebis(4-phenyl-1-indenyl)zirconium dichloride (hereinafter referred to as metallocene compound (4)) was obtained.
¹ H NMR (270 MHz, CDCl ₃ ) δ 7.74 (2H, d, J=8.9 Hz, Ar-H), 7.58 (4H, d, J=8.9 Hz, Ar-H), 7. 45-7.27 (8H, m, Ar-H), 7.15-7.10 (2H, m, Ar-H), 6.80 (2H, d, J = 3.6 Hz, Cp-H) , 6.23 (2H, d, J = 3.6 Hz, Cp-H), 2.41 (6H, s, C-CH ₃ ) ppm
FD-Mass Spec (M ⁺ ): 584

[Comparative Example 3]
Isopropylidenebis(1-indenyl)zirconium dichloride (metallocene compound (5)) is described in J. Am. Organomet. Chem. 1997, 530, 75. described methods, and J. Organomet. Chem. 1997, 527, 297. Synthesized according to the described method.

[Example 3]
[Example 3-1]
0.53 g (22.0 mmol) of magnesium pieces were introduced into a 200 mL reactor that was sufficiently dried and replaced with argon, and vigorously stirred for 30 minutes while heating under reduced pressure. After cooling to room temperature, one piece of iodine and 22 mL of tetrahydrofuran were charged and stirred. To this solution, Eur. J. Org. Chem. 2006, 2727. and a diluted solution of 5.69 g (20.0 mmol) of 4-bromo-2,6-di-iso-propyl-N,N-dimethylaniline synthesized by the method described in WO2007/034975 in 30 mL of tetrahydrofuran was slowly added, The mixture was heated to reflux in an oil bath at 80° C. for 1 hour. After cooling this reaction solution to −78° C., 2.50 mL (22.5 mmol) of trimethoxyborane was slowly added, and stirring was continued for 18 hours while the temperature was slowly returned to room temperature. Organometallics 2006, 25, 1217. 7-bromo-2-methylindene synthesized by the described method 3.71 g (17.7 mmol), tripotassium phosphate 8.42 g (39.7 mmol), palladium acetate 0.08 g (0.36 mmol), 2-dicyclohexyl 0.22 g (0.53 mmol) of phosphino-2′,6′-dimethoxybiphenyl (S-Phos) and 10 mL of distilled water were charged, and heated under reflux in an oil bath for 2 hours. After cooling the reaction solution to room temperature, 1.0 M hydrochloric acid aqueous solution was added, the soluble matter was extracted with ethyl acetate, the resulting fraction was washed with saturated brine and dried over anhydrous magnesium sulfate. After filtering magnesium sulfate, methanol was added to the residue obtained by distilling off the filtrate to prepare a suspension, insoluble matter was filtered off, and the residue was dried under reduced pressure to give the following formula (6a ) (hereinafter referred to as compound (6a)) was obtained in an amount of 4.52 g (yield 76%).
¹ H NMR (270 MHz, CDCl ₃ ) δ 7.35-7.19 (4H, m, Ar-H), 7.14 (1H, dd, J=7.4 and 1.3 Hz, Ar-H),6. 58-6.50 (1H, m, Ar—CH═C), 3.49-3.31 (4H, m, Ar—CH ₂ —C
and —CH(CH ₃ ) ₂ ), 2.89 (6H, s, —NC(CH ₃ ) ₂ ), 2.15 (3H, s, CH—CH ₃ ), 1.25 (12H, d, J = 6.9 Hz, -CH( _CH3 ) ₂ ) ppm

[Example 3-2]
3.34 g (10.0 mmol) of the compound (6a) obtained in Example 3-1 and 35 mL of tetrahydrofuran were charged into a 200 mL reactor sufficiently dried and purged with argon and stirred. 6.20 mL of n-butyllithium solution (hexane solution, 1.63 M, 10.1 mmol) was added to this solution under ice-cooling, and the mixture was stirred at room temperature for 2 hours. After adding 1.10 mL (11.7 mmol) of 1,3-dimethyl-2-imidazolidinone to this solution, the solution was cooled to −30° C., 0.60 mL (5.00 mmol) of dichlorodimethylsilane was added, and the mixture was slowly cooled to room temperature. Stirring was continued for 17 hours while returning to A saturated aqueous ammonium chloride solution was added, the soluble matter was extracted with n-hexane, the resulting fraction was washed with saturated brine and dried over anhydrous magnesium sulfate. After filtering magnesium sulfate, the residue obtained by evaporating the filtrate was purified by silica gel column chromatography to obtain 3.03 g of the target compound represented by the following formula (6b) (hereinafter referred to as compound (6b)) ( Yield 84%) as a mixture of isomers.
¹ H NMR (270 MHz, CDCl ₃ ) δ 7.60-7.04 (10H, m, Ar—H), 6.93-6.50 (2H, m, Ar—CH=C), 3.94- 3.77 (2H, m, CH—Si—CH), 3.42 (4H, sep, J=6.8 Hz, —CH(CH ₃ ) ₂ ), 2.90 (12H, s, —NC(CH ₃ ) ₂ ), 2.35-2.20(6H, m, C—CH ₃ ), 1.28(24H, dd, J=6.5 and 4.7 Hz, —CH(CH ₃ ) ₂ ), —0 .10--0.28(6H,m,Si—CH ₃ ) ppm

[Example 3-3]
0.36 g (0.50 mmol) of the compound (6b) obtained in Example 3-2, 10 mL of toluene and 0.1 mL of tetrahydrofuran were charged into a 100 mL reactor sufficiently dried and purged with argon and stirred. To this solution, 0.62 mL of n-butyllithium solution (hexane solution, 1.63 M, 1.01 mmol) was added at room temperature, and the mixture was stirred in an oil bath at 40° C. for 3 hours. After distilling off the solvent of the reaction solution, 10 mL of n-hexane and 0.5 mL of diethyl ether were added to the resulting solid. The solution was cooled to 0° C., 0.12 g (0.50 mmol) of zirconium tetrachloride was added, and stirring was continued at room temperature for 21 hours. After distilling off the solvent of the reaction solution, dichloromethane was added to the resulting solid to adjust the suspension, and insoluble matter was removed with a membrane syringe filter. After the obtained solution was concentrated under reduced pressure, a suspension was adjusted by adding n-hexane, and insoluble matter was filtered off with a glass filter. After concentrating the obtained solution under reduced pressure, n-hexane is added to adjust the suspension, the insoluble matter is filtered off, and the residue is dried under reduced pressure to obtain an orange powder represented by the following formula (6). 0.05 g of the compound dimethylsilylenebis(4-(3,5-di-iso-propyl-4-dimethylaminophenyl)-2-methyl-1-indenyl)zirconium dichloride (hereinafter referred to as metallocene compound (6)) (11% yield, 100% racemic purity).
¹ H NMR (270 MHz, CDCl ₃ ) δ 7.64 (2H, d, J = 8.7 Hz, Ar-H), 7.46-7.36 (6H, m, Ar-H), 7.12 ( 1H, d, J = 8.7 Hz, Ar-H), 7.09 (1H, d, J = 8.7 Hz, Ar-H), 6.99 (2H, s, Cp-H), 3.33 (4H, sep, J = 6.9 Hz, -CH( _CH3 ) ₂ ), 2.84 (12H, s, -NC( _CH3 ) ₂ ), 2.27 (6H, s, Cp- _CH3 ) , 1.34 (6H, s, Si—CH ₃ ), 1.25 (12H, d, J=6.9 Hz, —CH(CH ₃ ) ₂ ), 1.14 (12H, d, J=6. 9Hz, -CH( _CH3 ) ₂ )ppm
FD-mass spectroscopy (M ⁺ ): 882

[Comparative Example 4]
Dimethylsilylenebis(4-(4-dimethylaminophenyl)-2-methyl-1-indenyl)zirconium dichloride (metallocene compound (7)) is described in Organometallics 2006, 25, 1217. Synthesized according to the described method.

