JP2017145240A - Transition metal compound, catalyst for olefin polymerization and method for producing olefin polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a novel transition metal compound to be a catalyst for olefin polymerization that can increase a molecular weight, facilitates the reaction of (higher) α-olefin with a controllable density, has high polymerization activity, or can polymerize propylene or 1-butene with high stereoregularity.SOLUTION: The present invention provides a transition metal metallocene compound such as isopropylidene bis(4-(3,5-di-iso-propyl-4-dimethyl aminophenyl)-1-indenyl) zirconium dichloride.SELECTED DRAWING: None

Description

  The present invention relates to 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 the presence of the catalyst. A process for producing an olefin polymer, particularly a process for producing an olefin polymer in which ethylene is homopolymerized or copolymerized with ethylene and an α-olefin, a homopolymer of propylene or a copolymer of propylene and an α-olefin A process for producing an olefin polymer, a process for producing an olefin polymer in which ethylene, a cyclic olefin and an aromatic vinyl compound are copolymerized, or a homopolymerization of 1-butene or a copolymer of 1-butene and an α-olefin. The present invention relates to a method for producing an olefin polymer for polymerization.

  A metallocene catalyst is composed of a transition metal atom and an organic compound called a ligand. The structure of this ligand can be changed by changing the position of the substituent and the steric electronic effect of the substituent. The physical properties of the polymer obtained by this are widely controlled. In order to synthesize characteristic polymers, many bridged metallocene compounds having a specific structure have been synthesized.

  For example, Patent Document 1 discloses an olefin polymerization catalyst comprising a transition metal complex having a ligand obtained by crosslinking indene with dimethylsilylene and methylalumoxane, and Patent Documents 2 and 3 disclose 4-position of the indene ring. A technique for highly controlling the stereoregularity and regioregularity of the resulting polyolefin by introducing an aromatic substituent into the above is disclosed.

  Patent Document 4 uses an azulene skeleton with an aromatic substituent introduced at the 4-position as a ligand, and Patent Document 5 introduces a heterocyclic substituent at the 2-position of the indene ring. A method for controlling the polymerization activity and the molecular weight and regularity of the resulting polyolefin is disclosed.

  Thus, various polymers are synthesized by changing the structure of the ligand in the metallocene catalyst. Furthermore, in order to synthesize more characteristic polymers and to achieve further high activation, synthesis of metallocene complexes having various structures is expected.

  In Non-patent Document 1, introduction of an electron-donating substituent, particularly a highly electron-donating substituent containing a heteroatom, into a cyclopentadienyl-type ligand is difficult in terms of polymerization activity in quantum scientific model calculations. Reported desirable.

  However, in actual studies using metallocene complexes with heteroatom-containing electron-donating substituents introduced as catalysts for olefin polymerization, they are far from industrial use in terms of catalyst activity and molecular weight of the polyolefin produced. As its cause, the interaction between the heteroatom of the electron-donating substituent and the aluminum compound in the polymerization system has been suggested (Non-patent Documents 2 and 3).

Patent Documents 6 and 7 disclose a metallocene complex having a specific structure as a method for solving these problems, but a complicated and long synthesis step is essential.
Patent Document 8 also discloses a metallocene complex having a ligand in which indene is bridged with isopropylidene, similar to those described in the claims, but it has an effect on the effect of introducing an electron-donating substituent. There is no mention or description of the examples.

JP-A-4-268307 Japanese Patent Application Laid-Open No. 6-100579 Japanese Patent Laid-Open No. 7-286005 Japanese Patent Laid-Open No. 10-226712 JP 2004-2259 A Special table 2014-525950 gazette Special table 2014-505136 gazette JP 2014-193846 A

Organometallics 2001, 20, 5375. Organometallics 1992, 11, 115. J. et al. Organomet. Chem. 1996, 520, 63.

  The present invention has been made in order to solve the above-described problems. The object of the present invention is to use a metallocene catalyst containing a transition metal compound having a specific structure to produce a polyolefin having a sufficient molecular weight and various high market values. A method for producing various olefin polymers such as a linear low density olefin polymer having a good olefin polymerization activity, a transition metal compound suitable for the olefin polymer, and a catalyst containing the transition metal compound It is to provide. That is, an 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 a (higher) α-olefin which can have a high molecular weight and whose density can be adjusted, and which has a high polymerization activity.

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

As a result of diligent research in view of such circumstances, the present inventor has introduced a specific group of substituents, that is, a heteroatom-containing electron-donating substituent and a substituent at a close position into the metallocene complex. It has been found that a transition metal compound having an olefin copolymerization property and giving an olefin polymer having a high molecular weight and a relatively narrow molecular weight distribution with good olefin polymerization activity can be obtained. That is, the inventors have found a catalyst and a method for producing an olefin polymer that are advantageous for producing various olefin polymers such as an ethylene copolymer having a sufficient molecular weight and a low density, and have completed the present invention.
The transition metal compound [A] of the present invention is represented by the following general formula [1].

In general formula [1], M is a periodic table group 4 transition metal atom, 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 that can be coordinated by a lone pair, and the anionic ligand is a halogen-containing group, silicon-containing group, oxygen-containing group, sulfur-containing group, nitrogen-containing group, phosphorus A containing group, a boron-containing group, an aluminum-containing group or a conjugated diene-based divalent derivative group, and when n is 2 or more, a plurality of groups represented by X may be the same or different from each other, and are bonded to each other. And Q may be a divalent hydrocarbon group, a divalent silicon-containing group, or a divalent germanium-containing group, and R ^{1 to} R ⁴ each independently represent a hydrogen atom, a carbon number of 1 ~ 40 hydrocarbon groups, halogen-containing groups, silicon-containing groups, oxygen-containing groups A nitrogen-containing group or a sulfur-containing group, may be the same as or different from each other, adjacent substituents of up to R ¹ to R ⁴ may be bonded to each other to form a ring, R ¹¹ to R ¹⁴ is Each independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, which may be the same or different, and R ^{a1 to} R ^a4 are each independently a hydrocarbon group having 1 to 20 carbon atoms, 6 to 40 aromatic hydrocarbon groups or silicon-containing groups, which may be the same or different, and each of R ^a1 and R ¹¹ , R ^a2 and R ¹² , R ^a3 and R ¹³ , R ^a4 and R ¹⁴ are R ^b1 and R ^b2 may be bonded to each other to form a ring, and R ^b1 and R ^b2 each represents a substituent represented by the following general formula [2] or a mother skeleton containing at least one atom selected from nitrogen, oxygen, and sulfur. A 5-membered ring, optionally substituted heterocyclic aromatic group Each may be the same or different, each Z ¹ and Z ² are independently, to the carbon atom to which they are attached form an optionally fused ring may have the same substituents as R ¹ to R ⁴ Represents a saturated or unsaturated hydrocarbon group having 3 or 4 carbon atoms, the substituent on Z ¹ is bonded to R ¹¹ and R ^12, and the substituent on Z ² is bonded to R ¹³ and R ¹⁴ to form a ring May be formed.

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, and R ^c is independently a hydrogen atom, 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 and R ^c forming R ^b2 may be bonded to each other and at least one selected from R ^a3 and R ^a4 to form an optionally substituted ring, and when m is 2 These may be the same or different, and R ^c may be bonded to each other to form a ring that may have a substituent.
The transition metal compound [A] is preferably represented by the following general formula [3].

In the 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 M, X in the general formula [1], respectively. , 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 are each independently a hydrogen atom, carbon number 1 ˜40 hydrocarbon groups, halogen-containing groups, silicon-containing groups, oxygen-containing groups, nitrogen-containing groups or sulfur-containing groups, each of which may be the same or different, 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 be bonded to each other to form a ring.

In the general formula [3], R ^b1 and R ^b2 are preferably a substituent represented by the general formula [2].
In the general formula [3], M is a zirconium atom or a hafnium atom, X is independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms or an oxygen-containing group, and Q is It is preferably 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, which may be the same or different, and R ² and R ⁴ are A hydrogen atom, and R ^{5 to} R ¹⁰ are each independently 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 or 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 1 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 40 carbon atoms, or a silicon-containing group, wherein R ^c is a hydrogen atom or a carbon number in the substituent represented by the general formula [2] 1 to 20 hydrocarbon groups, 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 Is a saturated ring when they are bonded to each other to form a ring structure, and when m is 2, when R ^c is bonded to each other to form a ring structure, it is preferably a saturated ring.

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, dialkyls An amino group or a pyrrolidinyl group is preferred.

The catalyst for olefin polymerization of the present invention comprises the transition metal compound [A] of the present invention.
Moreover, the manufacturing method of the olefin polymer of this invention is characterized by including the process of superposing | polymerizing an olefin in presence of the catalyst for olefin polymerization of this invention.

  In this specification, the term “polymerization” is used to mean not only homopolymerization but also copolymerization, and the term “polymer” includes not only a homopolymer but also a copolymer. Used in the inclusive sense.

  The catalyst for olefin polymerization containing the transition metal compound (A) according to the present invention has good olefin polymerization activity when olefin polymerization, particularly ethylene homopolymerization or ethylene and α-olefin copolymerization is performed. In addition, while producing an olefin polymer having a sufficient molecular weight, it exhibits particularly excellent α-olefin copolymerizability. Further, the molecular weight distribution of the obtained polymer tends to be relatively narrow, preferably in a low density region.

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

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

[[A] transition metal compound]
The transition metal compound [A] constituting the olefin polymerization catalyst of the present invention is a compound represented by the general formula [1], and preferably a compound represented by the general formula [3].
In the general formula [1], M is a Group 4 transition metal atom in 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. It is.

n is an integer of 1 to 4 that satisfies the valence of M, and is preferably 1 or 2.
X is a hydrogen atom, a halogen atom (X), a hydrocarbon group (G1), an anionic ligand, or a neutral ligand (L1) that can be coordinated by a lone pair of electrons, 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), An aluminum-containing group (Al) or a conjugated diene 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, a plurality of groups represented by X may be the same as or different from each other, and may be bonded to each other to form a ring. Further, when a plurality of the rings are present, they may be the same as or different from each other.

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 effects of the present invention are exhibited. 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, thiamil (1,2-dimethylpropyl) group, iso-hexyl (4-methylpentyl) group, 2,2-dimethylbutyl group, 2,3-dimethylbutyl group, 3,3-dimethylbutyl group, texyl (2,3-dimethylbutane - yl) group, a linear or branched alkyl group, such as 4,4-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-dien-1- Yl 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 (Buta-1,3-dienyl) group, penta-4-en-1-yl group, penta-3-en-1-yl group, penta-2-en-1-yl group, iso-pentenyl (3- Methylbut-3-en-1-yl) group, 2-methylbut-3-en-1-yl group, penta-4-en-2-yl group, prenyl (3-methylbut-2-en-1-yl) Linear or branched alkenyl groups or unsaturated double bonds such as Yumoto;
Linear or branched alkynyl group or unsaturated triple bond-containing group such as ethynyl group, prop-2-yn-1-yl group, propargyl (prop-1-yn-1-yl) group;
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 such as tri-iso-propylbenzyl group, 4-tert-butylbenzyl group, 3,5-di-tert-butylbenzyl group, 1-phenylethyl group, benzhydryl (diphenylmethyl) group An alkyl group and an unsaturated double bond-containing group;
Cyclic saturated hydrocarbon groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cycloheptatrienyl group, norbornyl group, norbornenyl group, 1-adamantyl group, 2-adamantyl group;
Phenyl group, tolyl (methylphenyl) group, xylyl (dimethylphenyl) group, mesityl (2,4,6-trimethylphenyl) group, cumenyl (iso-propylphenyl) group, duryl (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 And aromatic substituted (aryl) groups such as naphthyl group, biphenyl group, ter-phenyl group, binaphthyl group, acenaphthalenyl group, phenanthryl group, anthracenyl group, pyrenyl group, ferrocenyl group, and the like.

  Among the hydrocarbon groups, a methyl group, iso-butyl (2-methylpropyl) group, neopentyl (2,2-dimethylpropyl) group, thiamil (1,2-dimethylpropyl) group, benzyl group, phenyl group are preferable. Group, tolyl (methylphenyl) group, xylyl (dimethylphenyl) group, mesityl (2,4,6-trimethylphenyl) group, cumenyl (iso-propylphenyl) group.

  The halogen-containing group (H1) is not particularly limited as long as the effects of the present invention are exhibited. For example, a fluoromethyl group, a trifluoromethyl group, a trichloromethyl group, a pentafluoroethyl group, 2,2,2-trifluoro Examples thereof include an ethyl group, a fluorophenyl group, a difluorophenyl group, a trifluorophenyl group, a tetrafluorophenyl group, a pentafluorophenyl group, a trifluoromethylphenyl group, a bistrifluoromethylphenyl group, and a hexachloroantimonate anion.

Among the halogen-containing groups, a pentafluorophenyl group is preferable.
The silicon-containing group (Si1) is not particularly limited as long as the effects of the present invention are exhibited. For example, a trimethylsilyl group, a triethylsilyl group, a tri-iso-propylsilyl group, a diphenylmethylsilyl group, a tert-butyldimethylsilyl group Tert-butyldiphenylsilyl group, triphenylsilyl group, tris (trimethylsilyl) silyl group, trimethylsilylmethyl group and the like.

Among the silicon-containing groups, a trimethylsilylmethyl group is preferable.
The oxygen-containing group (O1) is not particularly limited as long as the effects of the present invention can be obtained. For example, a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an allyloxy group, an 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, And periodate anions.

Among the oxygen-containing groups, a methoxy group, an ethoxy group, an iso-propoxy group, and a tert-butoxy group are preferable.
The sulfur-containing group (S1) is not particularly limited as long as the effects of the present invention can be obtained. Groups, nonafryl (nonafluorobutanesulfonyl) group, mesylate (methanesulfonate) group, tosylate (p-toluenesulfonate) group, triflate (trifluoromethanesulfonate) group, nonaflate (nonafluorobutanesulfonate) group, etc. be able to.

Among the sulfur-containing groups, a triflate (trifluoromethanesulfonate) group is preferable.
The nitrogen-containing group (N1) is not particularly limited as long as the effects of the present invention can be obtained. Group, benzylamino group, dibenzylamino group, pyrrolidinyl group, piperidinyl group, morpholyl group, pyrrolyl group, bistrifurylimide group and the like.

Among the nitrogen-containing groups, a dimethylamino group, a diethylamino group, a pyrrolidinyl group, a pyrrolyl group, and a bistrifurylimide group are preferable.
Although it does not specifically limit as said phosphorus containing group (P) as long as there exists an effect of this invention, For example, a hexafluorophosphate anion etc. can be mentioned.

The boron-containing group (B) is not particularly limited as long as the effects of the present invention are exhibited. For example, 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, alkyl group, substituent An aryl group which may have a halogen atom or the like).

The aluminum-containing group (Al) is not particularly limited as long as the effect of the present invention is exhibited. 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 aryl group which may have a substituent or a halogen atom, etc.) capable of forming a four-membered ring can be mentioned.

  The conjugated diene-based divalent derivative group (DE) is not particularly limited as long as the effects of the present invention can be obtained. For example, a 1,3-butadienyl group, an isoprenyl (2-methyl-1,3-butadienyl) group, piperenyl Examples thereof include metallocyclopentene groups such as (1,3-pentadienyl) group, 2,4-hexadienyl group, 1,4-diphenyl-1,3-pentadienyl group, and cyclopentadienyl group.

  The neutral ligand (L1) capable of coordinating with a lone electron pair is not particularly limited as long as the effects of the present invention are exhibited. For example, ethers such as diethyl ether, tetrahydrofuran, dioxane, and 1,2-dimethoxyethane , Amines such as triethylamine and diethylamine, heterocyclic compounds such as pyridine, picoline, lutidine, oxazoline, oxazole, thiazole, imidazole and thiophene, organophosphorus compounds such as triphenylphosphine, tricyclohexylphosphine and tri-tert-butylphosphine Can be mentioned.

  Q is a divalent group that binds 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 the divalent hydrocarbon group include hydrocarbon groups having 1 to 20 carbon atoms such as an alkylene group, a substituted alkylene group, a cycloalkylene group, and an alkylidene group.
Specific examples of the divalent alkylene group having 1 to 20 carbon atoms, substituted alkylene group, cycloalkylene group and alkylidene group 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 Substituted alkylene groups such as 1-methylethylene, 1,2-dimethylethylene, 1-ethyl-2-methylethylene, ditolylmethylene, methylnaphthylmethylene, dinaphthylmethylene, benzylphenylmethylene, dibenzylmethylene, 1-methylethylene, 1,2-dimethylethylene, 1-ethyl-2-methylethylene;
Cycloalkylene groups such as cyclopropylidene, cyclobutylidene, cyclopentylidene, cyclohexylidene, cycloheptylidene, bicyclo [3.3.1] nonylidene, norbornylidene, adamantylidene, tetrahydronaphthylidene, dihydroindanilidene ;
Examples include alkylidene groups such as ethylidene, propylidene and butylidene.

  Examples of divalent silicon-containing groups include silylene, methylsilylene, dimethylsilylene, diisopropylsilylene, dibutylsilylene, methylbutylsilylene, methyl-t-butylsilylene, dicyclohexylsilylene, methylcyclohexylsilylene, methylphenylsilylene, diphenylsilylene, and ditolyl. Examples include silylene, methylnaphthylsilylene, dinaphthylsilylene, cyclodimethylenesilylene, cyclotrimethylenesilylene, cyclotetramethylenesilylene, cyclopentamethylenesilylene, cyclohexamethylenesilylene, cycloheptamethylenesilylene group, preferably dimethylsilylene, Dibutylsilylene, diphenylsilylene, cyclotrimethylenesilylene, cyclotetramethylenesilylene, cyclopentamethylenesilylene It is.

Examples of the divalent germanium-containing group include a group obtained by converting silicon into germanium in the divalent silicon-containing group.
Preferred groups for Q are alkylene groups having 1 to 20 carbon atoms, substituted alkylene groups, cycloalkylene groups, and silicon-containing groups.

R ^{1 to} R ⁴ are each independently 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), or a nitrogen-containing group. A group (N2) or a sulfur-containing hydrocarbon group (S2), which may be the same or different, and adjacent substituents R ^{1 to} R ⁴ may be bonded to each other to form a ring. Further, when a plurality of the rings are present, they may be the same as or different from each other.

  The hydrocarbon group having 1 to 40 carbon atoms (G2) is preferably a hydrocarbon group having 1 to 20 carbon atoms (excluding aromatic hydrocarbon groups) and an aromatic having 6 to 40 carbon atoms. It refers to a 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 (arylalkyl group).

