JP6890398B2 - Method for producing transition metal compound, catalyst for olefin polymerization and olefin polymer - Google Patents

Description

The present invention relates to a transition metal compound having a specific structure useful as a catalyst for olefin polymerization or a catalyst component (also referred to as a metallocene compound in the present invention), a catalyst for olefin polymerization containing the transition metal compound, and the presence of the catalyst. The present invention relates to a method for producing an olefin polymer, particularly a method for producing an olefin polymer, which comprises homopolymerizing ethylene or copolymerizing ethylene with α-olefin.

The metallocene catalyst is composed of a transition metal atom and an organic compound called a ligand, and the polymerization reaction is carried out by changing the structure of this ligand by changing the position of the substituent and the steric electronic effect of the substituent. Widely controls the physical properties of the polymer obtained in. Many crosslinked metallocene compounds having a specific structure have been synthesized in order to synthesize a characteristic polymer.

For example, Patent Document 1 discloses an olefin polymerization catalyst composed of a non-crosslinked transition metal complex having a plurality of alkyl substituents on a cyclopentadienyl ring and methylarmoxane, and Patent Document 2 discloses cyclopenta. A method for highly activating and highly controlling the polymer terminal of the obtained polyolefin by introducing an aromatic substituent into the dienyl ring is disclosed.

Further, Patent Document 3 and Non-Patent Document 1 disclose a method for synthesizing a crosslinked metallocene complex in which an aromatic substituent is introduced into a cyclopentadienyl ring, detailed analysis of the complex, and use as an olefin polymerization catalyst. Has been done.

Further, in Patent Documents 4 and 5, the polymerization activity and the molecular weight and regularity of the obtained polyolefin are described by introducing a heterocyclic substituent at the 2-position of the cyclopentadienyl ring or the 2-position of the indene ring of the crosslinked metallocene complex. The method of control is disclosed.

In this way, 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 2, the introduction of an electron-donating substituent to a cyclopentadienyl-type ligand, particularly a highly electron-donating substituent containing a hetero atom, is used in terms of polymerization activity in quantum scientific model calculation. It has been reported to be desirable.

However, in an actual study using a metallocene complex having a heteroatom-electron donating substituent introduced as a catalyst for olefin polymerization, the catalytic activity and the molecular weight of the produced polyolefin are far from industrial use. As the 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 3 and 4).
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 indispensable.

Japanese Unexamined Patent Publication No. 63-222179 Japanese Unexamined Patent Publication No. 5-214027 Japanese Unexamined Patent Publication No. 11-279189 Special Table 2002-535339 Japanese Unexamined Patent Publication No. 2004-2259 Special Table 2014-525950 Japanese Patent Application Laid-Open No. 2014-505136

J. Organomet. Chem. 2005, 690, 952. Organometallics 2001, 20, 5375. Organometallics 1992, 11 and 2115. J. Organomet. Chem. 1996, 520, 63.

The present invention has been made to solve the above problems, and an object of the present invention is to use a metallocene catalyst containing a transition metal compound having a specific structure to obtain a polyolefin having a sufficient molecular weight and various products having high market value. It is an object of the present invention to provide a method for producing a linear low-density olefin polymer having a high density with good olefin polymerization activity, a transition metal compound suitable for the olefin polymer, and a catalyst containing the transition metal compound. That is, it is an object of the present invention to provide a transition metal compound having a high molecular weight, an adjustable density (higher) α-olefin, and a high polymerization activity, a catalyst containing the same, and a method for producing an olefin polymer.

As a result of diligent research in view of these circumstances, the present inventor has found a group of specific substituents on the metallocene complex, that is, heteroatom-electron donating substituents and aromatic substituents having substituents in the near position. It has been found that by introducing directly into the enyl ring, a transition metal compound having particularly excellent α-olefin copolymerizability and further providing a high molecular weight olefin polymer with good olefin polymerization activity can be obtained. .. That is, they have found a catalyst and a method for producing an olefin polymer which are advantageous for producing an ethylene-based 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] or general formula [2].