[Example 4]
<(2) Preparation of solid carrier>
Silica gel (manufactured by Fuji Silysia Chemical Co., Ltd.: Cumulative 50% particle size 70 μm in volume distribution by laser light diffraction scattering method, specific surface area 340 m ² /g, pore volume 1.3 cm ³ /g, dried at 250°C for 10 hours) was suspended in 77 L of toluene, and then cooled to 0-5°C. To this suspension, 19.4 liters of a toluene solution of methylaluminoxane (3.5 mol/L in terms of Al atoms) was added dropwise over 30 minutes. At this time, the temperature in the system was kept at 0 to 5°C.

Then, after contacting at 0 to 5° C. for 30 minutes, the temperature in the system was raised to 95° C. over 1.5 hours, and contact was continued at 95° C. for 4 hours. Thereafter, the temperature was lowered to room temperature, the supernatant was removed by decantation, and the mixture was washed twice with toluene to prepare a toluene slurry of the solid carrier in a total amount of 115 liters.
A part of the obtained slurry component was sampled and analyzed, and the solid content concentration was 122.6 g/L.

<(3) Preparation of solid catalyst component for olefin polymerization>
30 mL of toluene and 8.2 mL of the above solid carrier slurry (solid weight: 1.0 g) were charged into a reactor equipped with a stirrer and having an internal volume of 200 mL which was sufficiently purged with nitrogen. Then, a toluene solution of 0.025 mmol of the metallocene compound (1) obtained in Example 1 was added and brought into contact with the system at a temperature of 20 to 25° C. for 1 hour. After washing twice with a solution, a total amount of 50 ml of solid catalyst component slurry (I) for olefin polymerization was prepared.

[Example 5]
A solid catalyst component slurry (II) for olefin polymerization was prepared in the same manner as in Example 4, except that the metallocene compound (2) obtained in Example 2 was added instead of the metallocene compound (1).

[Comparative Example 5]
A solid catalyst component slurry (III) for olefin polymerization was prepared in the same manner as in Example 4, except that the metallocene compound (3) obtained in Comparative Example 1 was added instead of the metallocene compound (1).

[Comparative Example 6]
A solid catalyst component slurry (IV) for olefin polymerization was prepared in the same manner as in Example 4, except that the metallocene compound (4) obtained in Comparative Example 2 was added instead of the metallocene compound (1).

[Comparative Example 7]
A solid catalyst component slurry (V) for olefin polymerization was prepared in the same manner as in Example 4, except that the metallocene compound (5) obtained in Comparative Example 3 was added instead of the metallocene compound (1).

[Example 6]
A solid catalyst component slurry (VI) for olefin polymerization was prepared in the same manner as in Example 4, except that the metallocene compound (6) obtained in Example 3 was added instead of the metallocene compound (1).

[Comparative Example 8]
A solid catalyst component slurry (VII) for olefin polymerization was prepared in the same manner as in Example 4, except that the metallocene compound (7) obtained in Comparative Example 4 was added instead of the metallocene compound (1).

<(4) Olefin polymerization>
[Example 7]
500 mL of heptane was charged into a stainless steel autoclave having an internal volume of 1 L that was sufficiently purged with nitrogen, and after the system was replaced with ethylene, 0.375 mmol of triisobutylaluminum and the solid catalyst component slurry (I ) was added as a solid content, and the temperature in the system was raised to 80°C. Then, ethylene was continuously introduced to carry out a polymerization reaction for 90 minutes under conditions of a total pressure of 0.8 MPaG and 80°C. The polymer was collected by filtration and dried at 80° C. for 10 hours under reduced pressure to obtain 60.1 g of ethylene polymer. The polymerization activity was 600.3 g-PE/g-cat. was h.
The resulting polymer had a density of 931 kg/m ³ , a weight average molecular weight (Mw) of 451,600 and a number average molecular weight (Mn) of 128,800.

[Example 8]
500 mL of heptane was charged into a stainless steel autoclave having an internal volume of 1 L which was sufficiently purged with nitrogen, and after the system was replaced with ethylene, 10 mL of 1-hexene, 0.375 mmol of triisobutylaluminum and the solid obtained in Example 4 above were added. 60 mg of catalyst component slurry (I) was added as a solid content, and the temperature in the system was raised to 80°C. Then, ethylene was continuously introduced to carry out a polymerization reaction for 90 minutes under conditions of a total pressure of 0.8 MPaG and 80°C. The polymer was collected by filtration and dried at 80° C. for 10 hours under reduced pressure to obtain 46.1 g of ethylene polymer. The polymerization activity was 767.8 g-PE/g-cat. was h.

The resulting polymer had a density of 905 kg/m ³ , a 1-hexene content of 4.7 mol %, a weight average molecular weight (Mw) of 139,900 and a number average molecular weight (Mn) of 52,100. rice field.

[Example 9]
500 mL of heptane was charged into a stainless steel autoclave having an internal volume of 1 L that was sufficiently purged with nitrogen, and after the system was replaced with ethylene, 0.375 mmol of triisobutylaluminum and the solid catalyst component slurry obtained in Example 5 (II ) was added as a solid content, and the temperature in the system was raised to 80°C. Subsequently, ethylene was continuously introduced to carry out a polymerization reaction for 90 minutes under conditions of a total pressure of 0.8 MPaG and 80°C. The polymer was recovered by filtration and dried at 80° C. for 10 hours under reduced pressure to obtain 64.0 g of ethylene polymer. The polymerization activity was 638.7 g-PE/g-cat. was h.
The resulting polymer had a density of 931 kg/m ³ , a weight average molecular weight (Mw) of 490,500 and a number average molecular weight (Mn) of 122,500.

[Example 10]
500 mL of heptane was charged into a stainless steel autoclave having an internal volume of 1 L that had been sufficiently purged with nitrogen, and the system was replaced with ethylene. 60 mg of catalyst component slurry (II) was added as a solid content, and the temperature in the system was raised to 80°C. Then, ethylene was continuously introduced to carry out a polymerization reaction for 90 minutes under conditions of a total pressure of 0.8 MPaG and 80°C. The polymer was collected by filtration and dried at 80° C. under reduced pressure for 10 hours to obtain 42.8 g of ethylene polymer. Polymerization activity was 712.0 g-PE/g-cat. was h.

The resulting polymer had a density of 907 kg/m ³ , a 1-hexene content of 6.4 mol %, a weight average molecular weight (Mw) of 147,300 and a number average molecular weight (Mn) of 43,200. rice field.

[Comparative Example 9]
500 mL of heptane was charged into a stainless steel autoclave having an internal volume of 1 L that was sufficiently purged with nitrogen, and after the system was replaced with ethylene, 0.375 mmol of triisobutylaluminum and the solid catalyst component slurry obtained in Comparative Example 5 (III ) was added as a solid content, and the temperature in the system was raised to 80°C. Then, ethylene was continuously introduced to carry out a polymerization reaction for 90 minutes under conditions of a total pressure of 0.8 MPaG and 80°C. The polymer was collected by filtration and dried at 80° C. for 10 hours under reduced pressure to obtain 12.3 g of ethylene polymer. The polymerization activity was 121.7 g-PE/g-cat. was h.
The resulting polymer had a weight average molecular weight (Mw) of 410,000 and a number average molecular weight (Mn) of 73,200.

[Comparative Example 10]
500 mL of heptane was charged into a stainless steel autoclave having an internal volume of 1 L that had been sufficiently purged with nitrogen, and the system was replaced with ethylene. 100 mg of catalyst component slurry (III) was added as a solid content, and the temperature in the system was raised to 80°C. Then, ethylene was continuously introduced to carry out a polymerization reaction for 90 minutes under conditions of a total pressure of 0.8 MPaG and 80°C. The polymer was collected by filtration and dried at 80° C. for 10 hours under reduced pressure to obtain 42.7 g of ethylene polymer. The polymerization activity was 426.1 g-PE/g-cat. was h.
The resulting polymer had a 1-hexene content of 4.2 mol %, a weight average molecular weight (Mw) of 136,800, and a number average molecular weight (Mn) of 27,000.