Although it does not specifically limit as said C1-C40 hydrocarbon group (G2) as long as there exists an effect of this invention, For example, a methyl group, an ethyl group, 1-propyl group, 1-butyl group, 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, thiamil (1,2-dimethylpropyl) group, Ntan-3-yl group, 2-methylpentyl 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, texyl (2,3-dimethylbutane -2-yl) group, 3-methylpentan-3-yl group, 3,3-dimethylbut-2-yl group, hexane-3-yl group, 2-methylpentan-3-yl group, heptane-4- Yl group, 2,4-dimethylpentan-3-yl group, 3-ethylpentane-3-yl group, 4,4-dimethylpentyl group, 4-methylheptan-4-yl group, 4-propylheptane-4- Ile group, 2, 3 3- trimethyl-2-yl group, a linear or branched alkyl group having 1 to 20 carbon atoms, such as 2,3,4-trimethylpentane-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-dien-1- Yl 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 (Buta-1,3-dienyl) group, penta-4-en-1-yl group, penta-3-en-1-yl group, penta-2-en-1-yl group, iso-pentenyl (3- Methylbut-3-en-1-yl) group, 2-methylbut-3-en-1-yl group, penta-4-en-2-yl group, prenyl (3-methyl-but-2-en-1- Yl) group, 2-methyl-but-2-en-1-yl group, penta-3-ene 2-yl group, 2-methyl-but-3-en-2-yl group, penta-1-en-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-buta-1,3-dien-1-yl) group, penta-2,4-diene- 2-yl group, hexa-5-en-1-yl group, hexa-4-en-1-yl group, hexa-3-en-1-yl group, hexa-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, hexa-5-ene- 2-yl group, 4-methyl-pent-3-en-1-yl group, 3-methyl-pent-3-en-1-yl group, 2,3-dimethyl Ru-but-2-en-1-yl group, 2-methylpent-4-en-2-yl group, 3-ethylpent-1-en-3-yl group, hexa-3,5-dien-1-yl Group, hexa-2,4-dien-1-yl group, 4-methylpenta-1,3-dien-1-yl group, 2,3-dimethyl-buta-1,3-dien-1-yl group, hexa A straight chain having 2 to 40 carbon atoms such as a -1,3,5-trien-1-yl group, a 2- (cyclopentadienyl) propan-2-yl group, and a 2- (cyclopentadienyl) ethyl group; A chain or branched alkenyl group or an unsaturated double bond-containing group;
Ethynyl group, prop-2-yn-1-yl group, propargyl (prop-1-in-1-yl) group, but-1-in-1-yl group, but-2-yn-1-yl group, But-3-yn-1-yl group, penta-1-in-1-yl group, penta-2-in-1-yl group, penta-3-in-1-yl group, penta-4-in- 1-yl group, 3-methyl-but-1-in-1-yl group, penta-3-in-2-yl group, 2-methyl-but-3-in-1-yl group, penta-4- In-2-yl group, hexa-1-in-1-yl group, 3,3-dimethyl-but-1-in-1-yl group, 2-methyl-pent-3-in-2-yl group, Carbon sources such as 2,2-dimethyl-but-3-yn-1-yl group, hexa-4-in-1-yl group, and hexa-5-in-1-yl group Linear or branched alkynyl group or unsaturated triple bond-containing group having 2 to 40;
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-phenyl) Yl) group, 2- (4-methylphenyl) propan-2-yl group, 2- (3,5-dimethylphenyl) propan-2-yl group, 2- (4-tert-butylphenyl) propan-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- Til-1-phenylpropan-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) propan-2-yl group, (1-benzoindenyl) diphenylmethyl group, 2- (1-benzoindenyl) L) ethyl group, 2- (9-fluorenyl) propan-2-yl group, (9-fluorenyl) diphenylmethyl group, 2- (9-fluorenyl) ethyl group, 2- (1-azurenyl) propan-2-yl Group, (1-azurenyl) diphenylmethyl group, 2- (1-azurenyl) ethyl group and the like, an aromatic-containing linear or branched alkyl group having 7 to 40 carbon atoms and an unsaturated double bond-containing group ;
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, cycloheptyl, cycloheptenyl, cycloheptatrienyl, 1-methylcycloheptyl, 1-allylcycloheptyl, 1-benzylcycloheptyl, cyclooctyl, cyclooctenyl, cycl Octadienyl 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- Methyl adamantyl), 1- (2-phenyladamantyl), 1- (3-phenyladamantyl), 1- (4-phenyladamantyl), 1- 3,5-dimethyladamantyl), 1- (3,5,7-trimethyladamantyl), 1- (3,5,7-triphenyladamantyl), pentarenyl group, indenyl group, fluorenyl group, indacenyl group, tetrahydroindace Cyclic saturated and unsaturated hydrocarbon groups having 3 to 40 carbon atoms, such as an nyl group, a benzoindenyl group, an azulenyl group;
Phenyl group, tolyl (methylphenyl) group, xylyl (dimethylphenyl) group, mesityl (2,4,6-trimethylphenyl) group, cumenyl (iso-propylphenyl) group, duryl (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, carbon atoms, such as ferrocenyl group aromatic substitution (aryl) groups having 6 to 40; and the like.

  Among the linear or branched alkyl groups having 1 to 40 carbon atoms, a methyl group, an ethyl group, a 1-propyl group, a 1-butyl group, a 1-pentyl group, a 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, texyl (2,3-dimethylbut-2-yl) group, -Methylpentan-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. Among them, methyl group, ethyl group, 1-propyl group, 1-butyl group, 1-pentyl group, 1-hexyl are more preferable. Group, iso-propyl group, 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 a vinyl group, an allyl group, a but-3-en-1-yl group, a crotyl group. (But-2-en-1-yl) group, methallyl (2-methylallyl) group, penta-4-en-1-yl group, prenyl (3-methyl-but-2-en-1-yl) group, Penta-1,4-dien-3-yl group, hexa-5-en-1-yl group, 2-methylpent-4-en-2-yl group, 2- (cyclopentadienyl) propan-2-yl Group, 2- (cyclopentadienyl) ethyl group, etc., among which, vinyl group, allyl group, but-3-en-1-yl group, penta-4-en-1-yl group are more preferable. , Prenyl (3-methyl-but-2-en-1-yl) A 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, ethynyl group, prop-2-yn-1-yl group, propargyl (prop-1 -In-1-yl) group, but-2-yn-1-yl group, but-3-in-1-yl group, penta-3-in-1-yl group, penta-4-in-1- Yl group, 3-methyl-but-1-in-1-yl group, 3,3-dimethyl-but-1-in-1-yl group, hexa-4-in-1-yl group, hexa-5- In-1-yl group and the like can be mentioned, and among them, prop-2-yn-1-yl group, propargyl (prop-1-in-1-yl) group, but-2-yne-1- are more preferable. An yl group and a but-3-yn-1-yl group.

  Among the aromatic-containing linear or branched alkyl group and unsaturated double bond-containing group having 7 to 40 carbon atoms, preferably a benzyl group, a 2-methylbenzyl group, a 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) L) 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, cyclopentadienyldiphenylmethyl 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, etc. More preferably, benzyl group, benzhydryl (diphenylmethyl) group, cumyl (2-phenylpropan-2-yl) group, 1,1-diphenylethyl group, trityl (triphenylmethyl) group, 2-phenylethyl group, 3 -A phenylpropyl group and a 2-cinnamyl (3-phenylallyl) group.

  Among the cyclic saturated and unsaturated hydrocarbon groups having 3 to 40 carbon atoms, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclopentenyl group, a cyclopentadienyl group, a 1-methylcyclopentyl group, 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, pentarenyl group, indenyl group, fluorenyl group and the like. Among them, more preferred are a cyclopentyl group, a cyclopentenyl group, a 1-methylcyclopentyl group, a cyclohexyl group, a cyclohexenyl group, a 1-methylcyclohexyl group, and a 1-adamantyl group.

  Among the aromatic substituted (aryl) groups having 6 to 40 carbon atoms, phenyl group, tolyl (methylphenyl) group, xylyl (dimethylphenyl) group, mesityl (2,4,6-trimethylphenyl) are preferable. 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, etc. 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 group, biphenyl group, phenanthryl group, and anthracenyl group.

  The halogen-containing group (H2) is not particularly limited as long as the effects of the present invention are exhibited. For example, a fluoromethyl group, a trifluoromethyl group, a trichloromethyl group, a 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, Fluoromethoxyphenyl group, vist Fluoromethoxyphenyl 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, tri Fluorophenoxy group, pentafluorophenoxy group, di-tert-butyl-fluorophenoxy group, trifluoromethylphenol Alkoxy groups, bis-trifluoromethylphenoxy group, and a trifluoromethoxy phenoxy group, bistrifluoroacetic methoxyphenoxy group, difluoromethylene dioxy phenyl group, bis-trifluoromethylphenyl imino methyl group, trifluoromethylthio group, and the like.

  Among the halogen-containing groups, a fluoromethyl group, a trifluoromethyl group, a pentafluoroethyl group, a 2,2,2-trifluoroethyl group, a 3,3,3-trifluoropropyl group, 4,4,4 are preferable. -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, difluoromethylenedioxy An enyl group, a trifluoromethylthio group, and the like. Among them, more preferably, a trifluoromethyl group, a fluorophenyl group, a pentafluorophenyl group, a trifluoromethylphenyl group, a bistrifluoromethylphenyl group, a pentafluorobiphenyl group, A trifluoromethoxy group and a pentafluorophenoxy group;

  The silicon-containing group (Si2) is not particularly limited as long as the effects of the present invention are exhibited. For example, a trimethylsilyl group, a triethylsilyl group, a tri-iso-propylsilyl group, a diphenylmethylsilyl group, a tert-butyldimethylsilyl group , Tert-butyldiphenylsilyl group, triphenylsilyl group, tris (trimethylsilyl) silyl group, cyclopentadienyldimethylsilyl group, di-n-butyl (cyclopentadienyl) silyl group, cyclopentadienyldiphenylsilyl group, Indenyldimethylsilyl group, di-n-butyl (indenyl) silyl group, indenyldiphenylsilyl group, fluorenyldimethylsilyl group, di-n-butyl (fluorenyl) silyl group, fluorenyldiphenylsilyl group, 4- Trimethylsilylphenyl 4-triethylsilylphenyl group, 4-tri-iso-propylsilylphenyl group, 4-tert-butyldiphenylsilylphenyl group, 4-triphenylsilylphenyl group, 4-tris (trimethylsilyl) silylphenyl group, etc. Can do.

  Among the silicon-containing groups, trimethylsilyl group, triethylsilyl group, tri-iso-propylsilyl group, tert-butyldimethylsilyl group, triphenylsilyl group, cyclopentadienyldimethylsilyl group, cyclopentadienyldiphenylsilyl are preferable. Group, indenyldimethylsilyl group, indenyldiphenylsilyl group, fluorenyldimethylsilyl group, fluorenyldiphenylsilyl group, 4-trimethylsilylphenyl group, 4-triethylsilylphenyl group, 4-tri-iso-propylsilylphenyl Group, 4-triphenylsilylphenyl group, etc. Among them, more preferred are trimethylsilyl group, triethylsilyl group, tert-butyldimethylsilyl group, 4-trimethylsilylphenyl group, 4-triethylsilyl group. Butylphenyl group, a 4-tri -iso- propyl silyl phenyl group.

  The oxygen-containing group (O2) is not particularly limited as long as the effects of the present invention are exhibited. For example, a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an allyloxy group, an n-butoxy group, sec- Butoxy, iso-butoxy, tert-butoxy, methallyloxy, prenyloxy, benzyloxy, methoxymethoxy, methoxyethoxy, phenoxy, naphthoxy, toluyloxy, iso-propylphenoxy, allylphenoxy Group, tert-butylphenoxy group, methoxyphenoxy group, iso-propoxyphenoxy group, allyloxyphenoxy group, biphenyloxy group, binaphthyloxy group, methoxymethyl group, allyloxymethyl group, benzyloxymethyl group, phenoxymethyl group, Toxiethyl 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, A furfuryl group, a benzofuryl group, a dibenzofuryl group, and the like can be given.

  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, toluyloxy group are preferable. , 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, Examples include oxyphenyl group, phenoxyphenyl group, methylenedioxyphenyl group, furyl group, methylfuryl group, tetrahydropyranyl group, furfuryl group, benzofuryl group, dibenzofuryl group and the like. Among them, 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, a dibenzofuryl group.

  The nitrogen-containing group (N2) is not particularly limited as long as the effect of the present invention is exhibited. For example, an amino group, a dimethylamino group, a diethylamino group, an allylamino group, a diallylamino group, a didecylamino group, a benzylamino group, and a dibenzyl Amino, pyrrolidinyl, piperidinyl, morpholyl, azepinyl, dimethylaminomethyl, dibenzylaminomethyl, pyrrolidinylmethyl, dimethylaminoethyl, benzylaminomethyl, benzylaminoethyl, pyrrolidinyl Ethyl group, dimethylaminovinyl group, benzylaminovinyl group, pyrrolidinylvinyl group, dimethylaminopropyl group, benzylaminopropyl group, pyrrolidinylpropyl group, dimethylaminoallyl group, benzylaminoallyl group, pyrrolidinylallyl group Ami Phenyl 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, indolinyl group Carbazolyl group, di-tert-butylcarbazolyl group, imidazolyl group, dimethylimidazolidinyl group, benzoimidazolyl group, oxazolyl group, oxazolidinyl group, benzoxazolyl group and the like.

  Among the nitrogen-containing groups, an 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, pyrrolidini Ruphenyl, pyrrolylphenyl, carbazolylphenyl, di-tert-butylcarbazolylphenyl, pyrrolyl, pyridyl, quinolyl, tetrahydroquinolyl, iso-quinolyl, tetrahydro-iso-quinolyl Group, in Ryl group, indolinyl group, carbazolyl group, di-tert-butylcarbazolyl group, imidazolyl group, dimethylimidazolidinyl group, benzoimidazolyl group, oxazolyl group, oxazolidinyl group, benzoxazolyl group, etc. Among them, more preferred are amino group, dimethylamino group, diethylamino group, pyrrolidinyl group, dimethylaminophenyl group, pyrrolidinylphenyl group, pyrrolyl group, pyridyl group, carbazolyl group, and imidazolyl group.

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

  Among the sulfur-containing groups, a thienyl group, a methylthienyl group, a thienofuryl group, a thienothienyl group, a benzothienyl group, a dibenzothienyl group, a thienobenzofuryl group, a benzodithienyl group, a thiazolyl group, and a benzothiazolyl group are preferable.

Among R ^{1 to} R ⁴ , when adjacent substituents are bonded to each other to form a ring, the ring is preferably a saturated ring. The ring may form a 5- or 8-membered saturated or unsaturated hydrocarbon group condensed to a 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. In this case, examples of the structure combined with the cyclopentadienyl part of the mother nucleus include, for example, substituted cyclopentathiophene, substituted indene, substituted cyclopentatetrahydronaphthalene, substituted 4,5,6,7-tetrahydro Inden etc. are mentioned.

R ¹ and R ³ are each independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms in the hydrocarbon group having 1 to 40 carbon atoms (G2), and R ² and R ⁴ are hydrogen atoms. It is preferable that

R ^{11 to} R ¹⁴ are each independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, which 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 as the hydrocarbon group having 1 to 40 carbon atoms (G2). Preferably, it is a hydrocarbon group selected from C1-C20 aliphatic or alicyclic hydrocarbon groups. The hydrocarbon group having 1 to 20 carbon atoms also includes a substituent having an aromatic structure such as an arylalkyl group (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), A C1-C20 hydrocarbon group and a C6-C40 aromatic hydrocarbon group are mentioned. Moreover, as said silicon-containing group, the silicon-containing group illustrated by the said silicon-containing group (Si2) is mentioned, for example.

  Examples of the hydrocarbon group having 1 to 20 carbon atoms include the aforementioned aliphatic hydrocarbon group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group having 1 to 20 carbon atoms, and an aryl having 1 to 20 carbon atoms. An alkyl group (arylalkyl group) is mentioned as a preferred group.

  Among the hydrocarbon groups having 1 to 20 carbon atoms, a 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, cyclo Kutadienyl 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-diphenylethyl group, trityl (triphenylmethyl) group, 2-phenylethyl group, 3-phenylpropyl group, 2-cinnamyl (3-phenylallyl) group.

  Among the aromatic hydrocarbon groups having 6 to 40 carbon atoms, a 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 A 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 are preferable. Group, 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 , and R ^a4 and R ¹⁴ may be bonded to 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 two or more rings exist, they may be the same as or different from each other. Although it is not particularly limited as long as the effect of the present invention is exerted, it is preferably a 5- or 6-membered ring. In this case, examples of the structure combined with the aromatic ring portion of the mother nucleus include substituted naphthalene, substituted anthracene, substituted phenanthrene, substituted indan And substituted tetrahydronaphthalene.

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. To 10 hydrocarbon groups.

R ^b1 and R ^{b2 each} have a substituent represented by the general formula [2] or a 5-membered ring having a mother skeleton containing at least one atom selected from nitrogen, oxygen, and sulfur. And may be the same or different from each other.

In the general formula [2], V is an atom selected from nitrogen, oxygen or sulfur, preferably nitrogen or oxygen.
In addition, the wavy line in the said General formula [2] shows the coupling | bond part with a benzene ring.
m is an integer of 1 or 2 satisfying the valence of V. When m is 2, 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), a silicon-containing group (Si2), an ether bond-containing hydrocarbon group or a tertiary amino group-containing hydrocarbon group; It is preferably a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.

  Among the hydrocarbon groups having 1 to 40 carbon atoms (G2), a methyl group, an ethyl group, a 1-propyl group, a 1-butyl group, a 1-pentyl group, a 1-hexyl group, and a 1-heptyl group are preferable. 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-adamanti 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, 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, ter-phenyl group.

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

  The tertiary amino group-containing hydrocarbon group is not particularly limited as long as the effects of the present invention are exerted. For example, 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-benzoimidazolyl group, N-oxazolyl group, N-oxazolidinyl group, N-benzoxazolyl group Group and the like.

R ^c forming R ^b1 has at least one selected from R ^a1 and R ^a2 and R ^c forming R ^b2 is bonded to at least one selected from R ^a3 and R ^a4 and has a substituent. A ring that may be formed may be formed. 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 is bonded to at least one selected from R ^a1 and R ^a2, and R ^c forming R ^b2 is bonded to at least one selected from R ^a3 and R ^a4 to form a ring structure In this case, a saturated ring is preferable. In addition, when there are a plurality of rings, they may be the same as or different from each other. Although it is not particularly limited as long as the effect of the present invention is exerted, it is preferably a 5- or 6-membered ring. In this case, as a structure combined with the aromatic ring portion of the mother nucleus, for example, a 2,7-dimethylbenzofuran-5-yl group 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-dimethylindoline-5-yl group, 1,9-dimethylcarbazole- And 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- - yl group, 9-julolidinyl (2,3,6,7-tetrahydro-1H, 5H-benzo [ij] quinolizine-9-yl) group.

R ^c , when V is a nitrogen atom and m is 2, R ^c may be bonded to each other to form a ring which may have a substituent, for example, a 5- to 8-membered saturated or unsaturated hydrocarbon group. May be. When R ^c is bonded to each other to form a ring structure, a saturated ring is preferable. 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. In this case, examples of the structure combined with the nitrogen atom portion of the mother nucleus include, for example, 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 group and the like are preferable, preferably N-pyrrolidinyl group, N-piperidinyl group , N-morpholyl group, N-methyl-N-piperazinyl group.

  Examples of the heterocyclic aromatic group which may have a substituent having a 5-membered mother skeleton containing at least one atom selected from nitrogen, oxygen and sulfur include, for example, the following general formula [4a] Group represented by ~ [4h].

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 R ^d is independently a hydrogen atom or a carbon number of 1 to 40 carbon atoms (G2). ˜20 hydrocarbon groups, which may be the same or different.

In addition, the wavy line in the said general formula [4a]-[4h] shows the coupling | bond part with a benzene ring.
Among the hydrocarbon groups having 1 to 20 carbon atoms, a 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, benzyl, benzhydryl (diphenylmethyl), cumyl (2-phenylpropan-2-yl), 1,1-diphenylethyl, trityl (triphenylmethyl), 2-phenylethyl, 3- Phenylpropyl group, 2-cinnamyl (3-phenylallyl) group, phenyl group, tolyl (methylphenyl) group, xylyl (dimethylphenyl) group, mesityl (2,4,6-trimethylphenyl) group, cumenyl (iso-propyl) Phenyl) 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, Nantryl 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.

R ^d is a 5- to 8-membered saturated or unsaturated hydrocarbon group which may have a substituent, wherein R ^d adjacent to each other are bonded to each other and independently fused to a 5-membered heterocyclic moiety. Although it is not particularly limited as long as the effect of the present invention is exerted, it is preferably a 5- or 6-membered ring. In this case, examples of the structure combined with the aromatic ring portion of the mother nucleus include, for example, benzofuran ring, benzo Examples include a thiophene ring, an indole ring, a carbazole ring, a benzoxazole ring, a benzothiazole ring, a benzimidazole ring, and a benzopyrazole ring.

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

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

Z ¹ and Z ² are each independently a saturated or unsaturated group having 3 or 4 carbon atoms forming a condensed ring which may have the same substituent as R ^{1 to} R ⁴ with respect to the carbon atom to which Z ¹ and Z ² are bonded. In this case, the structure combined with the cyclopentadienyl part of the mother nucleus is substituted cyclopentathiophene ring, substituted indene ring, substituted tetrahydroindene ring, substituted azulene ring, substituted dihydroazulene ring, substituted tetrahydroazulene A ring, a substituted hexahydroazulene ring, and the like, and a substituted indene ring is preferable.

The substituent on Z ¹ may be bonded to each other to form a ring with R ¹¹ and R ¹² and the substituent on Z ² may be combined with R ¹³ and R ^14. Examples of the structure combined with the portion and the aromatic ring portion include a 3,6-dihydrocyclopentafluorene ring, a cyclopentaphenanthrene ring, and a 6,7-dihydrocyclopentaphenanthrene ring. In addition, when two or more rings exist, they may be the same as or different from each other.

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 the 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 M, X in the general formula [1], respectively. , N, Q, R ^{1 to} R ⁴ , R ^{11 to} R ¹⁴ , R ^{a1 to} R ^a4 , R ^b1 and R ^b2 have the same meanings.