In the general formulas [1] and [2], M is a Group 4 transition metal atom in the periodic table, n is an integer of 1 to 4 satisfying the valence of M, and X is a hydrogen atom or a halogen atom. , A hydrocarbon group, an anion ligand or a neutral ligand capable of coordinating with an isolated electron pair, the anion ligand being a halogen-containing group, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, or nitrogen. It is a containing group, a phosphorus-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. ^{, R 1 to} R ¹⁰ may be independently bonded to each other to form a ring, each of which is a hydrogen atom, a hydrocarbon group having 1 to 40 carbon atoms, a halogen-containing group, a silicon-containing group, an oxygen-containing group, and nitrogen. It is a containing group or a sulfur-containing group, which may be the same or different, ^{and adjacent substituents R 1 to} R ⁵ and R ^{6 to} R ¹⁰ may be bonded to each other to form a ring, except that , R ^{1 to} R ¹⁰ are substituents represented by the following general formula [3], and when a plurality of them are present, they may be the same or different.

In the general formula [3], R ¹¹ and R ¹² are independently hydrogen atoms or hydrocarbon groups having 1 to 20 carbon atoms, and they may be the same or different, respectively, and R ¹³ and R ¹⁴ are respectively. 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, which may be the same or different, respectively, R ¹³ and R ¹¹ , R ¹⁴ and R. ¹² may be bonded to each other to form a ring, where Z is an atom selected from nitrogen, oxygen or sulfur, m is an integer of 1 or 2 which satisfies the valence of Z, and R ¹⁵ is. , Independently, hydrogen atoms, hydrocarbon groups having 1 to 40 carbon atoms, silicon-containing groups, ether bond-containing hydrocarbon groups or tertiary amino group-containing hydrocarbon groups, at least selected from ^{R 13} and R ^14. It may be bonded to one of them to form a ring which may have a substituent, and when m is 2, they may be the same or different from ^{each other, and R 15s} may be bonded to each other to have a substituent. It may form a ring which may be present.

In the general formula [2], Q is a divalent hydrocarbon group, a divalent silicon-containing group or a divalent germanium-containing group, and is at least one selected from ^{R 1} , R ⁴ , R ⁶ and R ^9. And may be bonded to each other to form a ring which may have a substituent independently of each other.

In the general formulas [1] and [2], M is a zirconium atom or a hafnium atom, and X is independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or an oxygen-containing group. In the general formula [2], Q is preferably a divalent hydrocarbon group or a divalent silicon-containing group.

In the general formulas [1] and [2], R ^{1 to} R ¹⁰ are independently hydrogen atoms or hydrocarbon groups having 1 to 20 carbon atoms, and may be the same or different from each other. In the substituent represented by [3], Z is preferably an atom selected from nitrogen or oxygen.

In the substituent represented by the general formula [3], R ¹¹ and R ¹² are hydrogen atoms, R ¹⁵ is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R ¹³ and R ¹⁴ It is a saturated ring when it is bonded to at least one of them to form a ring structure, and it is a saturated ring when m is 2 and R ¹⁵ are bonded to each other to form a ring structure. Is preferable.

Among the substituents represented by the general formula [3], R ¹³ and R ¹⁴ are hydrocarbon groups having 1 to 10 carbon atoms, and the ^{substituent represented by Z- (R 15} ) _m is an alkoxy group. , A dialkylamino group or a pyrrolidinyl group is preferred.
The catalyst for olefin polymerization of the present invention is characterized by containing the transition metal compound [A] of the present invention.

Further, the method for producing an olefin polymer of the present invention is characterized by including a step of polymerizing an olefin in the presence of the catalyst for olefin polymerization of the present invention.
In the present specification, the term "polymerization" is used to include not only homopolymerization but also copolymerization, and the term "polymer" includes not only homopolymers but also copolymers. It is used in an 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 carried out. While being able to produce 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 region where the density is low.

Next, the present invention will be specifically described.
<Catalyst for olefin polymerization>
Hereinafter, the catalyst for olefin polymerization of the present invention will be specifically described.
The olefin polymerization catalyst according to the present invention contains a novel transition metal compound [A] represented by the general formula [1] or the general formula [2], and further comprises [B] an organometallic compound (B-1). , Organic aluminum oxy compound (B-2), and at least one compound selected from the group consisting of the compound (B-3) that reacts with the transition metal compound [A] to form an ion pair. The transition metal compound [A] is also provided by the present invention. In addition, in this specification, an olefin means 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] or the general formula [2].