[Comparative Example 11]
500 mL of heptane was charged into a stainless steel autoclave having an internal volume of 1 L which was sufficiently purged with nitrogen, and after the system was replaced with ethylene, 0.375 mmol of triisobutylaluminum and the solid catalyst component slurry obtained in Comparative Example 6 (IV ) was added as a solid content, and the temperature in the system was raised to 80°C. Subsequently, ethylene was continuously introduced to carry out a polymerization reaction for 90 minutes under conditions of a total pressure of 0.8 MPaG and 80°C. The polymer was collected by filtration and dried at 80° C. under reduced pressure for 10 hours to obtain 22.4 g of ethylene polymer. The polymerization activity was 222.5 g-PE/g-cat. was h.
The resulting polymer had a density of 936 kg/m ³ , a weight average molecular weight (Mw) of 347,700 and a number average molecular weight (Mn) of 37,300.

[Comparative Example 12]
500 mL of heptane was charged into a stainless steel autoclave having an internal volume of 1 L that had been sufficiently purged with nitrogen, and after the system was replaced with ethylene, 10 mL of 1-hexene, 0.375 mmol of triisobutylaluminum and the solid obtained in Comparative Example 6 were added. 100 mg of catalyst component slurry (IV) was added as a solid content, and the temperature in the system was raised to 80°C. Subsequently, ethylene was continuously introduced to carry out a polymerization reaction for 90 minutes under conditions of a total pressure of 0.8 MPaG and 80°C. The polymer was recovered by filtration and dried at 80° C. for 10 hours under reduced pressure to obtain 88.8 g of ethylene polymer. The polymerization activity was 887.1 g-PE/g-cat. was h.

The resulting polymer had a density of 916 kg/m ³ , a 1-hexene content of 2.6 mol %, a weight average molecular weight (Mw) of 14,600 and a number average molecular weight (Mn) of 34,200. rice field.

[Comparative Example 13]
500 mL of heptane was charged into a stainless steel autoclave having an internal volume of 1 L that was sufficiently purged with nitrogen, and after the system was replaced with ethylene, 0.375 mmol of triisobutylaluminum and the solid catalyst component slurry (V ) was added as a solid content, and the temperature in the system was raised to 80°C. Subsequently, ethylene was continuously introduced to carry out a polymerization reaction for 90 minutes under conditions of a total pressure of 0.8 MPaG and 80°C. The polymer was recovered by filtration and dried at 80° C. for 10 hours under reduced pressure to obtain 19.0 g of ethylene polymer. The polymerization activity was 188.5 g-PE/g-cat. was h.
The resulting polymer had a density of 942 kg/m ³ , a weight average molecular weight (Mw) of 179,500 and a number average molecular weight (Mn) of 32,300.

[Comparative Example 14]
500 mL of heptane was charged into a stainless steel autoclave having an internal volume of 1 L that had been sufficiently purged with nitrogen, and the system was replaced with ethylene. 60 mg of catalyst component slurry (V) was added as a solid content, and the temperature in the system was raised to 80°C. Subsequently, ethylene was continuously introduced to carry out a polymerization reaction for 90 minutes under conditions of a total pressure of 0.8 MPaG and 80°C. The polymer was collected by filtration and dried at 80° C. for 10 hours under reduced pressure to obtain 48.0 g of ethylene polymer. The polymerization activity was 799.5 g-PE/g-cat. was h.

The resulting polymer had a density of 927 kg/m ³ , a 1-hexene content of 2.7 mol %, a weight average molecular weight (Mw) of 51,800 and a number average molecular weight (Mn) of 13,300. rice field.
The results of Examples 7 to 10 and Comparative Examples 9 to 14 are summarized in [Table 8].

Compared with Comparative Examples 13 and 14 using the known metallocene compound (5) described in Comparative Example 3, the metallocene compound (4 ) in Comparative Examples 11 and 12, an increase in the molecular weight of the produced polymer is observed, but no improvement in 1-hexene copolymerizability is observed.

Further, in Comparative Example 1 and Comparative Examples 9 and 10 using the metallocene compound (3) described in the claims of JP-A-2014-193846, 1-hexene Although an improvement in copolymerizability is observed, a decrease in polymerization activity is observed, presumably due to interaction between the heteroatom and the aluminum compound.

However, in Examples 7 to 10 using the metallocene compounds (1) and (2) described in the claims of the present invention, a significant decrease in polymerization activity was not observed, and rather, ethylene homopolymerization In certain Examples 16 and 18, a clear improvement in polymerization activity and higher molecular weight of the resulting polymer was observed.
Furthermore, in Examples 8 and 10, a marked improvement in 1-hexene copolymerizability, accompanied by a tendency toward lower density of the resulting polymer and narrower molecular weight distribution was observed.

[Example 11]
500 mL of heptane was charged into a stainless steel autoclave having an internal volume of 1 L that was sufficiently purged with nitrogen, and after the system was replaced with ethylene, 0.375 mmol of triisobutylaluminum and the solid catalyst component slurry obtained in Example 6 (VI ) was added as a solid content, and the temperature in the system was raised to 80°C. Subsequently, ethylene was continuously introduced to carry out a polymerization reaction for 90 minutes under conditions of a total pressure of 0.8 MPaG and 80°C. The polymer was collected by filtration and dried at 80° C. under reduced pressure for 10 hours to obtain 44.7 g of ethylene polymer. Polymerization activity was 446.0 g-PE/g-cat. was h.
The resulting polymer had a density of 937 kg/m ³ , a weight average molecular weight (Mw) of 466,500 and a number average molecular weight (Mn) of 88,800.

[Example 12]
500 mL of heptane was charged into a stainless steel autoclave having an internal volume of 1 L that had been sufficiently purged with nitrogen, and after the system was replaced with ethylene, 10 mL of 1-hexene, 0.375 mmol of triisobutylaluminum, and the solid obtained in Example 6 above were added. 40 mg of catalyst component slurry (VI) as a solid content was added, and the temperature in the system was raised to 80°C. Then, by continuously introducing ethylene, a polymerization reaction was carried out for 60 minutes under conditions of a total pressure of 0.8 MPaG and 80°C. The polymer was collected by filtration and dried at 80° C. for 10 hours under reduced pressure to obtain 39.6 g of ethylene polymer. The polymerization activity was 988.3 g-PE/g-cat. was h.

The resulting polymer had a density of 897 kg/m ³ , a 1-hexene content of 6.2 mol %, a weight average molecular weight (Mw) of 325,600 and a number average molecular weight (Mn) of 113,500. rice field.

[Comparative Example 15]
500 mL of heptane was charged into a stainless steel autoclave having an internal volume of 1 L that was sufficiently purged with nitrogen, and after the system was replaced with ethylene, 0.375 mmol of triisobutylaluminum and the solid catalyst component slurry obtained in Comparative Example 8 (VII ) was added as a solid content, and the temperature in the system was raised to 80°C. Then, ethylene was continuously introduced to carry out a polymerization reaction for 90 minutes under conditions of a total pressure of 0.8 MPaG and 80°C. The polymer was collected by filtration and dried at 80° C. for 10 hours under reduced pressure to obtain 32.3 g of ethylene polymer. Polymerization activity was 322.4 g-PE/g-cat. was h.
The resulting polymer had a density of 936 kg/m ³ , a weight average molecular weight (Mw) of 704,600 and a number average molecular weight (Mn) of 105,200.

[Comparative Example 16]
500 mL of heptane was charged into a stainless steel autoclave having an internal volume of 1 L that had been sufficiently purged with nitrogen, and the system was replaced with ethylene. 20 mg of catalyst component slurry (VII) was added as a solid content, and the temperature in the system was raised to 80°C. Subsequently, ethylene was continuously introduced to carry out a polymerization reaction for 90 minutes under conditions of a total pressure of 0.8 MPaG and 80°C. The polymer was recovered by filtration and dried at 80° C. for 10 hours under reduced pressure to obtain 6.55 g of ethylene polymer. The polymerization activity was 326.5 g-PE/g-cat. was h.