R ^{5 to} R ¹⁰ are each independently 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.

Examples and preferred examples of the hydrocarbon group having 1 to 40 carbon atoms (G2) include the same as those described above for R ^{1 to} R ⁴ .
Examples and preferred examples of the halogen-containing group (H2) include the same groups as those described above for R ^{1 to} R ⁴ .

Illustrative and preferred examples of the silicon-containing group (Si2) include the same as those described above for R ^{1 to} R ⁴ .
Illustrative and preferred examples of the oxygen-containing group (O2) include the same as those described for R ^{1 to} R ⁴ .

Examples and preferred examples of the nitrogen-containing group (N2) include the same groups as those described above for R ^{1 to} R ⁴ .
Examples and preferred examples of the sulfur-containing group (S2) include the same as those described above for R ^{1 to} R ⁴ .

The adjacent substituents from R ^{5 to} R ¹⁰ may be bonded to 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 fused to the aromatic ring portion. In addition, when two or more rings exist, they may be the same as or different from each other. Although it is not particularly limited as long as the effect of the present invention is exerted, it is preferably a 5- or 6-membered ring. In this case, as a structure combined with a cyclopentadienyl part and an aromatic ring part of the mother nucleus, for example, a substituted tetrahydroindacene ring And substituted cyclopentatetrahydronaphthalene, and examples of the condensed ring structure of the R ^{1 to} R ⁴ moieties include a substituted fluorene ring, which is preferably a substituted tetrahydroindacene ring. In addition, when R ⁵ and R ⁶ and R ⁸ and R ⁹ form a ring structure, a saturated ring is preferable.

R ⁵ and R ¹¹ or R ¹² , R ⁸ and R ¹³ or R ¹⁴ may be bonded to 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 fused to the aromatic ring portion. In addition, when two or more rings exist, they may be the same as or different from each other. 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. In this case, the structure combined with the cyclopentadienyl part and the aromatic ring part of the mother nucleus is, for example, 3,6-dihydro Examples include a cyclopentafluorene ring, a cyclopentaphenanthrene ring, and a 6,7-dihydrocyclopentaphenanthrene ring.

R ^{5 to} R ¹⁰ are each independently preferably a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms in the hydrocarbon group having 1 to 40 carbon atoms (G2), or an oxygen-containing group (O2). .
Of the hydrocarbon group having 1 to 20 carbon atoms, preferred examples include the same ones as mentioned above R ^a1 to R ^a4.

Of the oxygen-containing groups (O2), preferred examples include the same alkoxy groups as those described above for R ^b1 and R ^b2 .
R ^{5 to} R ¹⁰ are more preferably each independently a hydrogen atom or the hydrocarbon group having 1 to 20 carbon atoms.

Among the hydrocarbon groups having 1 to 20 carbon atoms, particularly preferred examples include a methyl group, an iso-propyl group, and a tert-butyl (2-methylpropan-2-yl) group.
R ^{5 to} R ¹⁰ are particularly preferably all hydrogen atoms.

[Production Method of 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 typical synthesis route is shown below, but the production method is not particularly limited.

  First, a 3,4,5-substituted aromatic compound having a heteroatom-containing electron-donating substituent at the 4-position and having a substituent introduced at the 3, 5-position in the vicinity is a known method. The manufacturing method is not particularly limited. Known production methods include, for example, “J. Am. Chem. Soc. 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. 2006, 2727. ", WO 2007/034975," J. Am. Chem. " Soc. 2014, 136, 10166. ”,“ Eur. J. Org. Chem. 2011, 6100. ”, WO 2013/011956, and the like.

  The aromatic substituted cyclopentadiene compound can be produced by a known method such as a cross-coupling reaction using the 3,4,5-substituted aromatic compound as a raw material, and the production method is particularly limited. is not. Known production methods include, for example, “Organometallics 2004, 23, 3267.”, WO 1998/040331, WO 1998/046547, JP-A 2004-2259, “Organometallics 2006, 25, 1217.”, US Pat. 7910783, Special Table 2011-500800, “Organometallics 2011, 30, 5744.”, “Chem. Eur. J. 2012, 18, 4174.”, “Organometallics 2012, 31, 4962.”, JP-A-2014-14. Japanese Patent Laid-Open No. 201519, Japanese Patent Application Laid-Open No. 7-286005, WO 2001/027124, WO 2004/029062, WO 2006/126608, etc. by the present applicant, etc. And the like.

  Further, 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. Absent. Known production methods include, for example, “J. Organomet. Chem. 1997, 530, 75.”, “J. Organomet. Chem. 2001, 619, 280. In addition to the above-mentioned methods for producing substituted cyclopentadiene compounds. JP, 2001-11089, JP, 2003-201259, JP, 2011-144157, JP, 2014-193846, etc. are mentioned.

  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. No. 5,972,822, JP-A-10-109996, “J. Organomet. Chem. 1997, 527”. , 297. ", JP 2002-88092 A," Organometallics 2012, 31, 4340. ", WO 2004/029062 by the present applicant, and the like.

  In addition, the transition metal compound [A] of the present invention has two directions of the surface of the cyclopentadienyl ring portion that binds to the central metal across the bridge portion (front and back surfaces). Therefore, when the two cyclopentadienyl ring moieties bonded to the central metal across the bridging moiety are the same, there are two types of structural isomers, racemic and meso isomers. When the dienyl ring moieties are different from each other, there are two types of structural isomers, pseudo-racemic and pseudo-meso. In the transition metal compound [A] represented by the general formula [1] or [3], the cyclopentadienyl ring partial aromatic substituents are located on different sides, and are a racemic body and a pseudo-racemic body. The meso form and the pseudo meso form are of the structure represented by the following general formula [5a] or [5b] in which the cyclopentadienyl ring partial aromatic substituent is located on the 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. . As the known production method, those mentioned as the production method of the transition metal compound [A] are listed.

  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 thereby. In the present invention, the transition metal compound [A] may be used alone or in combination of two or more thereof, a racemic body or a pseudo-racemic body may be used, and a structural isomer mixture is used. Or a combination of these.

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

Specific examples of the metal portion MX _{n is, 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 (CH 2 -Si (} Me) 3) 2, Ti (ОMe) 2, Ti (ОiPr) 2, Ti (NMe 2) 2, Ti (ОMs) 2, Ti (ОTs) 2, Ti (OTF) ₂ , ZrF ₂ , ZrCl ₂ , ZrBr ₂ , ZrI ₂ , Zr (Me) ₂ , Zr (Bn) ₂ , Zr (Allyl) ₂ , Zr (CH ₂ -tBu) ₂ , Zr (η ⁴ −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 (CH 2 -Si (} Me) 3) 2, Zr (ОMe) 2, Zr _{(ОiPr) 2, Zr (NMe} 2) 2, Zr (ОMs) 2, Zr (ОTs) 2, Zr (ОTf) 2, HfF 2, 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 (ОMe) ₂ , Hf (ОiPr) ₂ , Hf ( NMe ₂ ) ₂ , Hf (ОMs) ₂ , Hf (ОTs) ₂ , Hf (ОTf ₂ ). 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, NMe ₂ is a dimethylamino group, and OMs is methanesulfonate OTs is a p-toluenesulfonate group, and OTf is a trifluoromethanesulfonate group.

According to the above notation, the cyclopentadienyl ring portion is α-1 in [Table 1], and the cyclopentadienyl ring portion aromatic substituent (Ar) is β-1, cyclopenta in [Table 2]. In the dienyl ring partial aromatic substituent, the substituent (T) at positions 3 and 5 is γ-4 in [Table 3], and the substituent (Y) at position 4 in the cyclopentadienyl ring partial aromatic substituent is Δ-20 in [Table 4], the substituent (R) adjacent to the cyclopentadienyl ring partial bridge portion is ε-1 in [Table 5], and the bridge portion is η-16 in [Table 7]. When composed of a combination and MX _{n of} the metal part is ZrCl ₂ , the following compound [6] is exemplified.

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。

The cyclopentadienyl ring moiety is α-2 in [Table 1], the cyclopentadienyl ring partial aromatic substituent (Ar) is β-8 in [Table 2], and the cyclopentadienyl ring partial bridge Substituent substituent (R) is composed of a combination of ε-13 in [Table 5], a bridging portion is η-32 in [Table 7], and MX _{n of} the metal portion is Zr (NMe ₂ ) _2. In this case, 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。

The cyclopentadienyl ring moiety is α-11 in [Table 1], and the cyclopentadienyl ring partial aromatic substituent (Ar) is β-1, in [Table 2], the cyclopentadienyl ring partial fragrance. Substituents (T) at positions 3 and 5 in the aromatic substituent are γ-10 in [Table 3], and substituents (Y) at position 4 in the cyclopentadienyl ring partial aromatic substituent are in [Table 4]. Δ-33, the cyclopentadienyl ring partial bridge portion adjacent position (R) is a combination of ε-2 in [Table 5], and the bridge portion is a combination of η-26 in [Table 7], When MX _{n of the} metal portion 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 portions bonded to the metal portion MX _n are not the same or different, one cyclopentadienyl ring portion is represented by α-4, cyclohexane in [Table 1]. The pentadienyl ring partial aromatic substituent (Ar) is β-1 in [Table 2], and the substituents (T) at positions 3 and 5 in the cyclopentadienyl ring partial aromatic substituent are in [Table 3]. Γ-9 and γ-11, the substituent (Y) at the 4-position in the cyclopentadienyl ring partial aromatic substituent is δ-5 in [Table 4], the cyclopentadienyl ring partial bridge portion adjacent position The substituent (R) is ε-8 in [Table 5], and the other cyclopentadienyl ring portion is α-8 in [Table 1], the cyclopentadienyl ring partial aromatic substituent (Ar ) Is β-6 in [Table 2], and the substituent (R) at the position adjacent to the cyclopentadienyl ring partial bridge is [Table 5]. -11, a cyclopentadienyl ring partial oxygen atom-bonded alkyl substituent (Alk) is ζ-1 in [Table 6], and a bridging portion is composed of a combination of η-1 in [Table 7], When MX _{n of the} moiety is Ti (η ⁴ -1,3-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。

The reason why the above transition metal compound exhibits unique performance is not clear at present, but the inventor of the present application estimates as follows.

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

((B-1) Organometallic compound)
As the organometallic compound (B-1) used in the present invention, specifically, periodic table groups 1, 2, 12, and 13 represented by the following general formulas (B-1a) to (B-1c) And 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 from each other, and each represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, and Y represents a halogen atom. P is 0 <p ≦ 3, q is 0 ≦ q <3, r is 0 ≦ r <3, s is 0 ≦ s <3, and m + n + p + q = 3. Organoaluminum compounds;
M ³ AlR ^c1 ₄ (B-1b)
(In the general formula (B-1b), M ³ represents Li, Na or K, and R ^c1 represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms). Complex alkylated product of alkali metal of group 1 of the table and aluminum;
R ^{d Re} M ⁴ (B-1c)
(In the general formula (B-1c), R ^d and R ^e may be the same or different from each other, each represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, and M ⁴ represents Mg. , Zn or Cd.) Dialkyl compounds with Group 2 alkaline earth metals or Group 12 metals.

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 from each other, and represent a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, and p is preferably Is a number of 1.5 ≦ p ≦ 3.)
R ^a _p AlY _3-p (B-1a-2)
(In the formula (B-1a-2), Ra represents ^a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, Y represents a halogen atom, and p is preferably 0 <p <3. An organoaluminum compound represented by:
R ^a _p AlH _3-p (B-1a-3)
(In the formula (B-1a-3), Ra 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). An organoaluminum compound 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 from each other, and each represent a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, and Y represents a halogen atom. An organic aluminum compound represented by the following formula: p is an atom, p is 0 <p ≦ 3, q is a number 0 ≦ q <3, s is a number 0 ≦ s <3, and p + q + s = 3.

More specifically, as the organoaluminum compound belonging to the general formula (B-1a), trimethylaluminum, triethylaluminum, tri-n-butylaluminum, tripropylaluminum, tripentylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum Tri-n-alkylaluminum such as;
Triisopropylaluminum, triisobutylaluminum, trisec-butylaluminum, tritert-butylaluminum, tri-2-methylbutylaluminum, tri-3-methylbutylaluminum, tri-2-methylpentylaluminum, tri-3-methylpentylaluminum, tri-4 A tri-branched alkylaluminum such as methylpentylaluminum, tri-2-methylhexylaluminum, tri-3-methylhexylaluminum, tri-2-ethylhexylaluminum;
Tricycloalkylaluminum such as tricyclohexylaluminum, tricyclooctylaluminum;
Triarylaluminums such as triphenylaluminum and tolylylaluminum;
Dialkylaluminum hydrides such as diisobutylaluminum hydride;
_{(I-C 4 H 9)} x Al y (C 5 H 10) z ( wherein, x, y, z are each a positive number, and z ≧ 2x.) Tri isoprenylaluminum represented by like Trialkenyl aluminum such as;
Alkyl aluminum alkoxides such as isobutyl aluminum methoxide, isobutyl aluminum ethoxide, isobutyl aluminum isopropoxide;
Dialkylaluminum alkoxides such as dimethylaluminum methoxide, diethylaluminum ethoxide, dibutylaluminum butoxide;
Alkylaluminum sesquialkoxides such as ethylaluminum sesquiethoxide and butylaluminum sesquibutoxide;
R ^a _2.5 Al (OR ^b ) Partially alkoxylated alkylaluminum having an average composition represented by _0.5 (wherein R ^a and R ^b may be the same or different from each other and have a carbon atom number of 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 sesquichlorides such as ethylaluminum sesquichloride, butylaluminum sesquichloride, ethylaluminum sesquibromide;
Partially halogenated alkylaluminums such as alkylaluminum dihalides such as ethylaluminum dichloride, propylaluminum dichloride, butylaluminum dibromide;
Dialkylaluminum hydrides such as diethylaluminum hydride, dibutylaluminum hydride;
Other partially hydrogenated alkylaluminums such as alkylaluminum dihydrides such as ethylaluminum dihydride, propylaluminum dihydride;
Examples include partially alkoxylated and halogenated alkylaluminums such as ethylaluminum ethoxychloride, butylaluminum butoxychloride, and ethylaluminum ethoxybromide.

A compound similar to (B-1a) can also be used in the present invention. Examples of such a compound include an organoaluminum compound in which two or more aluminum compounds are bonded via a nitrogen atom. Specific examples of such a compound include (C ₂ H ₅ ) ₂ AlN (C ₂ H ₅ ) Al (C ₂ H ₅ ) ₂ .

Examples of the compound belonging to the general formula (B-1b) include LiAl (C ₂ H ₅ ) ₄ and LiAl (C ₇ H ₁₅ ) ₄ .
Examples of the compound belonging to the general formula (B-1c) include dimethyl magnesium, diethyl magnesium, dibutyl magnesium, butyl ethyl magnesium, dimethyl zinc, diethyl zinc, diphenyl zinc, di-n-propyl zinc, diisopropyl zinc, di-n- Examples thereof include butyl zinc, diisobutyl zinc, bis (pentafluorophenyl) zinc, dimethyl cadmium, diethyl cadmium and the like.

  In addition, examples of the organometallic compound (B-1) include methyl lithium, ethyl lithium, propyl lithium, butyl lithium, methyl magnesium bromide, methyl magnesium chloride, ethyl magnesium bromide, ethyl magnesium chloride, propyl magnesium bromide, propyl magnesium. Chloride, butylmagnesium bromide, butylmagnesium chloride and the like can also be used.

  In addition, a compound capable of forming the organoaluminum compound in the polymerization system, such as a combination of an aluminum halide and an alkyllithium, or a combination of an aluminum halide and an alkylmagnesium is used as the organometallic compound (B-1). It 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 is used singly or in combination of two or more.

((B-2) Organoaluminum oxy compound)
The organoaluminum oxy compound (B-2) used in the present invention may be a conventionally known aluminoxane or a benzene-insoluble organoaluminum oxy compound as exemplified in JP-A-2-78687. May be.
A conventionally well-known aluminoxane can be manufactured, for example with the following method, and is normally obtained as a solution of a hydrocarbon solvent.

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

  (2) A method of allowing water, ice or water vapor to act directly on an organoaluminum compound such as trialkylaluminum in a medium such as benzene, toluene, ethyl ether or tetrahydrofuran.

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

  The aluminoxane may contain a small amount of an organometallic component. Further, after removing the solvent or unreacted organoaluminum compound by distillation from the recovered solution of the above aluminoxane, the obtained aluminoxane may be redissolved in a solvent or suspended in a poor aluminoxane solvent.

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

Of these, trialkylaluminum and tricycloalkylaluminum are preferable, and trimethylaluminum is particularly preferable.
The above organoaluminum compounds are used singly or in combination of two or more.

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

  The organoaluminum oxy compound (B-2) according to the present invention is represented by an aluminoxane having a structure represented by the following general formula (B-2a) or (B-2b), and the following general formula (B-2c). And an aluminoxane selected from at least one of aluminoxanes having 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, or 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, cyclohexane Examples of the hydrocarbon group include octyl group, phenyl group, tolyl group, and ethylphenyl group. Of these exemplified ones, in methyl group, an ethyl group, an isobutyl group are preferable, methyl group is particularly preferably the general formula (B-2a), and (B-2b) (B- 2c), the R ^e one Part may be substituted with a halogen atom such as chlorine or bromine, and the halogen content may be 40% by weight or less. In (B-2c) and (B-2d), a straight line in which one side 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 to 500, preferably 6 to 300, particularly preferably 10 to 100.
In the general formulas (B-2c) and (B-2d), s and t each represent an integer of 1 or more.

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

  The benzene-insoluble organoaluminum oxy compound used in the present invention has an Al component dissolved in benzene at 60 ° C. of usually 10% or less, preferably 5% or less, particularly preferably 2% or less in terms of Al atom, That is, it is preferably insoluble or hardly soluble in benzene. )

  Examples of the organoaluminum oxy compound (B-2) used in the present invention also include an organoaluminum oxy 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 four R ^{16 s} may be the same as or different from each other. And represents a hydrocarbon group having 1 to 10 atoms or carbon atoms.)

The organoaluminum oxy compound containing boron represented by the general formula (B-2e) comprises an alkyl boronic acid represented by the following general formula (B-2f) and an organoaluminum compound in an inert gas atmosphere. In an inert solvent at a temperature of −80 ° C. to room temperature for 1 minute to 24 hours.
R ¹⁵ -B (ОH) ₂ (B-2f)
(In the general formula (B-2f), R ¹⁵ represents the same group as R ¹⁵ in the general formula (B-2e).)

  Specific examples of the alkyl boronic acid represented by the general formula (B-2f) include methyl boronic acid, ethyl boronic acid, isopropyl boronic acid, n-propyl boronic acid, n-butyl boronic acid, isobutyl boronic acid, n- Examples include hexylboronic acid, cyclohexylboronic acid, phenylboronic acid, 3,5-difluoroboronic acid, pentafluorophenylboronic acid, 3,5-bis (trifluoromethyl) phenylboronic acid. Among these, methyl boronic acid, n-butyl boronic acid, isobutyl boronic acid, 3,5-difluorophenyl boronic acid, and pentafluorophenyl boronic acid are preferable. These may be used alone or in combination of two or more.

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

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

In addition to the transition metal compound [A], when an organoaluminum oxy compound (B-2) such as methylaluminoxane as a promoter component is used in combination, the olefin compound exhibits a very high polymerization activity.
The above organoaluminum oxy compounds (B-2) are used singly or in combination of two or more.

((B-3) Compound that reacts with transition metal compound [A] to form an ion pair)
As the compound (B-3) (hereinafter referred to as “ionized ionic compound”) which forms an ion pair by reacting with the transition metal compound [A] used in the present invention, JP-A-1-501950, Lewis described in JP-A-1-502036, JP-A-3-179005, JP-A-3-179006, JP-A-3-207703, JP-A-3-207704, US-5321106, etc. Examples thereof include acids, ionic compounds, borane compounds and carborane compounds. Furthermore, heteropoly compounds and isopoly compounds can also be mentioned.

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

  Examples of the ionic compound include compounds represented by the following general formula (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 formula [B-3a], R ¹⁷ is H ^+, a ferrocenium cation having carbonium cations, oxonium cation, an ammonium cation, a phosphonium cation, a cycloheptyltrienyl cation or a transition metal, R ¹⁸ ~ R ²¹ may be the same or different from each other, and 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 alkyls 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 cation, N, N-diethylanilinium cation, N, N-2,4,6-pentamethylanilinium cation A dialkylammonium cation such as a di (isopropyl) ammonium cation or a dicyclohexylammonium cation;

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

R ¹⁷ is preferably a carbonium cation or an ammonium cation, and particularly preferably a triphenylcarbonium cation, an N, N-dimethylanilinium cation, or an N, N-diethylanilinium cation.