The resulting polymer had a density of 912 kg/m ³ , a 1-hexene content of 3.5 mol %, a weight average molecular weight (Mw) of 275,700 and a number average molecular weight (Mn) of 79,600. rice field.
The results of Examples 11 and 12 and Comparative Examples 15 and 16 are summarized in [Table 9].

Compared to Comparative Examples 15 and 16 using the known metallocene compound (7) described in Comparative Example 4, the performance with the metallocene compound (6) described in Example 3 of the present claim Examples 11 and 12 showed extremely high polymerization activity. In Example 12, which is a copolymerization of ethylene and 1-hexene, a marked improvement in polymerization activity and a high molecular weight polymer produced were observed.
Furthermore, in Example 12, a marked improvement in 1-hexene copolymerizability was observed, accompanied by a tendency toward lower density and narrower molecular weight distribution of the resulting polymer.

[Example 13]
[Example 13-1]
0.42 g (17.2 mmol) of magnesium pieces were introduced into a 200 mL reactor that was sufficiently dried and replaced with argon, and vigorously stirred for 30 minutes while heating under reduced pressure. After cooling to room temperature, one piece of iodine and 15 mL of tetrahydrofuran were charged and stirred. To this solution, J. Am. Chem. Soc. 2006, 128, 16486. A diluted solution of 4.67 g (15.6 mmol) of 1-bromo-3,5-di-tert-butyl-4-methoxybenzene synthesized by the described method in 25 mL of tetrahydrofuran was slowly added, and the mixture was heated under reflux in an oil bath for 1 hour. bottom. After cooling the reaction solution to −78° C., 2.00 mL (18.0 mmol) of trimethoxyborane was slowly added, and stirring was continued for 21 hours while the temperature was slowly returned to room temperature. A 1.0 M hydrochloric acid aqueous solution was added, the soluble matter was extracted with diethyl ether, the resulting fraction was washed with water and saturated brine, and dried over anhydrous magnesium sulfate. After filtering the magnesium sulfate, the residue obtained by distilling off the filtrate was treated with Organometallics 2006, 25, 1217. 2.70 g (12.0 mmol) of 4-bromo-2-methyl-1-indanone synthesized by the described method, 6.69 g (31.5 mmol) of tripotassium phosphate, 0.03 g (0.13 mmol) of palladium acetate, 0.08 g (0.18 mmol) of 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl (S-Phos), 30 mL of tetrahydrofuran, and 6 mL of distilled water were charged, and heated under reflux in an oil bath for 2 hours. After the reaction solution was cooled to room temperature, saturated aqueous ammonium chloride solution was added, the soluble matter was extracted with ethyl acetate, the resulting fraction was washed with saturated brine and dried over anhydrous magnesium sulfate. After filtering magnesium sulfate, the residue obtained by evaporating the filtrate was purified by silica gel column chromatography to obtain 4.09 g of the target compound represented by the following formula (8a) (hereinafter referred to as compound (8a)) ( Yield 93%) was obtained.
¹ H NMR (270 MHz, CDCl ₃ ) δ 7.75 (1H, dd, J = 7.5 and 1.2 Hz, Ar-H), 7.61 (1H, dd, J = 7.5 and 1.2 Hz, Ar-H ), 7.45 (1H, t, J = 7.5 Hz, Ar-H), 7.33 (2H, s, Ar-H), 3.76 (3H, s, _-OCH3 ), 3.56 -3.39 (1H, m, CH--CH ₃ ), 2.85-2.65 (2H, m, Ar--CH ₂ --C), 1.48 (18H, s, --C(CH ₃ ) ₃ ), 1.33 (3H, d, J=7.3 Hz, CH—CH ₃ ) ppm

[Example 13-2]
4.07 g (11.2 mmol) of the compound (8a) obtained in Example 13-1, 15 mL of tetrahydrofuran and 5 mL of methanol were introduced into a 200 mL reactor sufficiently dried and purged with argon and stirred. The solution was cooled to 0° C., 0.85 g (22.6 mmol) of sodium hydroborate was slowly added in portions, and the mixture was stirred at room temperature for 2 hours. This solution was cooled to 0° C., 1.0 M hydrochloric acid aqueous solution was slowly added, the soluble matter was extracted with ethyl acetate, the resulting fraction was washed with saturated brine and dried over anhydrous magnesium sulfate. After filtering magnesium sulfate, 20 mL of toluene and 0.05 g (0.24 mmol) of p-toluenesulfonic acid monohydrate were added to the residue obtained by evaporating the filtrate, and the mixture was heated in an oil bath for 1 hour. refluxed. After cooling the reaction solution to room temperature, saturated aqueous sodium hydrogencarbonate solution was added, the soluble matter was extracted with n-hexane, the resulting fraction was washed with saturated brine and dried over anhydrous magnesium sulfate. After filtering magnesium sulfate, the residue obtained by evaporating the filtrate was purified by silica gel column chromatography to obtain 3.51 g of the target compound represented by the following formula (8b) (hereinafter referred to as compound (8b)) ( Yield 90%) was obtained.
¹ H NMR (270 MHz, CDCl ₃ ) δ 7.41 (2H, s, Ar—H), 7.35-7.17 (2H, m, Ar—H), 7.12 (1H, dd, J= 7.4 and 1.3 Hz, Ar-H), 6.53 (1H, dd, J=2.9 and 1.4 Hz, Ar-CH=C), 3.75 (3H, s, -OCH ₃ ), 3.38 (2H, s, Ar—CH ₂ —C), 2.15 (3H, s, C—CH ₃ ), 1.47 (18H, s, —C(CH ₃ ) ₃ ) ppm

[Example 13-3]
2.10 g (6.02 mmol) of the compound (8b) obtained in Example 13-2 and 15 mL of tetrahydrofuran were charged into a 200 mL reactor sufficiently dried and purged with argon and stirred. 3.90 mL of n-butyllithium solution (hexane solution, 1.55 M, 6.05 mmol) was added to this solution under ice-cooling, and the mixture was stirred at room temperature for 2 hours. After adding 0.60 mL (6.39 mmol) of 1,3-dimethyl-2-imidazolidinone to this solution, the solution was cooled to 0° C., 0.36 mL (3.01 mmol) of dichlorodimethylsilane was added, and the mixture was slowly cooled to room temperature. Stirring was continued for 16 hours while returning. A saturated aqueous ammonium chloride solution was added, the soluble matter was extracted with n-hexane, the resulting fraction was washed with saturated brine and dried over anhydrous magnesium sulfate. After filtering magnesium sulfate, the residue obtained by evaporating the filtrate was purified by silica gel column chromatography to obtain 1.42 g of the target compound represented by the following formula (8c) (hereinafter referred to as compound (8c)) ( Yield 63%) as a mixture of isomers.
¹ H NMR (270 MHz, CDCl ₃ ) δ 7.60-7.00 (10H, m, Ar—H), 6.99-6.65 (2H, m, Ar—CH=C), 3.95- 3.65 (2H, m, CH—Si—CH), 3.76 (6H, s, —OCH ₃ ), 2.40-1.90 (6H, m, C—CH ₃ ), 1.56- 1.36 (3H, m, Si—CH ₃ ), 1.49 (36 H, s, —C(CH ₃ ) ₃ ), −0.13——0.28 (3H, m, Si—CH ₃ ) ppm

[Example 13-4]
0.38 g (0.50 mmol) of the compound (8c) obtained in Example 13-3, 10 mL of toluene and 0.1 mL of tetrahydrofuran were charged into a 100 mL reactor sufficiently dried and purged with argon and stirred. After adding 0.65 mL of n-butyllithium solution (hexane solution, 1.54 M, 1.00 mmol) to this solution at room temperature, stirring was continued for 3 hours in an oil bath at 40°C. After distilling off the solvent of the reaction solution, 10 mL of n-hexane and 0.6 mL of diethyl ether were added to the resulting solid. The solution was cooled to 0° C., 0.12 g (0.50 mmol) of zirconium tetrachloride was added, and stirring was continued at room temperature for 18 hours. After distilling off the solvent of the reaction solution, dichloromethane was added to the resulting solid to adjust the suspension, and insoluble matter was removed with a membrane syringe filter. After the obtained solution was concentrated under reduced pressure, a suspension was adjusted by adding n-hexane, and insoluble matter was filtered off with a glass filter. The residue was dissolved in toluene, n-hexane was added, and the mixture was allowed to stand under cooling at 0° C. for 24 hours. Crystallized crystals were separated by filtration, and the residue was dried under reduced pressure to give an orange powdery compound dimethylsilylenebis(4-(3,5-di-tert-butyl-4-methoxy) represented by the following formula (8). 0.15 g of phenyl)-2-methyl-1-indenyl)zirconium dichloride (hereinafter referred to as metallocene compound (8)) was obtained (yield 33%, meso purity 92%). After the filtrate was concentrated under reduced pressure, n-hexane was added to adjust the suspension, insoluble matter was filtered off with a glass filter, and the residue was dried under reduced pressure to obtain 0.08 g of metallocene compound (8). (yield 18%, racemic purity 80%).
¹ H NMR (270 MHz, CDCl ₃ ) [meso-] δ 7.62 (2H, d, J = 8.5 Hz, Ar-H), 7.47 (4H, s, Ar-H), 7.08 ( 2H, d, J = 6.9 Hz, Ar-H), 6.86 (2H, dd, J = 7.0 and 8.7 Hz, Ar-H), 6.77 (2H, s, Cp-H), 3 .71 (6H, s, —OCH ₃ ), 2.46 (6H, s, Cp—CH ₃ ), 1.47 (3H, s, Si—CH ₃ ), 1.43 (36H, s, —C (CH ₃ ) ₃ ), 1.25 (3H, s, Si—CH ₃ ) ppm, [rac-] δ 7.64 (2H, d, J=8.7 Hz, Ar—H), 7.52 ( 4H, s, Ar-H), 7.38 (2H, d, J = 7.0 Hz, Ar-H), 7.10 (2H, dd, J = 7.0 and 8.7 Hz, Ar-H), 6 .93 (2H, s, Cp—H), 3.69 (6H, s, —OCH ₃ ), 2.27 (6H, s, Cp—CH ₃ ), 1.41 (36H, s, —C ( CH ₃ ) ₃ ), 1.34 (6H, s, Si—CH ₃ ) ppm
FD-mass spectroscopy (M ⁺ ): 912

[Comparative Example 17]
Dimethylsilylenebis(4-(3,5-di-tert-butylphenyl)-2-methyl-1-indenyl)zirconium dichloride (metallocene compound (9)) is synthesized by the method described in JP-A-2004-502699. (racemic purity 50%).

[Comparative Example 18]
Dimethylsilylenebis(4-phenyl-2-methyl-1-indenyl)zirconium dichloride (metallocene compound (10)) was synthesized by the method described in Japanese Patent No. 3737134 (racemic purity 100%).

[Example 14]
250 mL of toluene was charged into a 500 mL glass reactor that was sufficiently purged with nitrogen, and the temperature was raised to 85°C. While stirring the contents at 600 rpm, propylene was continuously supplied at a flow rate of 100 L/h to saturate the liquid phase and gas phase. Subsequently, while propylene was continuously supplied at the same flow rate, 1.0 mL (1.25 mmol) of a toluene solution (1.25 mol/L) of methylaluminoxane (PMAO) was added, and then obtained in Example 3-3. 0.001 mL (1.00 μmol) of a toluene solution (1.00 mol/L) of the obtained metallocene compound (6) was added, and polymerization was carried out at 85° C. for 5 minutes under normal pressure. The polymerization reaction was terminated by adding a small amount of isobutyl alcohol, and the resulting polymerization reaction solution was added to 2.0 L of methanol containing a small amount of hydrochloric acid to precipitate a polymer. The polymer was collected by filtration and dried at 80° C. under reduced pressure for 10 hours to obtain 4.01 g of a propylene polymer. The polymerization activity was 481,000 g-PP/mmol-Zr. was h.
The resulting polymer had a melting point of 152.0° C. and a number average molecular weight (Mn) of 32,600.

[Example 15]
Instead of the metallocene compound (6), 0.002 mL (2.00 μmol) of the toluene solution (1.00 mol/L) of the metallocene compound (8) having a racemic purity of 80% obtained in Example 13-4 was added. A polymerization reaction was carried out in the same manner as in Example 14, except for the above. The amount of propylene polymer obtained was 3.94 g, and the polymerization activity was 236,000 g-PP/mmol-Zr. was h.
The resulting polymer had a melting point of 152.4° C. and a number average molecular weight (Mn) of 32,600.

[Comparative Example 19]
Example 14 except that 0.002 mL (2.00 μmol) of the toluene solution (1.00 mol/L) of the metallocene compound (9) obtained in Comparative Example 17 was added instead of the metallocene compound (6). A polymerization reaction was carried out in the same manner. The amount of propylene polymer obtained was 1.12 g, and the polymerization activity was 67,000 g-PP/mmol-Zr. was h.
The resulting polymer had a melting point of 148.7° C. and a number average molecular weight (Mn) of 14,500.

[Comparative Example 20]
Example 14 except that 0.003 mL (3.00 μmol) of the toluene solution (1.00 mol/L) of the metallocene compound (10) obtained in Comparative Example 18 was added instead of the metallocene compound (6). A polymerization reaction was carried out in the same manner. The amount of propylene polymer obtained was 3.87 g, and the polymerization activity was 155,000 g-PP/mmol-Zr. was h.

The resulting polymer had a melting point of 142.4° C. and a number average molecular weight (Mn) of 7,600.
The results of Examples 14 and 15 and Comparative Examples 19 and 20 are summarized in [Table 10].

Compared to Comparative Examples 19 and 20 using the known metallocene compounds (9) and (10) described in Comparative Examples 17 and 18, the claimed Examples 3-3 and 13-4 Examples 14 and 15 using the metallocene compounds (6) and (8) described showed high polymerization activity.

In addition, by comparing the melting points of the obtained propylene polymers, it was found that the examples using the metallocene compounds (6) and (8) described in Examples 3-3 and 13-4, which are the scope of the present claims, In Nos. 14 and 15, high stereoregularity was exhibited, and a significant increase in molecular weight was also observed.

[Example 16]
216 mL of cyclohexane and 24 mL of hexane were introduced into a 500 mL internal volume glass reactor that was sufficiently purged with nitrogen, and the temperature was raised to 50°C. While stirring the contents at 600 rpm, ethylene was continuously supplied at a flow rate of 50 L/h to saturate the liquid phase and gas phase. Subsequently, tetracyclo[4.4.0.1 ^2,5 . 1 ^7,10 ]-3-dodecene (TD) 15.0 mL, styrene (ST) 3.80 mL, and triisobutylaluminum toluene solution (1.00 mol/L) 0.70 mL (0.7 mmol) were sequentially inserted. Furthermore, 3.00 mL (2.0 μmol) of the toluene solution (0.67 mmol/L) of the metallocene compound (1) obtained in Example 1-3 above, and then triphenylcarbenium tetrakis(pentafluorophenyl)borate 2.00 mL (8.0 μmol) of a toluene solution (4.00 mmol/L) of (TrB(C ₆ F ₅ ) ₄ ) was added, and polymerization was carried out at 50° C. for 10 minutes under normal pressure. The polymerization reaction was stopped by adding a small amount of isobutyl alcohol, and the resulting polymerization reaction solution was added to 1.25 L of methanol/acetone (1/3; v/v) mixed solvent containing a small amount of hydrochloric acid to obtain a polymer. was precipitated. The polymer was recovered by filtration and dried at 80° C. for 10 hours under reduced pressure to obtain 143 mg of ethylene/TD/ST copolymer. The polymerization activity was 430 g-Polym/mmol-Zr. was h.