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

  Specific examples of the trialkyl-substituted ammonium salt include triethylammonium tetra (phenyl) boron, tripropylammonium tetra (phenyl) boron, tri (n-butyl) ammonium tetra (phenyl) boron, and trimethylammonium tetra (p-tolyl). ) Boron, trimethylammonium tetra (o-tolyl) boron, tri (n-butyl) ammonium tetra (pentafluorophenyl) boron, tripropylammonium tetra (o, p-dimethylphenyl) boron, tri (n-butyl) ammonium tetra (M, m-dimethylphenyl) boron, tri (n-butyl) ammonium tetra (p-trifluoromethylphenyl) boron, tri (n-butyl) ammonium tetra (3,5-ditrifluoromethyl) Enyl) boron, tri (n-butyl) ammonium tetra (o-tolyl) boron, di (octadecyl) methylammonium tetraphenylboron, di (octadecyl) methylammonium tetrakis (p-tolyl) boron, di (octadecyl) methylammonium tetrakis (O-tolyl) boron, di (octadecyl) methylammonium tetrakis (pentafluorophenyl) boron, di (octadecyl) methylammonium tetrakis (2,4-dimethylphenyl) boron, di (octadecyl) methylammonium tetrakis (3,5- Dimethylphenyl) boron, di (octadecyl) methylammonium tetrakis (4-trifluoromethylphenyl) boron, di (octadecyl) methylammonium tetrakis (3,5-ditrif Oro-methylphenyl) has a higher alkyl of lower of said di (octadecyl) methylammonium boron or the like can be exemplified an alkyl ammonium salt.

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

  Specific examples of the dialkylammonium salt include di (1-propyl) ammonium tetra (pentafluorophenyl) boron and dicyclohexylammonium tetra (phenyl) boron.

  Further, as ionic compounds, triphenylcarbenium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, ferrocenium tetra (pentafluorophenyl) borate, triphenylcarbenium pentaphenyl Mention may also be made of cyclopentadienyl complexes, N, N-diethylanilinium pentaphenylcyclopentadienyl complexes, boron compounds represented by the following formula (B-3b) or (B-3c), and the like.

（式（Ｂ−３ｂ）中、Ｅｔはエチル基を示す。）

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

（式（Ｂ−３ｃ）中、Ｅｔはエチル基を示す。）

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

Specifically as a borane compound which is an example of an ionized ionic compound (compound (B-3)), for example, decaborane;
Bis [tri (n-butyl) ammonium] nonaborate, bis [tri (n-butyl) ammonium] decaborate, bis [tri (n-butyl) ammonium] undecaborate, bis [tri (n-butyl) ammonium] dodecaborate Salts of anions such as bis [tri (n-butyl) ammonium] decachlorodecaborate, bis [tri (n-butyl) ammonium] dodecachlorododecaborate;
Of metal borane anions such as tri (n-butyl) ammonium bis (dodecahydridododecaborate) cobaltate (III), bis [tri (n-butyl) ammonium] bis (dodecahydridododecaborate) nickate (III) Examples include salt.

Specific examples of carborane compounds that are examples of ionized ionic compounds include, for example, 4-carbanonaborane, 1,3-dicarbanonaborane, 6,9-dicarbadecarborane, dodecahydride-1-phenyl-1,3- Dicarbanonaborane, dodecahydride-1-methyl-1,3-dicarbanonaborane, undecahydride-1,3-dimethyl-1,3-dicarbanonaborane, 7,8-dicarbaundecaborane, 2 , 7-dicarbaound decaborane, undecahydride-7,8-dimethyl-7,8-dicarbaound decaborane, dodecahydride-11-methyl-2,7-dicarbound decaborane, tri (n-butyl) ammonium 1-carbadecaborate, tri (n-butyl) ammonium 1-carbaundecaborate, tri (n- Til) 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-Dicarbaound Decabo , 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-dicarboundeborate, tri (n-butyl) ammonium undecahydride-4,6-dibromo-7-carbaundecaborate, etc. Anion salts;
Tri (n-butyl) ammonium bis (nonahydride-1,3-dicarbanonaborate) cobaltate (III), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarbaundecaborate) Ferrate (III), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarbaundecaborate) cobaltate (III), tri (n-butyl) ammonium bis (undecahydride-7) , 8-dicarbaundecaborate) nickelate (III), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarboundeborate) cuprate (III), tri (n-butyl) Ammonium bis (undecahydride-7,8-dicarbaundecaborate) aurate (III , Tri (n-butyl) ammonium bis (nonahydride-7,8-dimethyl-7,8-dicarboundecarboxylate) ferrate (III), tri (n-butyl) ammonium bis (nonahydride-7,8 -Dimethyl-7,8-dicarbaundecaborate) chromate (III), tri (n-butyl) ammonium bis (tribromooctahydride-7,8-dicarbaundecaborate) cobaltate (III), tris [Tri (n-butyl) ammonium] bis (undecahydride-7-carbaundecaborate) chromate (III), bis [tri (n-butyl) ammonium] bis (undecahydride-7-carbaundeca Borate) manganate (IV), bis [tri (n-butyl) ammonium] bis (undeca) Metal carborane anions such as idride-7-carbaundecaborate) cobaltate (III), bis [tri (n-butyl) ammonium] bis (undecahydride-7-carbaundecaborate) nickelate (IV) And the like.

  The heteropoly compound that is an example of the ionized ionic compound includes an atom selected from silicon, phosphorus, titanium, germanium, arsenic, and tin, and one or more atoms selected from vanadium, niobium, molybdenum, and tungsten. A compound. Specifically, phosphovanadic acid, germanovanadic acid, arsenic vanadic acid, phosphoniobic acid, germanoniobic acid, siliconomolybdic acid, phosphomolybdic acid, titanium molybdic acid, germanomolybdic acid, arsenic molybdic acid, tin molybdic acid, phosphorus Tungstic acid, germanotungstic acid, tin tungstic acid, phosphomolybdovanadic acid, phosphotungstovanadic acid, germano-tungstovanadic acid, phosphomolybdo-tungstovanadic acid, germano-molybdo-tungstovanadic acid, phosphomolybdotungstic acid , Phosphomolybdoniobic acid, and salts of these acids, but not limited thereto. In addition, the salt includes, for example, an alkali metal of Group 1 of the periodic table or an alkaline earth metal of Group 2, specifically lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium. , Salts with strontium, barium and the like, and organic salts such as triphenylethyl salt.

  An isopoly compound which is an example of an ionized ionic compound is a compound composed of a metal ion of one kind of atom selected from vanadium, niobium, molybdenum and tungsten, and is regarded as a molecular ionic species of a metal oxide. Can do. Specific examples include vanadic acid, niobic acid, molybdic acid, tungstic acid, and salts of these acids, but are not limited thereto. The salt includes, for example, metals of Group 1 or 2 of the periodic table, specifically lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium and the like. And organic salts such as triphenylethyl salt.

The above ionized ionic compounds (compound (B-3) that forms an ion pair by reacting with the transition metal compound [A]) are used singly or in combination of two or more.
Moreover, the catalyst for olefin polymerization according to the present invention includes the transition metal compound [A], an organometallic compound (B-1), an organoaluminum oxy compound (B-2), and an ionized ionic compound (B-3). In addition to at least one compound [B] selected from the group consisting of:

[[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 having a good morphology can be obtained.

As the inorganic compound, porous oxides, solid aluminoxane compounds, inorganic halides, clays, clay minerals, or ion-exchangeable layered compounds are preferable.
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 a composite or mixture containing these. Furthermore, natural or synthetic zeolites, SiO ₂ —MgO, SiO ₂ —Al ₂ O ₃ , SiO ₂ —TiO ₂ , SiO ₂ —V ₂ O ₅ , SiO ₂ —Cr ₂ O ₃ , SiO _2- TiO ₂ -MgO or the like can be used. Of these, the porous oxide is preferably one containing SiO ₂ and / or Al ₂ O ₃ as a main component.

The porous oxide contains a small amount of Na ₂ CO ₃ , K ₂ CO ₃ , CaCo ₃ , MgCo ₃ , Na ₂ SO ₄ , Al ₂ (SO ₄ ) ₃ , BaSO ₄ , KNO ₃ , Mg (NO _3). ) ₂ , Al (NO ₃ ) ₃ , Na ₂ O, K ₂ O, Li ₂ O and other carbonates, sulfates, nitrates and oxide components may be contained.

Such porous oxides have different properties depending on the type and production method, but the porous oxide preferably used in the present invention has a particle size of 10 to 300 μm, preferably 20 to 200 μm, and a specific surface area. It is desirable to be in the range of 50 to 1000 m ² / g, preferably 100 to 700 m ² / g, and the pore volume to be in the range of 0.3 to 3.0 cm ³ / g. Such a porous oxide is used after being calcined at 100 to 1000 ° C., preferably 150 to 700 ° C., if necessary.

Examples of the solid aluminoxane compound include aluminoxane selected from at least one of the aluminoxanes represented by the above (B-2a) to (B-2d).
The solid aluminoxane used in the present invention is different from conventionally known olefin polymerization catalyst carriers, and does not contain inorganic solid components such as silica and alumina, and organic polymer components such as polyethylene and polystyrene. Shows solidified as. The meaning of “solid” used in the present invention is to maintain a substantially solid state in a reaction environment in which the aluminoxane component (B-2) is used. More specifically, for example, when preparing the solid catalyst component for olefin polymerization by bringing the component [A] and the component [B] into contact as described later, an inert hydrocarbon solvent such as hexane or toluene used for the reaction. Among these, it represents that component [B] is in a solid state under a specific temperature and pressure environment. Further, for example, when suspension polymerization is performed using a solid catalyst component for olefin polymerization prepared by using the component [B] as described later, a specific temperature and pressure in a hydrocarbon solvent such as hexane, heptane, and toluene. It is also a necessary requirement that the component [B] contained in the catalyst component in the environment is in a solid state. 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.

  Whether the component [B] is in a solid state under the above environment is the simplest method for visual confirmation, but for example, it is often difficult to visually confirm during polymerization. In that case, for example, it is possible to judge from the properties of the polymer powder obtained after polymerization, the state of adhesion to the reactor, and the like. On the contrary, if the properties of the polymer powder are good and there is little adhesion to the reactor, even if some of the component [B] elutes in the polymerization environment, the gist of the present invention is not deviated. The index for judging the properties of the polymer powder includes the bulk density, the particle shape, the surface shape, the degree of presence of the amorphous polymer, etc., and the polymer bulk density is preferable from the viewpoint of quantitativeness. The bulk density in this invention is 0.01-0.9 normally, Preferably it is 0.05-0.6, More preferably, it exists in the range of 0.1-0.5.

  The solid aluminoxane used in the present invention is usually dissolved in a proportion of 0 to 40 mol%, preferably 0 to 20 mol%, particularly preferably 0 to 10 mol with respect to n-hexane maintained at a temperature of 25 ° C. % Range is satisfied.

  The dissolution ratio of the solid aluminoxane used in the present invention with respect to n-hexane was determined by adding 2 g of solid aluminoxane support to 50 ml of n-hexane maintained at 25 ° C., followed by stirring for 2 hours, and then G-4 glass. The solution portion was separated using a filter manufactured, and the aluminum concentration in the filtrate was measured. 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 the aluminoxane used.

  As the solid aluminoxane according to the present invention, a known solid aluminoxane can be used without limitation. Known manufacturing methods include, for example, JP-B-7-43001, JP-A-6-220126, JP-A-6-220128, JP-A-11-140113, JP-A-11-310607, JP-A-2000. -38410, JP-A-2000-95810, WO201055552 and the like.

The average particle size of the solid aluminoxane according to the present invention is generally 0.01 to 50000 μm, preferably 1 to 1000 μm, particularly preferably 1 to 200 μm.
The average particle size of the solid aluminoxane can be determined by observing the particles with a scanning electron microscope, measuring the particle size of 100 or more particles, and weight averaging. For the particle size of the solid aluminoxane, the maximum length of the Pythagorean method was measured from the particle image. That is, in each of the horizontal direction and the vertical direction, the length of the particle image sandwiched between two parallel lines is measured, and it can be calculated by the following formula.
Particle size = ((horizontal length) ² + (vertical length) ² ) ^0.5
The weight average particle diameter of the solid aluminoxane is obtained by the following formula using the particle diameter obtained above.
Average particle size = Σnd ⁴ / Σnd ³ (where n: number of particles, d: particle size)

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

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

  The clay is usually composed mainly of clay minerals. Moreover, the said ion exchange layered compound is a compound which has a crystal structure where the surface comprised by the ionic bond etc. was piled up in parallel with weak mutual binding force, and the ion to contain is exchangeable. Most clay minerals are ion-exchangeable layered compounds. In addition, these clays, clay minerals, and ion-exchange layered compounds are not limited to natural products, and artificial synthetic products can also be used.

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

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

Such a clay, clay mineral, or ion-exchange layered compound preferably has a pore volume of not less than 0.1 cc / g and not less than 0.3 to 5 cc / g as measured by mercury porosimetry. It is particularly preferred. Here, the pore volume is measured in a range of pore radius of 20 to 30000 mm by mercury porosimetry using a mercury porosimeter.
When a carrier having a pore volume with a radius of 20 mm or more and smaller than 0.1 cc / g is used as a carrier, high polymerization activity tends to be difficult to obtain.

  The clay and clay mineral used in the present invention are preferably subjected to chemical treatment. As the chemical treatment, any of a surface treatment that removes impurities adhering to the surface and a treatment that affects the crystal structure of clay can be used. Specific examples of the chemical treatment include acid treatment, alkali treatment, salt treatment, and organic matter treatment. In addition to removing impurities on the surface, the acid treatment increases the surface area by eluting cations such as Al, Fe, and Mg in the crystal structure. Alkali treatment destroys the crystal structure of the clay, resulting in a change in the structure of the clay. In the salt treatment and the organic matter treatment, an ion complex, a molecular complex, an organic derivative, and the like can be formed, and the surface area and interlayer distance can be changed.

The ion-exchangeable layered compound used in the present invention may be a layered compound in a state where the layers are expanded by exchanging the exchangeable ions between the layers with other large and bulky ions using the ion-exchange property. . Such bulky ions play a role of supporting pillars to support the layered structure, and are usually called pillars. Moreover, introducing another substance between the layers of the layered compound in this way is called intercalation. Examples of guest compounds to be intercalated include cationic inorganic compounds such as TiCl ₄ and ZrCl _4, and metal alkoxides such as Ti (OR) ₄ , Zr (OR) ₄ , PO (OR) ₃ , and B (OR) _3. R is a hydrocarbon group), metal hydroxide ions such as [Al ₁₃ O ₄ (ОH) ₂₄ ] ⁷⁺ , [Zr ₄ (ОH) ₁₄ ] ²⁺ , [Fe ₃ O (ОCOCH ₃ ) ₆ ] ⁺ Etc. These compounds are used alone or in combination of two or more. In addition, when intercalating these compounds, metal alkoxides such as Si (OR) ₄ , Al (OR) ₃ , Ge (OR) ₄ (R represents a hydrocarbon group, etc.) are hydrolyzed. The obtained polymer and colloidal inorganic compounds such as SiO ₂ can coexist. Examples of the pillar include oxides generated by heat dehydration after intercalation of the metal hydroxide ions between layers.

  The clay, clay mineral, and ion-exchangeable layered compound used in the present invention may be used as they are, or may be used after a treatment such as ball milling or sieving. Further, it may be used after newly adsorbing and adsorbing water or after heat dehydration treatment. Furthermore, you may use individually or in combination of 2 or more types.

Of these, preferred are clays or clay minerals, and particularly preferred are montmorillonite, vermiculite, pectolite, teniolite and synthetic mica.
As described above, the carrier [C] is an inorganic or organic compound, and examples of the organic compound include granular or particulate solids having a particle size in the range of 10 to 300 μm. Specifically, a polymer produced mainly from an α-olefin having 2 to 14 carbon atoms such as ethylene, propylene, 1-butene, 4-methyl-1-pentene, or vinylcyclohexane or styrene as a main component. As examples, polymers produced as follows, and modified products thereof can be exemplified.

  The catalyst for olefin polymerization according to the present invention comprises the transition metal compound [A], the compound [B], and the carrier [C] as necessary, and the following specific organic compound component [D] as necessary. It can also be included.

[[D] Organic compound component]
In the present invention, if necessary, the organic compound component [D] improves the polymerization performance of the olefin polymerization catalyst of the present invention and the physical properties of the produced polymer (for example, the molecular weight of the produced polymer). Used for the purpose. Examples of such organic compounds include, but are not limited to, alcohols, phenolic compounds, carboxylic acids, phosphorus compounds, and sulfonates.

As the alcohols and the phenolic compounds, those represented by R ²² —OH are usually used, wherein R ²² is a hydrocarbon group having 1 to 50 carbon atoms (in the case of phenols, a carbon atom). The number is 6 to 50) or a halogenated hydrocarbon group having 1 to 50 carbon atoms (6 to 50 carbon atoms in the case of phenols).

As alcohols, R ²² is preferably a halogenated hydrocarbon group. Moreover, as a phenolic compound, what substituted the (alpha) and (alpha) '-position of the hydroxyl group with the C1-C20 hydrocarbon is preferable.

As 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 preferable.

As the phosphorus compound, phosphoric acids having a P—O—H bond, P—OR, phosphates having a P═O bond, and phosphine oxide compounds are preferably used.
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 in the periodic table, and R ²⁴ is hydrogen, a hydrocarbon group having 1 to 20 carbon atoms, or a halogen having 1 to 20 carbon atoms. 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 And u is an integer from 1 to 7 and tu ≧ 1.)

<Production method of polyolefin>
In the polyolefin production method according to the present invention, a polyolefin is obtained by including a step of polymerizing (homopolymerizing or copolymerizing) an olefin in the presence of the olefin polymerization catalyst as described above. As described above, in the present specification, the olefin refers to any compound having a polymerizable double bond.

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

  The solid catalyst component in which the transition metal compound [A] is supported on the carrier [C] and the solid catalyst component in which the transition metal compound [A] and the compound [B] are supported on the carrier [C] It may be polymerized, and a catalyst component may be further supported on the prepolymerized solid catalyst component.

  In the present invention, the 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 the inert hydrocarbon medium used in the liquid phase polymerization method include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; cyclopentane, cyclohexane, and methylcyclopentane. Alicyclic hydrocarbons such as: aromatic hydrocarbons such as benzene, toluene and xylene; halogenated hydrocarbons such as ethylene chloride, chlorobenzene and dichloromethane, or mixtures thereof, and the olefin itself used for polymerization Can also be used as a solvent.

When the olefin polymerization is performed using the olefin polymerization catalyst as described above, the transition metal compound [A] is usually 10 ⁻¹² to 10 ⁻² mol, preferably 10 ⁻¹⁰ to 10 ⁻¹⁰ liter per reaction volume. Used in such an amount as to be ^-3 mol.

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

  The organic compound component [D] has a molar ratio [[D] / (B-1)] with the organometallic compound (B-1) of usually 0.01 to 10, preferably 0.1 to 5. Used in various amounts. The organic compound component [D] has a molar ratio [[D] / (B-2)] with the organoaluminum oxy compound (B-2) of usually 0.001 to 2, preferably 0.005 to 1. Used in such amounts. The organic compound component [D] has a molar ratio [[D] / (B-3)] with the ionized ionic compound (B-3) of usually 0.01 to 10, preferably 0.1 to 5. Used in such amounts.

Moreover, the polymerization temperature of the olefin using such an olefin polymerization catalyst is usually in the range of −50 to + 200 ° C., preferably 0 to 170 ° C. The polymerization pressure is usually from normal pressure to 100 kg / cm ² -G, preferably from normal pressure to 50 kg / cm ² -G, and the polymerization reaction is carried out in any of batch, semi-continuous and continuous methods. Can also be done. Furthermore, the polymerization can be performed in two or more stages having different reaction conditions.

  The molecular weight of the resulting polyolefin can be adjusted by the presence of hydrogen in the polymerization system or by changing the polymerization temperature. Furthermore, it can also adjust with the quantity of the compound [B] to be used.

The olefin that can be polymerized by the olefin polymerization catalyst of the present invention is not particularly limited as long as it has a polymerizable double bond, but has 2 to 30, preferably 2 to 20, more preferably carbon atoms. Are 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, preferably 3 to 20, more preferably 3 to 10 carbon atoms, such as cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene, 2-methyl-1 4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene and the like.