The resulting polymer had a glass transition temperature (Tg) of 81°C, an intrinsic viscosity [η] of 0.43 dL/g, and a content ratio (mol%) of each component of "E/TD/ST = 61 .0/20.5/18.4".

[Example 17]
A polymerization reaction was carried out in the same manner as in Example 16, except that the metallocene compound (2) obtained in Example 2-5 was added instead of the metallocene compound (1). The obtained ethylene/TD/ST copolymer was 218 mg and had a polymerization activity of 650 g-Polym/mmol-Zr. was h.

The resulting polymer had a glass transition temperature (Tg) of 89°C, an intrinsic viscosity [η] of 0.45 dL/g, and a content ratio (mol%) of each component of "E/TD/ST = 59 .7/22.0/18.2".

[Comparative Example 21]
A polymerization reaction was carried out in the same manner as in Example 16, except that the metallocene compound (3) obtained in Comparative Example 1-4 was added instead of the metallocene compound (1). The obtained ethylene/TD/ST copolymer was 15 mg, and the polymerization activity was 45 g-Polym/mmol-Zr. h, and the glass transition temperature (Tg) of the obtained polymer was 80°C.
The yield of the obtained polymer was so small that it was impossible to measure the intrinsic viscosity and the content of each monomer.

[Comparative Example 22]
A polymerization reaction was carried out in the same manner as in Example 16, except that the metallocene compound (5) obtained in Comparative Example 3 was added instead of the metallocene compound (1). The obtained ethylene/TD/ST copolymer was 1.41 g, and the polymerization activity was 4,230 g-Polym/mmol-Zr. was h.

The resulting polymer had a glass transition temperature (Tg) of 142°C, an intrinsic viscosity [η] of 0.59 dL/g, and a content ratio (mol%) of each component of "E/TD/ST = 58 .6/33.0/8.4".

The results of Examples 16 and 17 and Comparative Examples 21 and 22 are summarized in [Table 11].

Compared with Comparative Example 21 using the known metallocene compound (3) described in Comparative Examples 1-4, the metallocene compounds described in Examples 1-3 and 2-5 ( Examples 16 and 17 using 1) and (2) showed significantly higher polymerization activity. This is considered to be due to the aforementioned effect of reducing the interaction between the heteroatom and the aluminum compound.

In addition, in comparison with Comparative Example 22 using the known metallocene compound (5) described in Comparative Example 3, the metallocene compounds ( In Examples 16 and 17 using 1) and (2), high styrene copolymerizability was exhibited, indicating that they had extremely excellent styrene conversion.

[Example 18]
0.38 g (0.50 mmol) of the compound (8c) obtained in Example 13-3, 10 mL of toluene and 0.1 mL of tetrahydrofuran were charged into a 100 mL reactor sufficiently dried and purged with argon and stirred. After adding 0.61 mL of n-butyllithium solution (hexane solution, 1.64 M, 1.00 mmol) to this solution at room temperature, stirring was continued for 3 hours in an oil bath at 40°C. After distilling off the solvent of the reaction solution, 10 mL of n-hexane and 0.6 mL of diethyl ether were added to the resulting solid. This solution was cooled to 0° C., 0.16 g (0.51 mmol) of bonium tetrachloride was added, and stirring was continued at room temperature for 17 hours. After distilling off the solvent of the reaction solution, dichloromethane was added to the resulting solid to adjust the suspension, and insoluble matter was removed with a membrane syringe filter. After the resulting solution was concentrated to dryness under reduced pressure, n-hexane was added to prepare a suspension, and insoluble matter was filtered off through a glass filter. After concentrating the filtrate under reduced pressure, n-hexane was added to adjust the suspension, insoluble matter was filtered off through a glass filter, and the residue was dried under reduced pressure to obtain a yellow color represented by the following formula (11). Powdered compound dimethylsilylene bis(4-(3,5-di-tert-butyl-4-methoxyphenyl)-2-methyl-1-indenyl) hanium dichloride (hereinafter referred to as metallocene compound (11)) was added to 0. 12 g (yield 23%, racemic purity 100%) was obtained.
¹ H NMR (270 MHz, CDCl ₃ ) δ 7.68 (2H, d, J = 8.7 Hz, Ar-H), 7.51 (4H, s, Ar-H), 7.36 (2H, d, J = 6.3 Hz, Ar-H), 7.07 (2H, dd, J = 7.0 and 8.7 Hz, Ar-H), 6.85 (2H, s, Cp-H), 3.69 (6H , s, —OCH ₃ ), 2.36 (6H, s, Cp—CH ₃ ), 1.40 (36H, s, —C(CH ₃ ) ₃ ), 1.34 (6H, s, Si—CH ₃ ) ppm
FD-mass spectrometry (M ⁺ ): 1000

[Example 19]
0.36 g (0.50 mmol) of the compound (6b) obtained in Example 3-2, 10 mL of toluene and 0.1 mL of tetrahydrofuran were charged into a 100 mL reactor sufficiently dried and purged with argon and stirred. After adding 0.61 mL of n-butyllithium solution (hexane solution, 1.64 M, 1.00 mmol) to this solution at room temperature, stirring was continued for 3 hours in an oil bath at 40°C. After distilling off the solvent of the reaction solution, 10 mL of n-hexane and 0.6 mL of diethyl ether were added to the resulting solid. This solution was cooled to 0° C., 0.17 g (0.52 mmol) of hafnium tetrachloride was added, and stirring was continued at room temperature for 19 hours. After distilling off the solvent of the reaction solution, dichloromethane and toluene were added to the resulting solid to adjust the suspension, and insoluble matter was removed with a membrane syringe filter. After the resulting solution was concentrated to dryness under reduced pressure, dichloromethane was added to adjust the suspension, the insoluble matter was filtered off through a glass filter, and the residue was dried under reduced pressure to obtain the compound represented by the following formula (12). yellow powdery compound dimethylsilylene bis(4-(3,5-di-iso-propyl-4-dimethylaminophenyl)-2-methyl-1-indenyl) hanium dichloride (hereinafter referred to as metallocene compound (12)) 0.05 g (yield 11%, meso form purity 88%) was obtained. After the filtrate was concentrated under reduced pressure, the precipitated insoluble matter was separated by filtration through a glass filter. After the filtrate was concentrated to dryness under reduced pressure, a suspension was adjusted by adding n-hexane, and insoluble matter was filtered off with a glass filter. By drying the residue under reduced pressure, 0.07 g of metallocene compound (12) was obtained (yield 15%, racemic purity 100%).
¹ H NMR (270 MHz, CDCl ₃ ) [meso-] δ 7.64 (2H, d, J = 8.7 Hz, Ar-H), 7.31 (4H, s, Ar-H), 7.08 ( 2H, d, J = 6.8 Hz, Ar-H), 6.80 (2H, dd, J = 6.9 and 8.7 Hz, Ar-H), 6.72 (2H, s, Cp-H), 3 .34 (4H, sep, J=6.89 Hz, —CH(CH ₃ ) ₂ ), 2.86 (12H, s, —NC(CH ₃ ) ₂ ), 2.57 (6H, s, Cp—CH ₃ ), 1.46 (3H, s, Si—CH ₃ ), 1.27 (15H, d, J=6.9 Hz, Si—CH ₃ and—CH(CH ₃ ) ₂ ), 1.14 (12H , d, J=6.9 Hz, —CH(CH ₃ ) ₂ ) ppm, [rac-] δ 7.68 (2H, d, J=8.8 Hz, Ar—H), 7.42-7.35 (6H, m, Ar-H), 7.07 (2H, dd, J = 6.9 and 8.7 Hz, Ar-H), 6.91 (2H, s, Cp-H), 3.33 (4H, sep, J=6.73 Hz, --CH(CH ₃ ) ₂ ), 2.85 (12H, s, --NC(CH ₃ ) ₂ ), 2.36 (6H, s, Cp--CH ₃ ), 1. 33 (6H, s, Si—CH ₃ ), 1.25 (12H, d, J=6.9 Hz, —CH (CH ₃ ) ₂ ), 1.13 (12H, d, J=6.9 Hz, — CH( _CH3 ) ₂ )ppm
FD-mass spectroscopy (M ⁺ ): 970

[Comparative Example 23]
Dimethylsilylenebis(4-phenyl-2-methyl-1-indenyl)hafnium dichloride (metallocene compound (13)) was synthesized by the method described in JP-A-2001-253913 (racemic purity: 100%).

[Example 20]
A magnetic stirrer was placed in a sufficiently dried and nitrogen-substituted Schlenk tube, and 2.5 μmol of the metallocene compound (11) obtained in Example 18 was added as a catalyst. A certain amount of toluene and 200 equivalents of triisobutylaluminum (n-hexane solvent, 0.5 mmol in terms of aluminum atoms) were added with stirring to the catalyst (11) at room temperature to prepare a catalyst solution.

550 mL of heptane as a polymerization solvent and 1.5 mL of a hexane solution of triisobutylaluminum (Al=0.5 M, 0.75 mmol) were charged into a SUS autoclave having an internal volume of 1,500 mL which had been sufficiently dried and replaced with nitrogen, After adding 90 g of 1-butene while stirring at 850 rpm, the polymerization temperature was raised to 65°C. Further, at that temperature, the autoclave was pressurized with nitrogen until the internal pressure of the autoclave reached 0.5 MPaG.

The catalyst solution prepared above was charged into this autoclave, and then 10 equivalents of triphenylcarbenium tetrakis(pentafluorophenyl)borate (toluene solvent, 25 μmol in terms of boron atom) with respect to catalyst (11) was charged. After 10 minutes from the initiation of the polymerization, methanol was added to terminate the polymerization.

The polymerization liquid taken out from the cooled/depressurized autoclave was poured into methanol to precipitate the polymer, which was collected by filtration. After that, the recovered polymer was dried under reduced pressure at 80° C. for 12 hours to obtain 80.0 g of polymer for evaluation. The polymerization activity was 192.1 Kg-Polym/mmol-Hf. h, the crystallization temperature (Tc) was 76.6°C and the melting point of the polymer after crystal stabilization was 126.3°C.

[Example 21]
A magnetic stirrer was placed in a sufficiently dried and nitrogen-substituted Schlenk tube, and 2.0 μmol of the racemic metallocene compound (12) obtained in Example 19 was added as a catalyst. /mL of toluene and 200 equivalents of triisobutylaluminum (n-hexane solvent, 0.4 mmol in terms of aluminum atom) with respect to the catalyst (12) were added at room temperature with stirring to prepare a catalyst solution. .

550 mL of heptane as a polymerization solvent and 1.5 mL of a hexane solution of triisobutylaluminum (Al=0.5 M, 0.75 mmol) were charged into a SUS autoclave having an internal volume of 1,500 mL which had been sufficiently dried and replaced with nitrogen, After adding 90 g of 1-butene while stirring at 850 rpm, the polymerization temperature was raised to 65°C. Further, at that temperature, the autoclave was pressurized with nitrogen until the internal pressure of the autoclave reached 0.5 MPaG.

The catalyst solution prepared above was charged into this autoclave, and then 10 equivalents of triphenylcarbenium tetrakis(pentafluorophenyl)borate (toluene solvent, 20 μmol in terms of boron atoms) relative to catalyst (12) was charged. After 10 minutes from the initiation of the polymerization, methanol was added to terminate the polymerization.

The polymerization liquid taken out from the cooled/depressurized autoclave was poured into methanol to precipitate the polymer, which was collected by filtration. After that, the recovered polymer was dried under reduced pressure at 80° C. for 12 hours to obtain 47.1 g of polymer for evaluation. The polymerization activity was 141.4 Kg-Polym/mmol-Hf. h, the crystallization temperature (Tc) was 81.6°C and the melting point of the polymer after crystal stabilization was 127.9°C.

[Comparative Example 24]
A magnetic stirrer was placed in a sufficiently dried and nitrogen-substituted Schlenk tube, and 2.5 μmol of the metallocene compound (13) obtained in Comparative Example 23 was added as a catalyst. A certain amount of toluene and 200 equivalents of triisobutylaluminum (n-hexane solvent, 0.5 mmol in terms of aluminum atoms) were added with stirring to catalyst (13) at room temperature to prepare a catalyst solution.

550 mL of heptane as a polymerization solvent and 1.5 mL of a hexane solution of triisobutylaluminum (Al=0.5 M, 0.75 mmol) were charged into a SUS autoclave having an internal volume of 1,500 mL which had been sufficiently dried and replaced with nitrogen, After adding 90 g of 1-butene while stirring at 850 rpm, the polymerization temperature was raised to 65°C. Further, at that temperature, the autoclave was pressurized with nitrogen until the internal pressure of the autoclave reached 0.5 MPaG.

The catalyst solution prepared above was charged into this autoclave, and then 10 equivalents of triphenylcarbenium tetrakis(pentafluorophenyl)borate (toluene solvent, 25 μmol in terms of boron atoms) relative to catalyst (13) was charged. After 10 minutes from the initiation of the polymerization, methanol was added to terminate the polymerization.

The polymerization liquid taken out from the cooled/depressurized autoclave was poured into methanol to precipitate the polymer, which was collected by filtration. After that, the recovered polymer was dried under reduced pressure at 80° C. for 12 hours to obtain 51.1 g of polymer for evaluation. The polymerization activity was 122.7 Kg-Polym/mmol-Hf. h, the crystallization temperature (Tc) was 75.7°C and the melting point of the polymer after crystal stabilization was 125.9°C.

[Example 22]
A magnetic stirrer was placed in a sufficiently dried and nitrogen-substituted Schlenk tube, and 1.5 μmol of the metallocene compound (11) obtained in Example 18 was added as a catalyst. A certain amount of toluene and 200 equivalents of triisobutylaluminum (n-hexane solvent, 0.3 mmol in terms of aluminum atoms) were added with stirring to the catalyst (11) at room temperature to prepare a catalyst solution.

550 mL of heptane as a polymerization solvent and 1.5 mL of a hexane solution of triisobutylaluminum (Al=0.5 M, 0.75 mmol) were charged into a SUS autoclave having an internal volume of 1,500 mL which had been sufficiently dried and replaced with nitrogen, After adding 90 g of 1-butene while stirring at 850 rpm, the polymerization temperature was raised to 65°C. Further, after adding 35.5 NmL of hydrogen at that temperature, the autoclave was pressurized with nitrogen until the internal pressure of the autoclave reached 0.5 MPaG.

The catalyst solution prepared above was charged into this autoclave, and then 10 equivalents of triphenylcarbenium tetrakis(pentafluorophenyl)borate (toluene solvent, 15 μmol in terms of boron atom) relative to catalyst (11) was charged. After 10 minutes from the initiation of the polymerization, methanol was added to terminate the polymerization.

The polymerization liquid taken out from the cooled/depressurized autoclave was poured into methanol to precipitate the polymer, which was collected by filtration. After that, the recovered polymer was dried under reduced pressure at 80° C. for 12 hours to obtain 71.9 g of polymer for evaluation. The polymerization activity was 215.8 Kg-Polym/mmol-Hf. h, the crystallization temperature (Tc) was 79.4°C and the melting point of the polymer after crystal stabilization was 125.4°C.

[Example 23]
A magnetic stirrer was placed in a sufficiently dried and nitrogen-substituted Schlenk tube, and 1.5 μmol of the racemic metallocene compound (12) obtained in Example 19 was added as a catalyst. /mL of toluene and 200 equivalents of triisobutylaluminum (n-hexane solvent, 0.3 mmol in terms of aluminum atom) with respect to the catalyst (12) were added at room temperature with stirring to prepare a catalyst solution. .