  The 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. More preferably, it is used. The α-olefin may be used alone or in combination of two or more.

  In the case of copolymerization of ethylene and an α-olefin having 3 to 20 carbon atoms, preferably 3 to 10 carbon atoms, the α-olefin (hereinafter also referred to as olefin A) is not particularly limited as long as the effects of the present invention are exhibited. Are, for example, propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-octene and 1-decene. 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 olefin A is used, the ratio of ethylene to the olefin A used is ethylene: the olefin A (molar ratio), usually 1:10 to 5000: 1, preferably 1: 5. 1000: 1.

  The catalyst for olefin polymerization of the present invention is a homopolymer 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 preferred to use for copolymerization with olefins. The α-olefin may be used alone or in combination of two or more.

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

  In the case of copolymerization with 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) is Although it does not specifically limit as long as there exists an effect, For example, ethylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1 -Octene and 1-decene are preferred. These α-olefins may be used 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 use ratio of propylene to the olefin B is propylene: the olefin B (molar ratio), usually 1:10 to 5000: 1, preferably 1: 5. 1000: 1.

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

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

  In the case of copolymerization with 1-butene and 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 Although not particularly limited as long as the effects of the present invention are exhibited, for example, 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 olefin C is used, the amount ratio of 1-butene to the olefin C is 1-butene: the olefin C (molar ratio), usually 1:10 to 5000: 1, Preferably it is 1: 5-1000: 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.

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

Examples of the cyclic olefin include cyclic olefins having 3 to 30 carbon atoms, preferably 3 to 20 carbon atoms, more preferably 3 to 10 carbon atoms. Specific examples of the cyclic olefin include cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, and 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.

  Examples of the aromatic vinyl compound include aromatic vinyl compounds having 8 to 20 carbon atoms, preferably 8 to 18 carbon atoms, and more preferably 8 to 16 carbon atoms. Specific examples of the aromatic vinyl compound include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, o, p-dimethylstyrene, 3,5-dimethylstyrene, o-ethylstyrene, m-ethylstyrene, p-ethyl styrene, o-iso-propyl styrene, m-iso-propyl styrene, p-iso-propyl styrene, 3,5-iso-propyl styrene, o-tert-butyl styrene, m-tert-butyl styrene, p Mono- or polyalkyl styrene such as -tert-butyl styrene, 3,5-tert-butyl styrene, etc. may be mentioned.

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

The catalyst for olefin polymerization of the present invention may polymerize a chain-like 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, -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 , Unsaturated carboxylic acids such as bicyclo [2.2.1] -5-heptene-2-carboxylic acid, bicyclo [2.2.1] -5-heptene-2,3-dicarboxylic acid, and sodium salts thereof , Potassium salts, lithium salts, zinc salts, magnesium salts, calcium salts and the like, and methyl esters, ethyl esters, n-propyl esters, isopropyl esters, n-butyl esters, isobutyl esters of these unsaturated carboxylic acids, ( Unsaturated carboxylic acid esters such as 5-norbornen-2-yl) ester When the acid is a dicarboxylic acid, it may be a monoester or a diester), and amides of these unsaturated carboxylic acids, unsaturated carboxylic amides such as N, N-dimethylamide When the saturated carboxylic acid is a dicarboxylic acid, it may be a monoamide or a diamide);
Maleic anhydride, itaconic anhydride, allyl succinic anhydride, isobutenyl succinic anhydride, (2,7-octadien-1-yl) succinic anhydride, tetrahydrophthalic anhydride, bicyclo [2.2.1 ] Unsaturated carboxylic acid anhydrides such as -5-heptene-2,3-dicarboxylic acid anhydride;
Vinyl esters such as vinyl acetate, vinyl propionate, vinyl caproate, vinyl caprate, vinyl laurate, vinyl stearate;
Allyl esters such as allyl acetate, allyl propionate, allyl caproate, allyl caprate, allyl laurate, 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, 12-tridecenol And unsaturated esters thereof such as acetates, benzoates, propionates, caproates, caprates, laurates, stearates;
Substituted phenols such as vinylphenol and allylphenol, and unsaturated esters 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 acetate, benzoate, propionate, caproate, caprate, laurate and stearate;
Unsaturated ethers such as methyl vinyl ether, ethyl vinyl ether, allyl methyl ether, allyl propyl ether, allyl butyl ether, allyl methallyl ether, methoxy styrene, ethoxy styrene, allyl anisole;
Unsaturated epoxides such as butadiene monoxide, 1,2-epoxy-7-octene, 3-vinyl 7-oxabicyclo [4.1.0] heptane;
Unsaturated aldehydes such as acrolein and undecenal, and unsaturated acetals such as dimethyl acetal and diethyl acetal;
Unsaturated ketones such as methyl vinyl ketone, ethyl vinyl ketone, allyl methyl ketone, allyl ethyl ketone, allyl propyl ketone, allyl butyl ketone, and allyl benzyl ketone, and unsaturated acetals such as dimethyl acetal and diethyl acetal;
Unsaturated thioethers such as allyl methyl sulfide, allyl phenyl sulfide, allyl isopropyl sulfide, allyl n-propyl sulfide, 4-pentenyl phenyl sulfide;
Unsaturated sulfoxides such as allyl phenyl sulfoxide;
Unsaturated sulfones such as allyl phenyl sulfone;
Unsaturated phosphines such as allyldiphenylphosphine;
And unsaturated phosphine oxides such as allyldiphenylphosphine oxide.

  Furthermore, unsaturated hydrocarbons having two or more 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, Acrylic trimethylsilane, allyldimethyl (diisopropylamino) silane, 7-octenyltrimethoxysilane, allyloxytrimethylsilane, allyloxytriphenylsilane and the like may also be polymerized by the olefin polymerization catalyst of the present invention.

The olefin polymerization catalyst of the present invention may polymerize vinylcyclohexane, diene, polyene, or the like.
Examples of the diene or the 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, ethylidene norbornene, vinyl norbornene, dicyclopentadiene;
7-methyl-1,6-octadiene, 4-ethylidene-8-methyl-1,7-nonadiene, 5,9-dimethyl-1,4,8-decatriene;
Further, mono- or poly-aromatic vinyl compounds such as styrene, o-methyl styrene, m-methyl styrene, p-methyl styrene, o, p-dimethyl styrene, o-ethyl styrene, m-ethyl styrene, p-ethyl styrene, etc. Alkyl styrene;
Functional group-containing styrene derivatives such as methoxystyrene, ethoxystyrene, vinyl benzoic acid, methyl vinyl benzoate, vinyl benzyl acetate, hydroxystyrene, o-chlorostyrene, p-chlorostyrene, divinylbenzene; and 3-phenylpropylene, 4- Examples include phenylpropylene and α-methylstyrene.

  As described above, 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, and includes the compound [A]. The catalyst for use has α-olefin copolymerizability that is particularly superior to transition metal compounds having a conventional metallocene skeleton (having no specific substituent at a specific position), and good olefin polymerization activity. A low-density ethylene copolymer having a sufficient molecular weight can be produced.

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

[Olefin polymer]
According to the present invention, in the presence of a catalyst for olefin polymerization containing a useful and novel transition metal compound [A] having the specific structure described above, one or more α-olefins having 2 to 30 carbon atoms are used. Preferably, an olefin polymer can be efficiently produced by homopolymerizing ethylene or copolymerizing ethylene and an α-olefin having 3 to 20 carbon atoms (olefin A). .

  Further, in the present invention, propylene homopolymerization or propylene and an α- having 2 to 20 carbon atoms in the presence of an olefin polymerization catalyst containing a useful and novel transition metal compound [A] having the specific structure described above. An olefin polymer can also be efficiently produced by copolymerizing olefins (excluding propylene) (olefin B), and copolymerizes ethylene, a cyclic olefin, and an aromatic vinyl compound. Therefore, it is possible to efficiently produce an olefin polymer, such as homopolymerization of 1-butene, or 1-butene and an α-olefin having 2 to 20 carbon atoms (excluding 1-butene) (olefin) It is also possible to efficiently produce an olefin polymer by copolymerizing with C).

  As one aspect of the olefin polymer of the present invention, an ethylene-based polymer containing an ethylene-derived constitutional unit preferably in the range of 90 to 100 mol%, more preferably 92 to 100 mol%, still more preferably 95 to 100 mol%. Coalescence is mentioned. The ethylene-based polymer preferably contains the olefin A-derived structural units in a total amount of 0 to 10 mol%, more preferably 0 to 8 mol%, and still more preferably 0 to 5 mol%. However, the total of the content of the structural unit derived from ethylene and the content of the structural unit derived from the olefin A is 100 mol%. The ethylene-based polymer in which the structural unit derived from the olefin A is in the above range is excellent in molding processability. Further, other structural units may be included without departing from the spirit of the present invention. These contents can be measured by nuclear magnetic resonance spectroscopy or, if there is a reference substance, infrared spectroscopy.

  Among these polymers, ethylene homopolymer, ethylene / propylene copolymer, ethylene / 1-butene copolymer, ethylene / propylene / 1-butene copolymer, ethylene / 1-octene polymer, ethylene / 1 -Hexene polymer, ethylene / 4-methyl-1-pentene polymer, ethylene / propylene / 1-octene polymer, ethylene / propylene / 1-hexene polymer, ethylene / propylene / 4-methyl-1-pentene polymer Is particularly preferred. Moreover, what is called a block copolymer (impact copolymer) obtained by mixing or manufacturing continuously 2 or more types selected from these polymers may be sufficient.

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

  As another aspect of the olefin polymer of the present invention, the constituent unit derived from propylene is preferably 50 to 100 mol%, more preferably 55 to 100 mol%, still more preferably 80 to 100 mol%, particularly preferably 90. Examples thereof include propylene-based polymers contained in the range of ˜100 mol%. The propylene-based polymer preferably has 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 mol% of the structural units derived from the olefin B. Included in the range. However, the total of the content of the structural unit derived from propylene and the content of the structural unit derived from olefin B is 100 mol%. The propylene-based polymer in which the structural unit derived from the olefin B is in the above range is excellent in molding processability and strength. Further, other structural units may be included without departing from the spirit of the present invention. These contents can be measured by nuclear magnetic resonance spectroscopy or, if there is a reference substance, infrared spectroscopy.

  Among these polymers, propylene homopolymer, propylene / ethylene copolymer, propylene / 1-butene copolymer, propylene / ethylene / 1-butene copolymer, propylene / 1-octene polymer, 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. Moreover, what is called a block copolymer (impact copolymer) obtained by mixing or manufacturing continuously 2 or more types selected from these polymers may be sufficient.

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

  Another embodiment of the olefin polymer of the present invention includes an ethylene / cyclic olefin / aromatic vinyl compound copolymer obtained by copolymerization of ethylene, a cyclic olefin, and an aromatic vinyl compound. The ethylene / cyclic olefin / aromatic vinyl compound copolymer preferably contains a structural unit derived from ethylene in the range of 30 to 70 mol%, more preferably 35 to 70 mol%, and still more preferably 40 to 65 mol%, The constituent unit derived from the cyclic olefin is preferably contained in the range of 10 to 70 mol%, more preferably 20 to 60 mol%, and further preferably 20 to 45 mol%, and the constituent unit derived from the aromatic vinyl compound is preferably 0.00. 1 to 20 mol%, more preferably 1 to 20 mol%, still more preferably 5 to 20 mol%. However, the total of the content of the structural unit derived from ethylene, the content of the structural unit derived from the cyclic olefin, and the content of the structural unit derived from the aromatic vinyl compound is 100 mol%. The ethylene / cyclic olefin / aromatic vinyl compound copolymer in which the structural unit derived from each monomer is in the above range is excellent in heat resistance and optical properties such as transparency and refractive index. Further, other structural units may be included without departing from the spirit of the present invention. These contents can be measured by nuclear magnetic resonance spectroscopy or, if there is a reference substance, infrared spectroscopy.

Among these polymers, ethylene / tetracyclododecene / styrene copolymer,
An ethylene / norbornene / styrene copolymer is preferred. Moreover, what is called a block copolymer (impact copolymer) obtained by mixing or manufacturing continuously 2 or more types selected from these polymers may be sufficient.

  The ethylene / cyclic olefin / aromatic vinyl compound copolymer of the present invention is substantially a constituent unit derived from ethylene, a constituent unit derived from a cyclic olefin, and an aromatic vinyl among the polymers having the constituent units described above. A copolymer consisting only of a structural unit derived from a compound is preferred. “Substantially” means that the proportion of the structural unit derived from the monomer is 95% by weight or more based on the total structural unit.

  As another aspect of the olefin polymer of the present invention, the structural 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. Includes a 1-butene polymer contained in a range of 90 to 100 mol%. The 1-butene polymer preferably has 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 mol% of the structural units derived from the olefin C. Including in the range of mol%. However, the total of the content of the structural unit derived from 1-butene and the content of the structural unit derived from the olefin C is 100 mol%. The 1-butene polymer in which the structural unit derived from the olefin C is in the above range is excellent in molding processability and strength. Further, other structural units may be included without departing from the spirit of the present invention. These contents can be measured by nuclear magnetic resonance spectroscopy or, if there is a reference substance, infrared spectroscopy.

  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 polymer is particularly preferred. Moreover, what is called a block copolymer (impact copolymer) obtained by mixing or manufacturing continuously 2 or more types selected from these polymers may be sufficient.

  The 1-butene polymer of the present invention is preferably an α-olefin polymer consisting essentially of structural units derived from an α-olefin having 2 to 20 carbon atoms, among the polymers having the structural units described above. . “Substantially” means that the proportion of the structural unit derived from the α-olefin having 2 to 20 carbon atoms is 95% by weight or more with respect to all the structural units.

  In the ethylene polymer of the present invention, the weight average molecular weight measured by a gel permeation chromatography (GPC) method is not particularly limited, but is preferably 10,000 to 5,000,000, more preferably 10, 000 to 2,000,000, particularly preferably 20,000 to 1,000,000. The molecular weight distribution (Mw / Mn), which is the ratio between the weight average molecular weight (Mw) and the number average molecular weight (Mn), is not particularly limited, but is preferably 1 to 10, more preferably 1 to 7, and particularly preferably 1 to 1. 5. The molecular weight distribution can be adjusted by producing polymers having different molecular weights using a multistage polymerization method or the like, or by 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-olefin. The reason why such a phenomenon occurs can be estimated as described above.

In ethylene polymer of the present invention, the density is not particularly limited, it is preferably not more than 875kg / m ³ or more 975 kg / m ^3.
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. 1-10 dl / g.

  In the ethylene-based polymer of the present invention, the melt mass flow rate (MFR; unit is g / 10 minutes) measured under conditions of 190 ° C. and 2.16 kg load according to ASTM D1238-89 is not particularly limited, 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.

  Further, according to ASTM D1238-89, the value (I10 / I2) obtained by dividing the MFR value measured under the condition of 190 ° C. and 10 kg load by the MFR value measured under the condition of 190 ° C. and 2.16 kg load is 5 It is preferably 0.0 or more and less than 300.

  Details of the measurement conditions of the above physical property values are as described in the examples.

The following examples further illustrate the present invention. In addition, this invention is not limited to description of a following example.
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-QP2010 Ultra), It identified using FD-mass spectrometry (JEOL SX-102A).
Moreover, the method to measure the physical property and property of the polymer obtained by superposition | polymerization of an olefin in presence of the catalyst containing the transition metal compound of this invention was described below.

・ Density (kg / m ³ )
A sheet of 0.5 mm thickness was formed at a pressure of 100 kg / cm ² using a hydraulic heat press machine manufactured by Shindo Metal Industry Co., Ltd. set at 190 ° C. (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 machine manufactured by Shinfuji Metal Industry Co., Ltd. set to 20 ° C. A sample for measurement was prepared. As the hot plate, a 5 mm thick SUS plate was used.
The press 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 “Alliance GPC 2000” gel permeation chromatograph (high temperature size exclusion chromatograph) manufactured by Waters Co., and operating conditions are as follows:

[Devices used and conditions]
・ Molecular weight distribution and various average molecular weight measuring device; gel permeation chromatograph alliance GPC2000 (Waters)
Analysis software: Chromatography data system Empower (trademark, Waters)
Column; TSKgel GMH6-HT × 2 + TSKgel GMH6-HT × 2
(Inner diameter 7.5mm x length 30cm, Tosoh Corporation)
Mobile phase: o-dichlorobenzene [= ОDCB] (Wako Pure Chemicals special grade reagent)
Detector: Differential refractometer (built-in device)
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 Corp.) / Molecular weight 495 to molecular weight 20.6 million Molecular weight distribution and various average molecular weights Polym. Sci. , B5, 753. (1967) was calculated as a polyethylene molecular weight conversion according to the general calibration procedure described in (1967).

Melting point (Tm; ° C)
Using an RDC220 differential scanning calorimeter manufactured by SII, about 10 mg of the sample was heated to 30 to 200 ° C. at a heating rate of 50 ° C./min in a nitrogen atmosphere, and held at that temperature for 10 minutes. Furthermore, after cooling to 30 ° C. at a temperature lowering rate of 10 ° C./min and holding at that temperature for 5 minutes, the temperature was raised to 200 ° C. at a temperature rising rate of 10 ° C./min. The endothermic peak observed during the second temperature increase was defined as the melting peak, and the temperature at which the melting peak appears 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 the crystallization temperature (Tc) of an olefin (co) polymer containing a structural unit derived from 1-butene was measured as follows using a DSC7020 manufactured by SII as a differential scanning calorimeter (DSC). 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, and (2) cooled to 30 ° C. at 10 ° C./min 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 vertex of the crystal melting peak in the temperature raising process (3), and the crystallization temperature (Tc) was calculated from the peak vertex of the crystallization peak in the temperature lowering process (2). In addition, in the olefin (co) polymer containing the structural unit derived from 1-butene 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 high temperature side peak 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 melting curve.

  In addition, the data described as “after crystal stabilization” is as follows. Under a nitrogen atmosphere (20 mL / min), the sample (about 5 mg) was heated to 220 ° C. and held at 220 ° C. for 10 minutes, and then cooled to room temperature. Then, the melting point (Tm) and heat of fusion (ΔH) were measured as follows.

  Under a nitrogen atmosphere (20 mL / min), the sample (about 5 mg) was (1) cooled from room temperature to −20 ° C. at 20 ° C./minute and held at −20 ° C. for 10 minutes, and (2) 200 ° C./minute at 200 ° C. The temperature was raised to ° C. The melting point (Tm) was calculated from the peak of the crystal melting peak in the temperature raising 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 the sample was heated to 30 to 200 ° C. at a heating rate of 50 ° C./min in a nitrogen atmosphere, and held at that temperature for 10 minutes. Further, after cooling to −100 ° C. at a temperature lowering rate of 10 ° C./min and holding at that temperature for 5 minutes, the temperature was raised to 200 ° C. at a temperature rising rate of 10 ° C./min. The glass transition temperature (Tg) is detected in such a manner that the DSC curve is bent due to a change in specific heat and the baseline is moved in parallel during the second temperature increase. The glass transition temperature (Tg) was determined as the glass transition temperature (Tg), which is the temperature at the intersection between the base line tangent lower than the bend and the point of contact where the inclination is maximum at the bent portion.

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

That is, about 20 mg of polymer 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. After adding 5 ml of decalin solvent to this decalin solution for dilution, the specific viscosity η _sp is measured in the same manner. This dilution operation is further repeated twice, and the value of η _sp / C when the concentration (C) is extrapolated to 0 is obtained 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, as a measurement sample, a film obtained by dissolving and stretching the copolymer-forming polymer obtained in Examples in a hot press heated to 135 ° C. and then cooling under pressure at room temperature. The measurement was performed at a wavelength of 5000 cm ^{−1 to} 400 cm ⁻¹ . Hexene _{content, C-CH 2 CH 2 CH} 2 CH 3 skeleton vibration based on hexene (1378 cm ^-1) as a key band, absorbance key band (D1378) and the internal standard band (4321cm ^-1: CH stretching vibration And the absorbance (D4321) of the combined sound of the methylene and methyl bending vibrations [D1378 / D4321].

  A calibration curve specifying the relationship between the comonomer content and the [D1378 / D4321] is used to determine the comonomer content. The calibration curve is prepared in advance based on the [D1378 / D4321] results obtained by performing FT-IR measurement on ethylene copolymers having various compositions whose comonomer content is 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) copolymer content ratio (hereinafter referred to as E / TD / ST; mol%) is ECX400P type nuclear magnetic manufactured by JEOL Ltd. It calculated | required on the following measurement conditions using the resonance apparatus.

〔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 count: 128 times Measurement solvent: 1,1,2,2-tetrachloroethane-d2
Sample concentration; ca. 20mg / 0.6mL
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 bond carbon, the peak intensity derived from phenyl group protons, and the peak intensity of other protons.

<(1) Synthesis of transition metal compound>
[Example 1]
[Example 1-1]
A 200 mL reactor thoroughly dried and purged with argon was charged with 0.53 g (21.8 mmol) of magnesium pieces and stirred vigorously for 30 minutes while heating under reduced pressure. After cooling to room temperature, a piece of iodine and 22 mL of tetrahydrofuran were charged and stirred. To this solution, Eur. J. et al. Org. Chem. 2006, 2727. And slowly adding a 30 ml 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, The mixture was heated to reflux for 1 hour in an oil bath at 80 ° C. After the reaction solution was cooled to -78 ° C, 2.50 mL (22.5 mmol) of trimethoxyborane was slowly added, and stirring was continued for 18 hours while slowly returning 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 -2 ', 6'-dimethoxybiphenyl (S-Phos) 0.11 g (0.26 mmol) and 10 mL of distilled water were charged, and the mixture was heated to reflux for 2 hours in an oil bath. The reaction mixture was cooled to room temperature, 1.0 M aqueous hydrochloric acid solution was added, the soluble portion was extracted with ethyl acetate, and the obtained 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 the filtrate and stirred. This 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, and the soluble portion was extracted with ethyl acetate. The obtained fraction was washed with saturated brine and dried over anhydrous magnesium sulfate. After filtering the 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 distilling the filtrate, and in an oil bath at 120 ° C. Heated to reflux for 2 hours. After the reaction solution was cooled to room temperature, a saturated aqueous sodium hydrogen carbonate solution was added, the soluble component was extracted with hexane, and the obtained fraction was washed with saturated brine and dried over anhydrous magnesium sulfate. After filtering the magnesium sulfate, the residue obtained by distilling off the filtrate was purified by silica gel column chromatography. As a result, 3.62 g of the desired product (hereinafter referred to as the compound (1a)) represented by the following formula (1a) Yield 66%).
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 = 6.9Hz, -CH (CH 3) 2) ppm

[Example 1-2]
In a 300 mL reactor, 3.61 g (11.3 mmol) of the compound (1a) obtained in Example 1-1, 1.16 g (29.0 mmol) of sodium hydroxide, 8 mL of tetrahydrofuran, 15-crown 5-ether 0. A solution of 0.06 g (0.29 mmol) in 2 mL of tetrahydrofuran was charged, and the mixture was heated to reflux in an oil bath at 80 ° C. for 2 hours. The solution was cooled to 0 ° C., 0.42 mL (5.70 mmol) of acetone was added to the solution, stirred at room temperature for 10 minutes, and then heated to 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, and the soluble portion was extracted with ethyl acetate. The obtained fraction was washed with saturated brine and dried over anhydrous magnesium sulfate. After filtering the magnesium sulfate, hexane was added to the residue obtained by distilling the filtrate to prepare a suspension, the insoluble matter was filtered off, and the residue was dried under reduced pressure to obtain the following formula (1b). ) (1.88 g, yield 49%) was obtained (hereinafter referred to as compound (1b)).
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 = 1.7Hz, = CH-CH 2 - ), 3.39 (4H, sep, J = 6.9Hz, -CH (CH 3) 2), 2.89 (12H, s, -NC (CH 3) 2), 1.80 (6H, s, _{C-CH 3), 1.24 (} 24H, d, J = 6.9Hz, -CH (CH 3) 2) ppm

[Example 1-3]
In a 100 mL reactor sufficiently dried and purged with argon, 1.02 g (1.50 mmol) of the compound (1b) obtained in Example 1-2 and 15 mL of toluene were charged and stirred. To this solution, 0.41 g (1.52 mmol) of tetrakis (dimethylamino) zirconium was charged 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 the solvent of the reaction solution was distilled off, 10 mL of toluene and 0.40 mL (3.17 mmol) of chlorotrimethylsilane were added to the residue, and then stirring was continued in an oil bath at 70 ° C. for 3 hours. After the solvent of the reaction solution was distilled off, dichloromethane was added to the obtained solid to prepare a suspension, and insoluble matter was filtered off with a glass filter. The filtrate was concentrated under reduced pressure, and hexane was added to prepare a suspension. The insoluble material was filtered off, and the residue was dried under reduced pressure to give an orange powdery compound isopropylidenebis (4- (3,5-di-iso-propyl-4-dimethylaminophenyl) represented by the following formula (1). ) -1-Indenyl) zirconium dichloride (hereinafter referred to as metallocene compound (1)) was obtained in an amount of 0.40 g (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 = 3.6Hz, Cp-H), 3.34 (4H, sep, J = 6.8Hz, -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 = 6.8Hz , -CH (CH 3) 2) ppm
FD-mass spectrometry (M ⁺ ): 838

[Example 2]
[Example 2-1]
A 200 mL reactor thoroughly dried and purged with argon was charged with 0.53 g (21.8 mmol) of magnesium pieces and stirred vigorously for 30 minutes while heating under reduced pressure. After cooling to room temperature, a piece of iodine and 20 mL of tetrahydrofuran were charged and stirred. To this solution, J. Org. Am. Chem. Soc. 2006, 128, 16486. Slowly add a 30 mL diluted solution of 5.99 g (20.0 mmol) of 1-bromo-3,5-di-tert-butyl-4-methoxybenzene synthesized by the method described in 1 ml in an oil bath at 80 ° C. Heated to reflux for hours. After the reaction solution was cooled to -78 ° C, 2.50 mL (22.5 mmol) of trimethoxyborane was slowly added, and stirring was continued for 21 hours while slowly returning to room temperature. A 1.0 M aqueous hydrochloric acid solution was added, and the soluble component was extracted with diethyl ether. The obtained fraction was washed with water and saturated brine, and dried over anhydrous magnesium sulfate. After filtering the magnesium sulfate, the filtrate was distilled off and the residue obtained was 3.67 g (17.4 mmol) of 4-bromo-1-indanone, 8.54 g (40.2 mmol) of tripotassium phosphate, acetic acid. In an oil bath, 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. And heated at reflux for 2 hours. After the reaction solution was cooled to room temperature, a saturated aqueous ammonium chloride solution was added, the soluble component was extracted with ethyl acetate, and the obtained fraction was washed with saturated brine and dried over anhydrous magnesium sulfate. After filtering the magnesium sulfate, the residue obtained by distilling off the filtrate was purified by silica gel column chromatography to obtain 5.86 g of the desired product (hereinafter referred to as compound (2a)) represented by the following formula (2a). Yield 96%).
¹ H NMR (270 MHz, CDCl ₃ ) δ 7.75 (1H, dd, J = 7.6 and 1.1 Hz, Ar—H), 7.61 (1 H, dd, J = 7.5 and 1.2 Hz, Ar—H) ), 7.46 (1H, t, J = 7.5Hz, Ar-H), 7.34 (2H, s, Ar-H), 3.76 (3H, s, -ОCH 3), 3.25 -3.15 (2H, m, Ar- CH 2 -C), 2.73-2.68 (2H, m, Ar-CО-CH 2 -), 1.48 (18H, s, -C (CH ₃ ) ₃ ) ppm

[Example 2-2]
In a 500 mL reactor, 5.85 g (16.7 mmol) of the compound (2a) obtained in Example 2-1 was added to 20 mL of tetrahydrofuran and 8 mL of methanol, followed by stirring. The solution was cooled to 0 ° C., 1.27 g (33.7 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, and the soluble portion was extracted with ethyl acetate. The obtained fraction was washed with saturated brine and dried over anhydrous magnesium sulfate. After filtering the 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 the filtrate, and in an oil bath at 120 ° C. Heated to reflux for 2 hours. After the reaction solution was cooled to room temperature, a saturated aqueous sodium hydrogen carbonate solution was added, the soluble component was extracted with hexane, and the obtained fraction was washed with saturated brine and dried over anhydrous magnesium sulfate. After filtering the magnesium sulfate, the residue obtained by distilling off the filtrate was purified by silica gel column chromatography to obtain 4.38 g of the desired product (hereinafter referred to as compound (2b)) represented by the following formula (2b). Yield 78%).
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 = 6.6and2.3Hz, 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]
In a 100 mL reactor, 4.36 g (13.0 mmol) of the compound (2b) obtained in Example 2-2, 7 mL of tetrahydrofuran, 15 mL of 5-crown ether 0.07 g (0.33 mmol) in 1 mL of tetrahydrofuran, Sodium hydroxide 1.32 g (32.9 mmol) and acetone 0.48 mL (6.51 mmol) were charged, and the mixture was heated to 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, soluble components were extracted with hexane, and the obtained fractions were washed with saturated brine and dried over anhydrous magnesium sulfate. After filtration of magnesium sulfate, diethyl ether 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 obtain the following formula ( 1.87 g (yield 41%) of the target 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, -ОCH 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]
Tetrakis (dimethylamino) zirconium (0.67 g, 2.52 mmol) and toluene (5 mL) were charged into a 100 mL reactor thoroughly dried and purged with argon and stirred. The suspension was cooled to −78 ° C., and a suspension of 1.77 g (2.50 mmol) of the compound (2c) obtained in Example 2-3 in 15 mL of toluene was added, and then the oil suspension at 120 ° C. was added. And stirring was continued for 6 hours. After the solvent of the reaction solution was distilled off, hexane was added to the residue to prepare a suspension, the insoluble matter was filtered off with a glass filter, and the residue was dried under reduced pressure to give a pink-orange color represented by the following formula (2d). 1.36 g (yield 61%, racemic purity 88%) of a powdery compound (hereinafter referred to as metallocene compound (2d)) was obtained.
¹ H NMR (270 MHz, C ₆ D ₆ ) δ 7.80-7.70 (2H, m, Ar—H), 7.20-7.00 (10H, m, Ar—HandCp—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. 4Hz, Cp-H), 3.38 (6H, s, -ОCH 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]
In a 100 mL reactor sufficiently dried and purged with argon, 0.45 g (0.51 mmol) of the metallocene compound (2d) obtained in Example 2-4 and 6 mL of toluene were charged and stirred. To this suspension, 0.15 mL (1.19 mmol) of chlorotrimethylsilane was added at room temperature, and stirring was continued in an oil bath at 70 ° C. for 3 hours. After distilling off the solvent of the reaction solution, dichloromethane and hexane were added to the resulting solid to prepare a suspension. Insoluble matter was filtered off with a glass filter, and the residue was dried under reduced pressure to obtain the following formula (2). The isopropylidenebis (4- (3,5-di-tert-butyl-4-methoxyphenyl) -1-indenyl) zirconium dichloride (hereinafter referred to as the metallocene compound (2)) represented by the formula 35 g (yield 78%, racemic 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 = 3.7Hz, Cp-H), 3.69 (6H, s, -ОCH 3), 2.42 (6H, s, C-CH 3), 1.41 (36H, s, -C (CH 3) 3) ppm
FD-mass spectrometry (M ⁺ ): 868

[Comparative Example 1]
[Comparative Example 1-1]
In a 200 mL reactor, 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, An oil bath was charged with 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. Heated to reflux for 2 hours. After the reaction solution was cooled to room temperature, a saturated aqueous ammonium chloride solution was added, the soluble component was extracted with ethyl acetate, and the obtained fraction was washed with saturated brine and dried over anhydrous magnesium sulfate. After filtering the magnesium sulfate, the residue obtained by distilling off the filtrate was purified by silica gel column chromatography. As a result, 2.60 g (the compound (3a)) of the desired product represented by the following formula (3a) Yield 91%).
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, -ОCH 3), 3.21 -3.12 (2H, m, Ar- CH 2 -C), 2.73-2.65 (2H, m, Ar-CО-CH 2 -) ppm

[Comparative Example 1-2]
In a 200 mL reactor, 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 were charged and stirred. The solution was cooled to 0 ° C., 0.84 g (22.1 mmol) of sodium hydroborate was slowly added little by little, 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, and the soluble portion was extracted with ethyl acetate. The obtained fraction was washed with saturated brine and dried over anhydrous magnesium sulfate. After filtering the 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 distilling off the filtrate, and in an oil bath at 120 ° C. Heated to reflux for 2 hours. After the reaction solution was cooled to room temperature, a saturated aqueous sodium hydrogen carbonate solution was added, the soluble component was extracted with ethyl acetate, and the obtained fraction was washed with saturated brine and dried over anhydrous magnesium sulfate. After filtering the magnesium sulfate, the residue obtained by distilling off the filtrate was purified by silica gel column chromatography. As a result, 1.43 g Yield 63%).
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]
To a 300 mL reactor, 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) in 2 mL of tetrahydrofuran was charged and heated under reflux in an oil bath at 80 ° C. for 2 hours. The solution was cooled to 0 ° C., 0.25 mL (3.39 mmol) of acetone was added to the solution, stirred at room temperature for 10 minutes, and then heated to 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, and the soluble portion was extracted with ethyl acetate. The obtained fraction was washed with saturated brine and dried over anhydrous magnesium sulfate. After filtering the magnesium sulfate, the filtrate was distilled off, and diethyl ether and hexane were added to the resulting residue to prepare a suspension. The insoluble matter was filtered off, and the residue was dried under reduced pressure. 0.79 g (yield 51%) of the target compound represented by 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, -ОCH 3), 3.46 (4H, d, J = 1.9Hz, = CH-CH 2 -), 1.79 (6H, s, C-CH ₃₎ ppm

[Comparative Example 1-4]
In a 100 mL reactor sufficiently dried and purged with argon, 0.73 g (1.50 mmol) of the compound (3c) obtained in Comparative Example 1-3 and 15 mL of toluene were charged and stirred. The solution was cooled to −78 ° C., charged with 0.41 g (1.53 mmol) of tetrakis (dimethylamino) zirconium, stirred at room temperature for 10 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, 8 mL of toluene and 0.40 mL (3.17 mmol) of chlorotrimethylsilane were added to the residue, and stirring was continued in an oil bath at 70 ° C. for 3 hours. After distilling off the solvent of the reaction solution, dichloromethane was added to the obtained solid to prepare a suspension, the insoluble matter was filtered off with a glass filter, and the residue was dried under reduced pressure to obtain the following formula (3). 0.54 g (yield 56%, racemic purity 93%) of isopropylidenebis (4- (4-methoxyphenyl) -1-indenyl) zirconium dichloride (hereinafter referred to as metallocene compound (3)) )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 = 3.6Hz, Cp-H), 6.10 (meso-, d, J = 3.6Hz, Cp-H), 3.82 (6H, s, -ОCH 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 spectrometry (M ⁺ ): 644

[Comparative Example 2]
[Comparative Example 2-1]
Tetrakis (dimethylamino) zirconium (680 mg, 2.54 mmol) and toluene (5 mL) were charged into a 100 mL reactor thoroughly dried and purged with argon and 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 solution, stirring was continued in an oil bath at 120 ° C. for 2 hours. After the solvent of the reaction solution was distilled off, hexane was added to the residue to prepare a suspension, and the insoluble material was filtered off with a glass filter. A suspension is prepared by concentrating the obtained solution under reduced pressure, and the obtained solid is filtered and dried to obtain an orange powdery compound represented by the following formula (4a) (hereinafter referred to as a metallocene compound (4a). ) Was obtained 0.80 g (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 = 3.4Hz, Cp-H) , 2.49 (12H, s, -N (CH 3) 2), 2.08 (6H, s, C-CH 3) ppm

[Comparative Example 2-2]
Into a 30 mL reactor sufficiently dried and purged with argon, 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 and stirred. To this suspension, 0.13 mL (1.0 mmol) of chlorotrimethylsilane was added at room temperature, and stirring was continued 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 with a glass filter, and the residue was dried under reduced pressure. As a result, 0.17 g (yield 56%, racemic purity 100%) of 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 = 3.6Hz, Cp-H), 2.41 (6H, s, C-CH 3) ppm
FD-mass spectrometry (M ⁺ ): 584

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

Example 3
[Example 3-1]
A 200 mL reactor thoroughly dried and purged with argon was charged with 0.53 g (22.0 mmol) of magnesium pieces and stirred vigorously for 30 minutes while heating under reduced pressure. After cooling to room temperature, a piece of iodine and 22 mL of tetrahydrofuran were charged and stirred. To this solution, Eur. J. et al. Org. Chem. 2006, 2727. And slowly adding a 30 ml 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, The mixture was heated to reflux for 1 hour in an oil bath at 80 ° C. After the reaction solution was cooled to -78 ° C, 2.50 mL (22.5 mmol) of trimethoxyborane was slowly added, and stirring was continued for 18 hours while slowly returning to room temperature. In this reaction solution, Organometallics 2006, 25, 1217. 7.71 g (17.7 mmol) of 7-bromo-2-methylindene synthesized by the described method, 8.42 g (39.7 mmol) of tripotassium phosphate, 0.08 g (0.36 mmol) of palladium acetate, 2-dicyclohexyl Phosphino-2 ′, 6′-dimethoxybiphenyl (S-Phos) 0.22 g (0.53 mmol) and distilled water 10 mL were charged, and the mixture was heated to reflux for 2 hours in an oil bath. The reaction mixture was cooled to room temperature, 1.0 M aqueous hydrochloric acid solution was added, the soluble portion was extracted with ethyl acetate, and the obtained fraction was washed with saturated brine and dried over anhydrous magnesium sulfate. After filtering the magnesium sulfate, methanol was added to the residue obtained by evaporating the filtrate to prepare a suspension, the insoluble matter was filtered off, and the residue was dried under reduced pressure to obtain the following formula (6a). ) (4.52 g, yield 76%) was obtained (hereinafter referred to as compound (6a)).
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 _{= 6.9Hz, -CH (CH 3)} 2) ppm

[Example 3-2]
Into a 200 mL reactor sufficiently dried and purged with argon, 3.34 g (10.0 mmol) of the compound (6a) obtained in Example 3-1 and 35 mL of tetrahydrofuran were charged and stirred. Under ice-cooling, 6.20 mL of n-butyllithium solution (hexane solution, 1.63 M, 10.1 mmol) was added to this solution and stirred at room temperature for 2 hours. 1,3-Dimethyl-2-imidazolidinone 1.10 mL (11.7 mmol) was added to this solution, and then cooled to −30 ° C., 0.60 mL (5.00 mmol) of dichlorodimethylsilane was added, and the mixture was slowly added to room temperature. Stirring was continued for 17 hours while returning to. A saturated aqueous ammonium chloride solution was added, the soluble component was extracted with n-hexane, and the resulting fraction was washed with saturated brine and dried over anhydrous magnesium sulfate. After filtering the magnesium sulfate, the residue obtained by distilling off the filtrate was purified by silica gel column chromatography. As a result, 3.03 g (the compound (6b)) of the desired product represented by the following formula (6b) Yield 84%) as an isomer mixture.
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 = 6.8Hz, -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]
In a 100 mL reactor sufficiently dried and purged with argon, 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 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 then stirring was continued 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 obtained 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 the solvent of the reaction solution was distilled off, dichloromethane was added to the obtained solid to prepare a suspension, and insoluble matter was removed with a membrane syringe filter. After concentrating the obtained solution under reduced pressure, n-hexane was added to adjust the suspension, and the insoluble material was filtered off with a glass filter. The resulting solution was concentrated under reduced pressure, and then the suspension was adjusted by adding n-hexane, the insoluble matter was filtered off, and the residue was dried under reduced pressure to give an orange powder represented by the following formula (6). 0.05 g of dimethylsilylenebis (4- (3,5-di-iso-propyl-4-dimethylaminophenyl) -2-methyl-1-indenyl) zirconium dichloride (hereinafter referred to as metallocene compound (6)) (Yield 11%, racemic purity 100%).
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 = 6.9Hz , -CH (CH 3) 2), 2.84 (12H, s, -NC (CH 3) 2), 2.27 (6H, s, Cp-CH 3) , 1.34 (6H, s, Si -CH 3), 1.25 (12H, d, J = 6.9Hz, -CH (CH 3) 2), 1.14 (12H, d, J = 6. _{9Hz, -CH (CH 3) 2} ) ppm
FD-mass spectrometry (M ⁺ ): 882

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

Example 4
<(2) Preparation of solid carrier>
Using a reactor equipped with a stirrer with an internal volume of 270 L, under a nitrogen atmosphere, silica gel (manufactured by Fuji Silysia Chemical Co., Ltd .: 50% cumulative volume distribution of laser light diffraction scattering method, particle size 70 μm, specific surface area 340 m ² / g, pore volume 10 kg of 1.3 cm ³ / g, dried at 250 ° C. for 10 hours) was suspended in 77 L of toluene, and then cooled to 0 to 5 ° C. To this suspension, 19.4 liters of a toluene solution of methylaluminoxane (3.5 mol / L in terms of Al atom) was added dropwise over 30 minutes. At this time, the system temperature was kept at 0 to 5 ° C.