550 mL of heptane as a polymerization solvent and 1.5 mL of a hexane solution of triisobutylaluminum (Al=0.5 M, 0.75 mmol) were charged into a SUS autoclave having an internal volume of 1,500 mL which had been sufficiently dried and replaced with nitrogen, After adding 90 g of 1-butene while stirring at 850 rpm, the polymerization temperature was raised to 65°C. Further, after adding 35.5 NmL of hydrogen at that temperature, the autoclave was pressurized with nitrogen until the internal pressure of the autoclave reached 0.5 MPaG.

The catalyst solution prepared above was charged into this autoclave, and then 10 equivalents of triphenylcarbenium tetrakis(pentafluorophenyl)borate (toluene solvent, 15 μmol in terms of boron atoms) relative to catalyst (12) was charged. After 10 minutes from the initiation of the polymerization, methanol was added to terminate the polymerization.

The polymerization liquid taken out from the cooled/depressurized autoclave was poured into methanol to precipitate the polymer, which was collected by filtration. After that, the recovered polymer was dried under reduced pressure at 80° C. for 12 hours to obtain 76.1 g of polymer for evaluation. The polymerization activity was 303.5 Kg-Polym/mmol-Hf. h, the crystallization temperature (Tc) was 75.3°C and the melting point of the polymer after crystal stabilization was 125.4°C.

[Comparative Example 25]
A magnetic stirrer was placed in a sufficiently dried and nitrogen-substituted Schlenk tube, and 2.0 μmol of the metallocene compound (13) obtained in Comparative Example 23 was added as a catalyst. A certain amount of toluene and 200 equivalents of triisobutylaluminum (n-hexane solvent, 0.4 mmol in terms of aluminum atoms) were added with stirring to catalyst (13) at room temperature to prepare a catalyst solution.

550 mL of heptane as a polymerization solvent and 1.5 mL of a hexane solution of triisobutylaluminum (Al=0.5 M, 0.75 mmol) were charged into a SUS autoclave having an internal volume of 1,500 mL which had been sufficiently dried and replaced with nitrogen, After adding 90 g of 1-butene while stirring at 850 rpm, the polymerization temperature was raised to 65°C. Further, after adding 35.5 NmL of hydrogen at that temperature, the autoclave was pressurized with nitrogen until the internal pressure of the autoclave reached 0.5 MPaG.

The catalyst solution prepared above was charged into this autoclave, and then 10 equivalents of triphenylcarbenium tetrakis(pentafluorophenyl)borate (toluene solvent, 20 μmol in terms of boron atoms) relative to catalyst (13) was charged. After 10 minutes from the initiation of the polymerization, methanol was added to terminate the polymerization.

The polymerization liquid taken out from the cooled/depressurized autoclave was poured into methanol to precipitate the polymer, which was collected by filtration. After that, the recovered polymer was dried under reduced pressure at 80° C. for 12 hours to obtain 64.7 g of polymer for evaluation. The polymerization activity was 194.4 Kg-Polym/mmol-Hf. h, the crystallization temperature (Tc) was 68.9°C and the melting point of the polymer after crystal stabilization was 121.5°C.
The results of Examples 20 to 23 and Comparative Examples 24 and 25 are summarized in [Table 12].

Compared to Comparative Examples 24 and 25 using the known metallocene compound (13) described in Comparative Example 23, metallocene compounds (11) and ( Examples 20 to 23 using 12) exhibited extremely high polymerization activity.

Further, by comparing the melting points of the obtained 1-butene polymers, it was found that the In Comparative Example 23, compared with Comparative Examples 24 and 25 using the known metallocene compound (13) described in Comparative Example 23, high stereoregularity was observed.

By using the olefin polymerization catalyst containing the novel transition metal compound introduced with the specific substituent according to the present invention, when homopolymerization of ethylene or copolymerization of ethylene and α-olefin is performed, good It is capable of producing an olefin polymer having olefin polymerization activity and sufficient molecular weight, and exhibits particularly excellent α-olefin copolymerizability and a narrowing tendency of molecular weight distribution. By using the present invention, it is expected that a polyolefin having an excellent balance of impact resistance, light weight, and transparency, which makes the most of these characteristics, can be provided with high productivity. Therefore, it can be said that the present invention has extremely high industrial value.

Further, by using the olefin polymerization catalyst containing the novel transition metal compound introduced with the specific substituent according to the present invention, it is possible to polymerize a propylene-based polymer, co-polymerize ethylene with a cyclic olefin, and an aromatic vinyl compound. Polymerization and polymerization of 1-butene polymers can also be carried out with good polymerization activity. The obtained propylene-based polymer has high stereoregularity and high molecular weight, and the obtained 1-butene-based polymer has high stereoregularity. In addition, the obtained copolymer of ethylene, cyclic olefin and aromatic vinyl compound has an excellent conversion rate of the aromatic vinyl compound. Therefore, the industrial value of the present invention is high.

Claims (8)

An olefin polymerization catalyst comprising a transition metal compound [A] represented by the following general formula [3].

(In general formula [3],
M is a zirconium atom or a hafnium atom ,
n is an integer from 1 to 4 that satisfies the valence of M,
X is a halogen atom , a methyl group, or a benzyl group , and when n is 2 or more, multiple groups represented by X may be the same or different, and are bonded to each other to form a ring. may be
Q is a divalent dimethylsilylene group or isopropylidene group,
R ² and R ⁴ are hydrogen atoms, R ¹ and R ³ are each independently a hydrogen atom, a methyl group, an ethyl group, or a 1-propyl group , which may be the same or different,
R ¹¹ to R ¹⁴ are hydrogen atoms,
R ^a1 to R ^a4 are each independently a methyl group, an ethyl group, an iso-propyl group, or a tert-butyl group , and may be the same or different;
R ^b1 and R ^b2 are substituents represented by the following general formula [2],
R ⁵ to R ¹⁰ are each independently a hydrogen atom, a methyl group, an ethyl group, an iso-propyl group, a tert-butyl group, or a methoxy group , and may be the same or different;
R ⁵ and R ⁶ and R ⁸ and R ⁹ may combine with each other to form a saturated 5-membered ring. )

(In general formula [2],
V is nitrogen or oxygen when Q is a divalent isopropylidene group, or nitrogen when Q is a divalent dimethylsilylene group;
m is an integer of 1 or 2 that satisfies the valence of V;
each R ^c is independently a hydrogen atom , a methyl group, an ethyl group, an iso-propyl group, or a tert-butyl group ;
R ^c forming R ^b1 and at least one selected from R ^a1 and R ^a2 and R ^c forming R ^b2 and at least one selected from R ^a3 and R ^a4 are bonded to each other to form a saturated ring. may be formed. ) In the general formula [3],
R ⁵ to R ¹⁰ are hydrogen atoms ,
R ^b1 and R ^b2 are a methoxy group or a dialkylamino group when Q is a divalent isopropylidene group, and a dialkylamino group when Q is a divalent dimethylsilylene group. The catalyst for olefin polymerization according to claim 1 . Furthermore, [B] (B-1) an organometallic compound,
(B-2) an organoaluminum oxy compound, and (B-3) at least one compound selected from the group consisting of a compound that forms an ion pair by reacting with the transition metal compound [A]. The olefin polymerization catalyst according to claim 1 or 2 . A method for producing an olefin polymer, comprising a step of polymerizing an olefin in the presence of the olefin polymerization catalyst according to any one of claims 1 to 3 . 5. The method for producing an olefin polymer according to claim 4 , wherein the olefin polymerization is homopolymerization of ethylene or copolymerization of ethylene and an α-olefin having 3 to 20 carbon atoms. 5. The olefin polymer according to claim 4 , wherein the olefin polymerization is homopolymerization of propylene or copolymerization of propylene and an α-olefin having 2 to 20 carbon atoms (excluding propylene). manufacturing method. 5. The method for producing an olefin polymer according to claim 4 , wherein the olefin polymerization is copolymerization of ethylene, a cyclic olefin, and an aromatic vinyl compound. 4. The olefin polymerization is homopolymerization of 1-butene or copolymerization of 1-butene and an α-olefin having 2 to 20 carbon atoms (excluding 1-butene). The method for producing the olefin polymer according to 1.