Subsequently, after making it contact at 0-5 degreeC for 30 minutes, the system temperature was heated up to 95 degreeC over 1.5 hours, and it was made to contact at 95 degreeC continuously for 4 hours. Thereafter, the temperature was lowered to room temperature, the supernatant was removed by decantation, and further washed twice with toluene, and then a total amount of 115 liters of a solid support toluene slurry was prepared.
When a part of the obtained slurry component was collected and analyzed, the solid content concentration was 122.6 g / L.

<(3) Preparation of solid catalyst component for olefin polymerization>
A reactor equipped with a stirrer with an internal volume of 200 mL that had been sufficiently purged with nitrogen was charged with 30 mL of toluene and 8.2 mL of the above solid carrier slurry (solid weight 1.0 g). Subsequently, 0.025 mmol of a toluene solution of the metallocene compound (1) obtained in Example 1 was added and contacted at a system temperature of 20 to 25 ° C. for 1 hour, and then the supernatant was removed by decantation, and heptane was further removed. After washing twice, 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
A stainless steel autoclave with an internal volume of 1 L that was sufficiently purged with nitrogen was charged with 500 mL of heptane, and the system was substituted with ethylene. Then, 0.375 mmol of triisobutylaluminum and the solid catalyst component slurry (I ) As a solid component, and the temperature inside the system was raised to 80 ° C. Next, by continuously introducing ethylene, a polymerization reaction was carried out for 90 minutes under the 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 60.1 g of an ethylene polymer. The polymerization activity was 600.3 g-PE / g-cat. h.
The density of the obtained polymer was 931 kg / m ³ , the weight average molecular weight (Mw) was 451,600, and the number average molecular weight (Mn) was 128,800.

Example 8
A stainless steel autoclave with an internal volume of 1 L, which was sufficiently purged with nitrogen, was charged with 500 mL of heptane and the inside of the system was substituted with ethylene. Then, 10 mL of 1-hexene, 0.375 mmol of triisobutylaluminum and the solid obtained in Example 4 were used. 60 mg of the catalyst component slurry (I) was added as a solid component, and the temperature in the system was raised to 80 ° C. Next, by continuously introducing ethylene, a polymerization reaction was carried out for 90 minutes under the 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 46.1 g of an ethylene polymer. The polymerization activity was 767.8 g-PE / g-cat. h.

The density of the obtained polymer was 905 kg / m ³ , the 1-hexene content was 4.7 mol%, the weight average molecular weight (Mw) was 139,900, and the number average molecular weight (Mn) was 52,100. It was.

Example 9
A stainless steel autoclave with an internal volume of 1 L that had been sufficiently purged with nitrogen was charged with 500 mL of heptane, and the system was substituted with ethylene. Then, 0.375 mmol of triisobutylaluminum and the solid catalyst component slurry (II) obtained in Example 5 above (II) ) As a solid component, and the temperature inside the system was raised to 80 ° C. Next, by continuously introducing ethylene, a polymerization reaction was carried out for 90 minutes under the 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 64.0 g of an ethylene polymer. The polymerization activity was 638.7 g-PE / g-cat. h.
The density of the obtained polymer was 931 kg / m ³ , the weight average molecular weight (Mw) was 490,500, and the number average molecular weight (Mn) was 122,500.

Example 10
A stainless steel autoclave with an internal volume of 1 L that has been sufficiently purged with nitrogen was charged with 500 mL of heptane, and the system was substituted with ethylene. Then, 10 mL of 1-hexene, 0.375 mmol of triisobutylaluminum, and the solid obtained in Example 5 were used. 60 mg of the catalyst component slurry (II) was added as a solid component, and the temperature in the system was raised to 80 ° C. Next, by continuously introducing ethylene, a polymerization reaction was carried out for 90 minutes under the 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 42.8 g of an ethylene polymer. The polymerization activity was 712.0 g-PE / g-cat. h.

The density of the obtained polymer was 907 kg / m ³ , the 1-hexene content was 6.4 mol%, the weight average molecular weight (Mw) was 147,300, and the number average molecular weight (Mn) was 43,200. It was.

[Comparative Example 9]
A stainless steel autoclave with an internal volume of 1 L, which was sufficiently purged with nitrogen, was charged with 500 mL of heptane and the system was substituted with ethylene. Then, 0.375 mmol of triisobutylaluminum and the solid catalyst component slurry (III ) As a solid component, and the temperature inside the system was raised to 80 ° C. Next, by continuously introducing ethylene, a polymerization reaction was carried out for 90 minutes under the 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 12.3 g of an ethylene polymer. The polymerization activity was 121.7 g-PE / g-cat. h.
The weight average molecular weight (Mw) of the obtained polymer was 410,000, and the number average molecular weight (Mn) was 73,200.

[Comparative Example 10]
A stainless steel autoclave with an internal volume of 1 L that has been sufficiently purged with nitrogen was charged with 500 mL of heptane, and the system was substituted with ethylene. 100 mg of catalyst component slurry (III) was added as a solid component, and the temperature in the system was raised to 80 ° C. Next, by continuously introducing ethylene, a polymerization reaction was carried out for 90 minutes under the 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 an ethylene polymer. The polymerization activity was 426.1 g-PE / g-cat. h.
The 1-hexene content of the obtained polymer was 4.2 mol%, the weight average molecular weight (Mw) was 136,800, and the number average molecular weight (Mn) was 27,000.

[Comparative Example 11]
500 mL of heptane was charged into a 1 L stainless steel autoclave sufficiently purged with nitrogen, and the system was substituted with ethylene. ) As a solid component, and the temperature inside the system was raised to 80 ° C. Next, by continuously introducing ethylene, a polymerization reaction was carried out for 90 minutes under the 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 22.4 g of an ethylene polymer. The polymerization activity was 222.5 g-PE / g-cat. h.
The density of the obtained polymer was 936 kg / m ³ , the weight average molecular weight (Mw) was 347,700, and the number average molecular weight (Mn) was 37,300.

[Comparative Example 12]
500 mL of heptane was charged into a 1 L stainless steel autoclave sufficiently purged with nitrogen, and the system was substituted with ethylene. 100 mg of catalyst component slurry (IV) was added as a solid component, and the temperature in the system was raised to 80 ° C. Next, by continuously introducing ethylene, a polymerization reaction was carried out for 90 minutes under the 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 88.8 g of an ethylene polymer. The polymerization activity was 887.1 g-PE / g-cat. h.

The density of the obtained polymer was 916 kg / m ³ , the 1-hexene content was 2.6 mol%, the weight average molecular weight (Mw) was 14,600, and the number average molecular weight (Mn) was 34,200. It was.

[Comparative Example 13]
A stainless steel autoclave with an internal volume of 1 L that was sufficiently purged with nitrogen was charged with 500 mL of heptane, and the system was substituted with ethylene. Then, the solid catalyst component slurry (V ) As a solid component, and the temperature inside the system was raised to 80 ° C. Next, by continuously introducing ethylene, a polymerization reaction was carried out for 90 minutes under the 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 an ethylene polymer. The polymerization activity was 188.5 g-PE / g-cat. h.
The density of the obtained polymer was 942 kg / m ³ , the weight average molecular weight (Mw) was 179,500, and the number average molecular weight (Mn) was 32,300.

[Comparative Example 14]
A stainless steel autoclave with an internal volume of 1 L that has been sufficiently purged with nitrogen is charged with 500 mL of heptane and the system is substituted with ethylene. 60 mg of the catalyst component slurry (V) was added as a solid component, and the temperature in the system was raised to 80 ° C. Next, by continuously introducing ethylene, a polymerization reaction was carried out for 90 minutes under the 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 48.0 g of an ethylene polymer. The polymerization activity was 799.5 g-PE / g-cat. h.

The density of the obtained polymer was 927 kg / m ³ , the 1-hexene content was 2.7 mol%, the weight average molecular weight (Mw) was 51,800, and the number average molecular weight (Mn) was 13,300. It was.
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, Comparative Example 2 and the metallocene compound (4 described in the claims of JP-A No. 2014-193846) In Comparative Examples 11 and 12 using), an increase in the molecular weight of the produced polymer was observed, but no improvement in 1-hexene copolymerizability was observed.

  In Comparative Examples 9 and 10 using the metallocene compound (3) described in the claims of Comparative Example 1 and JP-A No. 2014-193848, 1-hexene, which is considered to be an effect of introducing an electron-donating substituent. Although an improvement in copolymerizability is observed, a decrease in polymerization activity, which is thought to be due to the interaction between the heteroatom and the aluminum compound, is observed.

However, in Examples 7 to 10 using the metallocene compounds (1) and (2) described in the claims, in addition to the fact that no significant decrease in polymerization activity is observed, rather than ethylene homopolymerization. In certain Examples 16 and 18, a clear improvement in polymerization activity and a higher molecular weight of the produced polymer were observed.
Further, in Examples 8 and 10, a marked improvement in 1-hexene copolymerizability, a resulting decrease in the density of the produced polymer, and a tendency to narrow the molecular weight distribution were observed.

Example 11
A stainless steel autoclave with an internal volume of 1 L that had been sufficiently purged with nitrogen was charged with 500 mL of heptane, and the inside of the system was substituted with ethylene. Then, 0.375 mmol of triisobutylaluminum and the solid catalyst component slurry (VI ) As a solid component, and the temperature inside the system was raised to 80 ° C. Next, by continuously introducing ethylene, a polymerization reaction was carried out for 90 minutes under the 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 44.7 g of an ethylene polymer. The polymerization activity was 446.0 g-PE / g-cat. h.
The density of the obtained polymer was 937 kg / m ³ , the weight average molecular weight (Mw) was 466,500, and the number average molecular weight (Mn) was 88,800.

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

The density of the obtained polymer was 897 kg / m ³ , the 1-hexene content was 6.2 mol%, the weight average molecular weight (Mw) was 325,600, and the number average molecular weight (Mn) was 113,500. It was.

[Comparative Example 15]
A stainless steel autoclave with an internal volume of 1 L that had been sufficiently purged with nitrogen was charged with 500 mL of heptane, and the inside of the system was substituted with ethylene. ) As a solid component, and the temperature inside the system was raised to 80 ° C. Next, by continuously introducing ethylene, a polymerization reaction was carried out for 90 minutes under the 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 32.3 g of an ethylene polymer. The polymerization activity was 322.4 g-PE / g-cat. h.
The density of the obtained polymer was 936 kg / m ³ , the weight average molecular weight (Mw) was 704,600, and the number average molecular weight (Mn) was 105,200.

[Comparative Example 16]
A stainless steel autoclave having an internal volume of 1 L that has been sufficiently purged with nitrogen was charged with 500 mL of heptane, and the system was substituted with ethylene. 20 mg of the catalyst component slurry (VII) was added as a solid component, and the temperature in the system was raised to 80 ° C. Next, by continuously introducing ethylene, a polymerization reaction was carried out for 90 minutes under the 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 6.55 g of an ethylene polymer. The polymerization activity was 326.5 g-PE / g-cat. h.

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

Compared with Comparative Examples 15 and 16 using the known metallocene compound (7) described in Comparative Example 4 and using the metallocene compound (6) described in Example 3 which is the scope of the present patent claims Examples 11 and 12 showed very high polymerization activity. In Example 12, which is a copolymerization of ethylene and 1-hexene, a remarkable improvement in polymerization activity and an increase in the molecular weight of the produced polymer were observed.
Furthermore, in Example 12, the tendency of remarkable improvement of 1-hexene copolymerization, the resulting low density of the produced polymer and narrowing of the molecular weight distribution was observed.

Example 13
[Example 13-1]
A 200 mL reactor that had been thoroughly dried and purged with argon was charged with 0.42 g (17.2 mmol) of magnesium pieces and stirred vigorously for 30 minutes while heating under reduced pressure. After cooling to room temperature, a piece of iodine and 15 mL of tetrahydrofuran were charged and stirred. To this solution, J. Org. Am. Chem. Soc. 2006, 128, 16486. Slowly add a diluted solution of 4.67 g (15.6 mmol) of 1-bromo-3,5-di-tert-butyl-4-methoxybenzene synthesized in the described manner in 25 mL of tetrahydrofuran, and heat to reflux in an oil bath for 1 hour. did. After the reaction solution was cooled to -78 ° C, 2.00 mL (18.0 mmol) of trimethoxyborane was slowly added, and stirring was continued for 21 hours while slowly returning to room temperature. A 1.0 M aqueous hydrochloric acid solution was added, and the soluble component was extracted with diethyl ether. The obtained fraction was washed with water and saturated brine, and dried over anhydrous magnesium sulfate. After filtering the magnesium sulfate, the filtrate was distilled off to obtain a residue obtained from Organometallics 2006, 25, 1217. 4-bromo-2-methyl-1-indanone 2.70 g (12.0 mmol), tripotassium phosphate 6.69 g (31.5 mmol), palladium acetate 0.03 g (0.13 mmol) synthesized by the method described 2-dicyclohexylphosphino-2 ′, 6′-dimethoxybiphenyl (S-Phos) 0.08 g (0.18 mmol), 30 mL of tetrahydrofuran and 6 mL of distilled water were charged, and the mixture was heated to reflux for 2 hours in an oil bath. After the reaction solution was cooled to room temperature, a saturated aqueous ammonium chloride solution was added, the soluble component was extracted with ethyl acetate, and the obtained fraction was washed with saturated brine and dried over anhydrous magnesium sulfate. After filtering the magnesium sulfate, the residue obtained by distilling off the filtrate was purified by silica gel column chromatography. As a result, 4.09 g of the desired product (hereinafter referred to as compound (8a)) represented by the following formula (8a) was obtained. Yield 93%).
¹ H NMR (270 MHz, CDCl ₃ ) δ 7.75 (1H, dd, J = 7.5 and 1.2 Hz, Ar—H), 7.61 (1 H, dd, J = 7.5 and 1.2 Hz, Ar—H) ), 7.45 (1H, t, J = 7.5Hz, Ar-H), 7.33 (2H, s, Ar-H), 3.76 (3H, s, -OCH 3), 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]
In a 200 mL reactor sufficiently dried and purged with argon, 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 charged and stirred. The solution was cooled to 0 ° C., 0.85 g (22.6 mmol) of sodium hydroborate was slowly added little by little, 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, and the soluble portion was extracted with ethyl acetate. The obtained 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 distilling the filtrate, and heated in an oil bath for 1 hour. Refluxed. After the reaction solution was cooled to room temperature, a saturated aqueous sodium hydrogen carbonate solution was added, the soluble component was extracted with n-hexane, and the resulting fraction was washed with saturated brine and dried over anhydrous magnesium sulfate. After filtering the magnesium sulfate, the residue obtained by distilling off the filtrate was purified by silica gel column chromatography. As a result, 3.51 g of the desired product (hereinafter referred to as the compound (8b)) represented by the following formula (8b) was obtained. Yield 90%).
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 = 7.4and1.3Hz, Ar-H), 6.53 (1H, dd, J = 2.9and1.4Hz, 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]
Into a 200 mL reactor sufficiently dried and purged with argon, 2.10 g (6.02 mmol) of the compound (8b) obtained in Example 13-2 and 15 mL of tetrahydrofuran were charged and stirred. To this solution was added 3.90 mL of n-butyllithium solution (hexane solution, 1.55 M, 6.05 mmol) to this solution under ice cooling, and the mixture was stirred at room temperature for 2 hours. To this solution, 0.60 mL (6.39 mmol) of 1,3-dimethyl-2-imidazolidinone was added and then cooled to 0 ° C., 0.36 mL (3.01 mmol) of dichlorodimethylsilane was added slowly to room temperature. Stirring was continued for 16 hours while returning. A saturated aqueous ammonium chloride solution was added, the soluble component was extracted with n-hexane, and the resulting fraction was washed with saturated brine and dried over anhydrous magnesium sulfate. After filtering the magnesium sulfate, the residue obtained by distilling off the filtrate was purified by silica gel column chromatography. As a result, 1.42 g of the desired product (hereinafter referred to as the compound (8c)) represented by the following formula (8c) was obtained. (Yield 63%) as an isomer mixture.
¹ H NMR (270 MHz, CDCl ₃ ) δ 7.60-7.00 (10H, m, Ar-H), 699-6.65 (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 (36H, s, -C (CH 3) 3), - 0.13--0.28 (3H, m, Si-CH 3) ppm

[Example 13-4]
In a 100 mL reactor sufficiently dried and purged with argon, 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 and stirred. To this solution, 0.65 mL of n-butyllithium solution (hexane solution, 1.54 M, 1.00 mmol) was added at room temperature, and then stirring was continued 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 0.6 mL of diethyl ether were added to the obtained 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 the solvent of the reaction solution was distilled off, dichloromethane was added to the obtained solid to prepare a suspension, and insoluble matter was removed with a membrane syringe filter. After concentrating the obtained solution under reduced pressure, n-hexane was added to adjust the suspension, and the insoluble material was filtered off with a glass filter. The residue was dissolved in toluene, n-hexane was added, and the mixture was allowed to stand for 24 hours under cooling at 0 ° C. The crystallized crystals were filtered off, 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 (yield 33%, meso form purity 92%) of phenyl) -2-methyl-1-indenyl) zirconium dichloride (hereinafter referred to as metallocene compound (8)) was obtained. After the filtrate was concentrated under reduced pressure, the suspension was adjusted by adding n-hexane, the insoluble matter was filtered off with a glass filter, and the residue was dried under reduced pressure to obtain 0.08 g of the 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 spectrometry (M ⁺ ): 912

[Comparative Example 17]
Dimethylsilylenebis (4- (3,5-di-tert-butylphenyl) -2-methyl-1-indenyl) zirconium dichloride (metallocene compound (9)) was synthesized by the method described in JP-T-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
To a glass reactor having an internal volume of 500 mL sufficiently purged with nitrogen, 250 mL of toluene was charged, 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 the gas phase. Subsequently, 1.0 ml (1.25 mmol) of a toluene solution (1.25 mol / L) of methylaluminoxane (PMAO) was obtained in the state where propylene was continuously supplied at the same flow rate, 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 performed at 85 ° C. for 5 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 2.0 L of methanol containing a small amount of hydrochloric acid to precipitate a polymer. The polymer was recovered by filtration and dried at 80 ° C. for 10 hours under reduced pressure to obtain 4.01 g of a propylene polymer. The polymerization activity was 481,000 g-PP / mmol-Zr. 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 a toluene solution (1.00 mol / L) of the metallocene compound (8) having a racemic purity of 80% obtained in Example 13-4 was added. The polymerization reaction was carried out in the same manner as in Example 14 except that. The obtained propylene polymer was 3.94 g, and the polymerization activity was 236,000 g-PP / mmol-Zr. 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 a 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 obtained propylene polymer was 1.12 g, and the polymerization activity was 67,000 g-PP / mmol-Zr. h.
The obtained polymer had a melting point of 148.7 ° C. and a number average molecular weight (Mn) of 14,500.

[Comparative Example 20]
Example 14 and Example 14 except that 0.003 mL (3.00 μmol) of a 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 performed in the same manner. The obtained propylene polymer was 3.87 g, and the polymerization activity was 155,000 g-PP / mmol-Zr. h.

The obtained 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, Examples 3-3 and 13-4 which are the scope of claims are as follows. Examples 14 and 15 using the described metallocene compounds (6) and (8) showed high polymerization activity.

  In addition, examples using the metallocene compounds (6) and (8) described in Examples 3-3 and 13-4 which are claims of the present invention by comparing the melting points of the obtained propylene polymers In 14 and 15, high stereoregularity was expressed, and a remarkable tendency to increase the molecular weight was also observed.

Example 16
A glass reactor having an internal volume of 500 mL sufficiently purged with nitrogen was charged with 216 mL of cyclohexane and 24 mL of hexane, 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 the gas phase. In the state where ethylene (E) was continuously supplied at the same flow rate, tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene (TD) 15.0 mL, styrene (ST) 3.80 mL, triisobutylaluminum in toluene solution (1.00 mol / L) 0.70 mL (0.7 mmol) were sequentially inserted. Furthermore, the toluene solution (0.67 mmol / L) of the metallocene compound (1) obtained in Example 1-3 was 3.00 mL (2.0 μmol), 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 performed 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 a methanol / acetone (1/3; v / v) mixed solvent containing a small amount of hydrochloric acid. Was precipitated. The polymer was recovered by filtration, and dried at 80 ° C. under reduced pressure for 10 hours to obtain 143 mg of an ethylene / TD / ST copolymer. The polymerization activity was 430 g-Polym / mmol-Zr. h.

  The obtained 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 was “E / TD / ST = 61. 0.020.5 / 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 the polymerization activity was 650 g-Polym / mmol-Zr. h.

  The obtained polymer has 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 is “E / TD / ST = 59. 0.7 / 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 small, and it was impossible to measure the intrinsic viscosity and the content of each monomer.

[Comparative Example 22]
A polymerization reaction was performed 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. h.

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

  Moreover, compared with Comparative Example 22 using the known metallocene compound (5) described in Comparative Example 3, the metallocene compounds described in Examples 1-3 and 2-5 (claims) In Examples 16 and 17 using 1) and (2), since high styrene copolymerizability was exhibited, it was found that the styrene conversion rate was very excellent.

Example 18
In a 100 mL reactor sufficiently dried and purged with argon, 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 and stirred. To this solution, 0.61 mL of n-butyllithium solution (hexane solution, 1.64 M, 1.00 mmol) was added at room temperature, and then stirring was continued 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 0.6 mL of diethyl ether were added to the obtained solid. This solution was cooled to 0 ° C., 0.16 g (0.51 mmol) of haunium tetrachloride was added, and stirring was continued at room temperature for 17 hours. After the solvent of the reaction solution was distilled off, dichloromethane was added to the obtained solid to prepare a suspension, and insoluble matter was removed with a membrane syringe filter. The resulting solution was concentrated to dryness under reduced pressure, and then n-hexane was added to adjust the suspension, and the insoluble material was filtered off with a glass filter. After the filtrate was concentrated under reduced pressure, the suspension was adjusted by adding n-hexane, the insoluble matter was filtered off with a glass filter, and the residue was dried under reduced pressure, whereby the yellow color represented by the following formula (11) was obtained. Powdered compound dimethylsilylene bis (4- (3,5-di-tert-butyl-4-methoxyphenyl) -2-methyl-1-indenyl) haonium dichloride (hereinafter referred to as metallocene compound (11)) 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
In a 100 mL reactor sufficiently dried and purged with argon, 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 and stirred. To this solution, 0.61 mL of n-butyllithium solution (hexane solution, 1.64 M, 1.00 mmol) was added at room temperature, and then stirring was continued 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 0.6 mL of diethyl ether were added to the obtained solid. The 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 the solvent of the reaction solution was distilled off, dichloromethane and toluene were added to the obtained solid to prepare a suspension, and insoluble matter was removed with a membrane syringe filter. The resulting solution was concentrated to dryness under reduced pressure, and then the suspension was adjusted by adding dichloromethane, the insoluble matter was filtered off with a glass filter, and the residue was dried under reduced pressure to obtain the following formula (12). Dimethylsilylenebis (4- (3,5-di-iso-propyl-4-dimethylaminophenyl) -2-methyl-1-indenyl) haonium dichloride (hereinafter referred to as metallocene compound (12)) 0.05 g (yield 11%, meso form purity 88%) was obtained. The filtrate was concentrated under reduced pressure, and the precipitated insoluble matter was filtered off with a glass filter. After the filtrate was concentrated to dryness under reduced pressure, n-hexane was added to adjust the suspension, and the insoluble matter was filtered off with a glass filter. The residue was dried under reduced pressure to obtain 0.07 g (yield 15%, racemic purity 100%) of the metallocene compound (12).
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 = 6.89Hz, -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 (15 H, d, J = 6.9 Hz, Si—CH ₃ and —CH (CH ₃ ) ₂ ), 1.14 (12H , d, J = 6.9Hz, -CH (CH 3) 2) ppm, [rac-] δ 7.68 (2H, d, J = 8.8Hz, Ar-H), 7. 2-7.35 (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 = 6.73Hz, -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 = _{6.9Hz, -CH (CH 3) 2} ) ppm
FD-mass spectrometry (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 Schlenk tube that had been sufficiently dried and purged with nitrogen, and 2.5 μmol of the metallocene compound (11) obtained in Example 18 was added as a catalyst. After the preparation, the catalyst (11) was 0.5 μmol / mL. An equivalent amount of triisobutylaluminum (n-hexane solvent, 0.5 mmol in terms of aluminum atom) was added at room temperature with stirring to an amount of toluene and catalyst (11) to prepare a catalyst solution.

  A SUS autoclave with an internal volume of 1,500 ml sufficiently dried and purged with nitrogen was charged with 550 mL of heptane and 1.5 mL of a hexane solution of triisobutylaluminum (Al = 0.5 M, 0.75 mmol) as a polymerization solvent, Next, 90 g of 1-butene was added with stirring at 850 rpm, and then the polymerization temperature was raised to 65 ° C. Furthermore, the autoclave was pressurized with nitrogen at that temperature until the internal pressure of the autoclave reached 0.5 MPaG.

  The autoclave was charged with the catalyst solution prepared above, and then 10 equivalents of triphenylcarbenium tetrakis (pentafluorophenyl) borate (toluene solvent, 25 μmol in terms of boron atom) was charged with respect to the catalyst (11). Then, the polymerization was started, and methanol was added 10 minutes after the start of the polymerization to stop the polymerization.

  The polymer solution taken out from the cooled / depressurized autoclave was put into methanol, and the polymer was precipitated and collected by filtration. Thereafter, the recovered polymer was dried under reduced pressure at 80 ° C. for 12 hours to obtain 80.0 g of a 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 Schlenk tube sufficiently dried and purged with nitrogen, and 2.0 μmol of the racemic metallocene compound (12) obtained in Example 19 was added as a catalyst. After the preparation, 0.5 μmol of the catalyst (12) was added. / Equivalent amount of toluene, 200 equivalents of triisobutylaluminum (n-hexane solvent, 0.4 mmol in terms of aluminum atom) was added at room temperature with stirring to prepare a catalyst solution. .

  A SUS autoclave with an internal volume of 1,500 ml sufficiently dried and purged with nitrogen was charged with 550 mL of heptane and 1.5 mL of a hexane solution of triisobutylaluminum (Al = 0.5 M, 0.75 mmol) as a polymerization solvent, Next, 90 g of 1-butene was added with stirring at 850 rpm, and then the polymerization temperature was raised to 65 ° C. Furthermore, the autoclave was pressurized with nitrogen at that temperature until the internal pressure of the autoclave reached 0.5 MPaG.

  The autoclave was charged with the catalyst solution prepared above, and then 10 equivalents of triphenylcarbenium tetrakis (pentafluorophenyl) borate (toluene solvent, 20 μmol in terms of boron atom) was charged with respect to the catalyst (12). Then, the polymerization was started, and methanol was added 10 minutes after the start of the polymerization to stop the polymerization.

  The polymer solution taken out from the cooled / depressurized autoclave was put into methanol, and the polymer was precipitated and collected by filtration. Thereafter, the collected polymer was dried under reduced pressure at 80 ° C. for 12 hours to obtain 47.1 g of a 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 Schlenk tube sufficiently dried and purged with nitrogen, and 2.5 μmol of the metallocene compound (13) obtained in Comparative Example 23 was added as a catalyst. After preparation, the catalyst (13) was 0.5 μmol / mL. An equivalent amount of triisobutylaluminum (n-hexane solvent, 0.5 mmol in terms of aluminum atom) was added at room temperature with stirring to an amount of toluene and catalyst (13) to prepare a catalyst solution.

  A SUS autoclave with an internal volume of 1,500 ml sufficiently dried and purged with nitrogen was charged with 550 mL of heptane and 1.5 mL of a hexane solution of triisobutylaluminum (Al = 0.5 M, 0.75 mmol) as a polymerization solvent, Next, 90 g of 1-butene was added with stirring at 850 rpm, and then the polymerization temperature was raised to 65 ° C. Furthermore, the autoclave was pressurized with nitrogen at that temperature until the internal pressure of the autoclave reached 0.5 MPaG.

  The autoclave was charged with the catalyst solution prepared above, and then 10 equivalents of triphenylcarbenium tetrakis (pentafluorophenyl) borate (toluene solvent, 25 μmol in terms of boron atom) was charged with respect to the catalyst (13). Then, the polymerization was started, and methanol was added 10 minutes after the start of the polymerization to stop the polymerization.

  The polymer solution taken out from the cooled / depressurized autoclave was put into methanol, and the polymer was precipitated and collected by filtration. Thereafter, the recovered polymer was dried under reduced pressure at 80 ° C. for 12 hours to obtain 51.1 g of a 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 Schlenk tube sufficiently dried and purged with nitrogen, and 1.5 μmol of the metallocene compound (11) obtained in Example 18 was added as a catalyst. After preparation, the catalyst (11) was 0.5 μmol / mL. To a certain amount of toluene and catalyst (11), 200 equivalents of triisobutylaluminum (n-hexane solvent, 0.3 mmol in terms of aluminum atom) was added at room temperature with stirring to prepare a catalyst solution.

  A SUS autoclave with an internal volume of 1,500 ml sufficiently dried and purged with nitrogen was charged with 550 mL of heptane and 1.5 mL of a hexane solution of triisobutylaluminum (Al = 0.5 M, 0.75 mmol) as a polymerization solvent, Next, 90 g of 1-butene was added with stirring at 850 rpm, and then the polymerization temperature was raised to 65 ° C. Further, 35.5 NmL of hydrogen was added at that temperature, and then pressurized with nitrogen until the internal pressure of the autoclave reached 0.5 MPaG.

  The autoclave was charged with the catalyst solution prepared above, and then 10 equivalents of triphenylcarbenium tetrakis (pentafluorophenyl) borate (toluene solvent, 15 μmol in terms of boron atom) was charged with respect to the catalyst (11). Then, the polymerization was started, and methanol was added 10 minutes after the start of the polymerization to stop the polymerization.

  The polymer solution taken out from the cooled / depressurized autoclave was put into methanol, and the polymer was precipitated and collected by filtration. Thereafter, the recovered polymer was dried under reduced pressure at 80 ° C. for 12 hours to obtain 71.9 g of a 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 Schlenk tube sufficiently dried and purged with nitrogen, and 1.5 μmol of the racemic metallocene compound (12) obtained in Example 19 was added as a catalyst. After the preparation, 0.5 μmol of the catalyst (12) was added. / Equivalent amount of toluene, 200 equivalents of triisobutylaluminum (n-hexane solvent, 0.3 mmol in terms of aluminum atom) was added at room temperature to the catalyst (12) with stirring to prepare a catalyst solution. .

  A SUS autoclave with an internal volume of 1,500 ml sufficiently dried and purged with nitrogen was charged with 550 mL of heptane and 1.5 mL of a hexane solution of triisobutylaluminum (Al = 0.5 M, 0.75 mmol) as a polymerization solvent, Next, 90 g of 1-butene was added with stirring at 850 rpm, and then the polymerization temperature was raised to 65 ° C. Further, 35.5 NmL of hydrogen was added at that temperature, and then pressurized with nitrogen until the internal pressure of the autoclave reached 0.5 MPaG.

  The autoclave was charged with the catalyst solution prepared above, and then 10 equivalents of triphenylcarbenium tetrakis (pentafluorophenyl) borate (toluene solvent, 15 μmol in terms of boron atom) was charged with respect to the catalyst (12). Then, the polymerization was started, and methanol was added 10 minutes after the start of the polymerization to stop the polymerization.

  The polymer solution taken out from the cooled / depressurized autoclave was put into methanol, and the polymer was precipitated and collected by filtration. Thereafter, the collected polymer was dried under reduced pressure at 80 ° C. for 12 hours to obtain 76.1 g of a 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 Schlenk tube that had been thoroughly dried and purged with nitrogen, and 2.0 μmol of the metallocene compound (13) obtained in Comparative Example 23 was added as a catalyst. A catalyst solution was prepared by adding 200 equivalents of triisobutylaluminum (n-hexane solvent, 0.4 mmol in terms of aluminum atom) at room temperature with stirring to an amount of toluene and catalyst (13).

  A SUS autoclave with an internal volume of 1,500 ml sufficiently dried and purged with nitrogen was charged with 550 mL of heptane and 1.5 mL of a hexane solution of triisobutylaluminum (Al = 0.5 M, 0.75 mmol) as a polymerization solvent, Next, 90 g of 1-butene was added with stirring at 850 rpm, and then the polymerization temperature was raised to 65 ° C. Further, 35.5 NmL of hydrogen was added at that temperature, and then pressurized with nitrogen until the internal pressure of the autoclave reached 0.5 MPaG.

  The autoclave was charged with the catalyst solution prepared above, and then 10 equivalents of triphenylcarbenium tetrakis (pentafluorophenyl) borate (toluene solvent, 20 μmol in terms of boron atom) was charged with respect to the catalyst (13). Then, the polymerization was started, and methanol was added 10 minutes after the start of the polymerization to stop the polymerization.

The polymer solution taken out from the cooled / depressurized autoclave was put into methanol, and the polymer was precipitated and collected by filtration. Thereafter, the recovered polymer was dried under reduced pressure at 80 ° C. for 12 hours to obtain 64.7 g of a 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 with Comparative Examples 24 and 25 using the known metallocene compound (13) described in Comparative Example 23, the metallocene compounds (11) and ( In Examples 20-23 using 12), extremely high polymerization activity was shown.

  Further, by comparing the melting points of the obtained 1-butene polymers, Examples 20 to 20 using the metallocene compounds (11) and (12) described in Examples 18 and 19 which are claims of the present invention are used. In 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 an olefin polymerization catalyst containing a novel transition metal compound into which a specific substituent according to the present invention has been introduced, ethylene is homopolymerized or copolymerized with ethylene and an α-olefin. An olefin polymer having an olefin polymerization activity and a sufficient molecular weight can be produced, and particularly excellent α-olefin copolymerizability and a tendency to narrow the molecular weight distribution are exhibited. If the present invention is used, it is expected that a polyolefin excellent in the balance of impact resistance, light weight and transparency utilizing these characteristics can be provided with high productivity. For this reason, it can be said that the present invention has extremely high industrial value.

  In addition, by using an olefin polymerization catalyst containing a novel transition metal compound into which a specific substituent according to the present invention is introduced, polymerization of a propylene polymer, copolymerization of ethylene, a cyclic olefin, and an aromatic vinyl compound can be achieved. The polymerization and the polymerization of the 1-butene polymer can also be performed with good polymerization activity. The resulting propylene polymer has high stereoregularity and a high molecular weight, and the resulting 1-butene polymer has high stereoregularity. Moreover, the obtained copolymer of ethylene, a cyclic olefin, and an aromatic vinyl compound has the conversion rate of the excellent aromatic vinyl compound. For this reason, the industrial value of the present invention is high.

Claims (14)

Transition metal compound [A] represented by the following general formula [1].

(In general formula [1],
M is a periodic table group 4 transition metal atom,
n is an integer of 1 to 4 that satisfies the valence of M;
X is a hydrogen atom, a halogen atom, a hydrocarbon group, an anionic ligand or a neutral ligand that can be coordinated by a lone pair, and the anionic ligand is a halogen-containing group, a silicon-containing group, oxygen Containing group, sulfur-containing group, nitrogen-containing group, phosphorus-containing group, boron-containing group, aluminum-containing group or conjugated diene-based divalent derivative group, and when n is 2 or more, a plurality of groups represented by X are They may be the same as or different from each other, and may combine with each other to 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 hydrocarbon group having 1 to 40 carbon atoms, a halogen-containing group, a silicon-containing group, an oxygen-containing group, a nitrogen-containing group, or a sulfur-containing group, and they are the same or different. The adjacent substituents from R ^{1 to} R ⁴ 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, which may be the same or different,
R ^a1 to R ^a4 each independently represents a hydrocarbon group having 1 to 20 carbon atoms, an aromatic hydrocarbon group or a silicon-containing group having 6 to 40 carbon atoms, each may be the same or different, and R ^a1 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,
R ^b1 and R ^b2 have a substituent represented by the following general formula [2] or a substituent having a 5-membered mother skeleton containing at least one atom selected from nitrogen, oxygen and sulfur. Heterocyclic aromatic groups that may be the same or different,
Z ¹ and Z ² are each independently a saturated or unsaturated group having 3 or 4 carbon atoms that forms a condensed ring which may have the same substituent as R ^{1 to} R ⁴ with respect to the carbon atom to which Z ¹ and Z ² are bonded. The substituents on Z ¹ may be bonded to R ¹¹ and R ^12, and the substituents on Z ² may be bonded to R ¹³ and R ¹⁴ to form a ring. )

(In the 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, 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 a ring optionally having a substituent formed by bonding at least one selected from R ^a1 and R ^a2 and at least one selected from R ^a3 and R ^a4 to R ^c forming R ^b2. May form,
When m is 2, they may be the same or different, and R ^c may be bonded to each other to form a ring that may have a substituent. ) The transition metal compound [A] represented by the following general formula [3].

(In the 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 in the general formula [1], X, n, Q, R ^{1 to} R ⁴ , R ^{11 to} R ¹⁴ , R ^{a1 to} R ^a4 , R ^b1 and R ^b2 have the same meanings,
R ^{5 to} R ¹⁰ are each independently a hydrogen atom, a hydrocarbon group having 1 to 40 carbon atoms, a halogen-containing group, a silicon-containing group, an oxygen-containing group, a nitrogen-containing group, or a sulfur-containing group, and they are the same or different. R ^{5 to} R ¹⁰ adjacent substituents, R ⁵ and R ¹¹ or R ¹² , R ⁸ and R ¹³ or R ¹⁴ may be bonded to each other to form a ring. ) The transition metal compound [A] according to claim 2, wherein in the general formula [3], R ^b1 and R ^b2 are substituents represented by the general formula [2]. In the general formula [3],
M is a zirconium atom or a hafnium atom,
Each X is independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms or an oxygen-containing group,
The transition metal compound [A] according to claim 3, wherein 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, which may be the same or different,
R ² and R ⁴ are hydrogen atoms;
R ^{5 to} R ¹⁰ are each independently 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 , R ⁸ and R ^9. Is a saturated ring when forming a ring structure,
In the substituent represented by the general formula [2],
The transition metal compound [A] according to claim 4, wherein V is 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 a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms,
R ^{a1 to} R ^a4 are a hydrocarbon group having 1 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 40 carbon atoms, or a silicon-containing group,
In the substituent represented by the general formula [2],
R ^c is a hydrogen atom or a hydrocarbon group having a carbon number of 1 to 20, R ^c forming the R ^b1 is at least one selected from R ^a1 and R ^a2, and R ^c to form the R ^b2 R ^a3 And at least one selected from R ^a4 are bonded to each other to form a ring structure, a saturated ring,
The transition metal compound [A] according to claim 5, wherein when m is 2, when R ^c are bonded to each other to form a ring structure, they are saturated rings. 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,
The transition metal compound [A] according to claim 6, wherein R ^b1 and R ^b2 are an alkoxy group, a dialkylamino group, or a pyrrolidinyl group.   An olefin polymerization catalyst comprising the transition metal compound [A] according to any one of claims 1 to 7. [B] (B-1) an organometallic compound,
It contains at least one compound selected from the group consisting of (B-2) an organoaluminum oxy compound, and (B-3) a compound that reacts with a transition metal compound [A] to form an ion pair. The olefin polymerization catalyst according to claim 8.   A method for producing an olefin polymer, comprising a step of polymerizing an olefin in the presence of the catalyst for olefin polymerization according to claim 8 or 9.   The method for producing an olefin polymer according to claim 10, wherein the polymerization of the olefin is homopolymerization of ethylene or copolymerization of ethylene and an α-olefin having 3 to 20 carbon atoms.   The olefin polymer according to claim 10, wherein the polymerization of the olefin is homopolymerization of propylene or copolymerization of propylene and an α-olefin having 2 to 20 carbon atoms (excluding propylene). Manufacturing method.   The method for producing an olefin polymer according to claim 10, wherein the polymerization of the olefin is copolymerization of ethylene, a cyclic olefin, and an aromatic vinyl compound.   The olefin polymerization is a homopolymerization of 1-butene or a copolymerization of 1-butene and an α-olefin having 2 to 20 carbon atoms (excluding 1-butene). The manufacturing method of the olefin polymer as described in any one of.