In the general formula [1] and the general formula [2], M is a transition metal atom of Group 4 of the periodic table, specifically, a titanium atom, a zirconium atom or a hafnium atom, preferably a zirconium atom or a hafnium atom. , Particularly preferably a zirconium atom.
n is an integer of 1 to 4 satisfying the valence of M, preferably 1 or 2.

X is a hydrogen atom, a halogen atom (X), a hydrocarbon group (G1), an anion ligand, or a neutral ligand (L1) capable of coordinating with an isolated electron pair, and the anion ligand is , Halogen-containing group (H1), silicon-containing group (Si1), oxygen-containing group (O1), sulfur-containing group (S1), nitrogen-containing group (N1), phosphorus-containing group (P), boron-containing group (B), It is an aluminum-containing group (Al) or a conjugated diene-based divalent derivative group (DE). X is preferably a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or an oxygen-containing group.

When n is 2 or more, a plurality of groups represented by X may be the same or different from each other, or may be bonded to each other to form a ring. Further, when a plurality of the rings are present, they may be the same or different from each other.

Specific examples of the halogen atom (X) include fluorine, chlorine, bromine, and iodine, but chlorine or bromine is preferable.
The hydrocarbon group (G1) is not particularly limited as long as the effects of the present invention are exhibited, but a hydrocarbon group having 1 to 20 carbon atoms is preferable. Examples of the hydrocarbon group (G1) include methyl group, ethyl group, 1-propyl group, 1-butyl group, 1-pentyl group, 1-hexyl group, 1-heptyl group, 1-octyl group and 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, siamil (1,2-dimethylpropyl) group, iso-hexyl (4-methylpentyl) group, 2,2- Linear or branched such as dimethylbutyl group, 2,3-dimethylbutyl group, 3,3-dimethylbutyl group, texyl (2,3-dimethylbut-2-yl) group, 4,4-dimethylpentyl group Alkyl group;
Vinyl group, allyl group, propenyl group (propa-1-ene-1-yl group), iso-propenyl group (propa-1-en-2-yl group), allenyl (propa-1,2-diene-1-yl) Il group) group, buta-3-en-1-yl group, crotyl (but-2-en-1-yl) group, buta-3-en-2-yl group, metalryl (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-) Methylbuta-3-ene-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 such as groups or unsaturated double bond containing groups;
Linear or branched alkynyl groups such as ethynyl groups, propa-2-in-1-yl groups, propargyl (propa-1-in-1-yl) groups or unsaturated triple bond-containing groups;
Benzyl group, 2-methylbenzyl group, 4-methylbenzyl group, 2,4,6-trimethylbenzyl group, 3,5-dimethylbenzyl group, Kuminyl (4-iso-propylbenzyl) group, 2,4,6- Aromatically containing linear or branched groups such as tri-iso-propylbenzyl group, 4-tert-butylbenzyl group, 3,5-di-tert-butylbenzyl group, 1-phenylethyl group, benzhydryl (diphenylmethyl) group. Alkyl group and 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, trill (methylphenyl) group, xsilyl (dimethylphenyl) group, mesityl (2,4,6-trimethylphenyl) group, cumenyl (iso-propylphenyl) group, juryl (2,3,5,6-tetra) Methylphenyl) group, 2,6-di-iso-propylphenyl group, 2,4,6-tri-iso-propylphenyl group, 4-tert-butylphenyl group, 3,5-di-tert-butylphenyl group , Afferous substituted (aryl) groups such as naphthyl group, biphenyl group, ter-phenyl group, binaphthyl group, acenaphthalenyl group, phenanthryl group, anthracenyl group, pyrenyl group, ferrosenyl group; and the like.

Among the above hydrocarbon groups, preferably, a methyl group, an iso-butyl (2-methylpropyl) group, a neopentyl (2,2-dimethylpropyl) group, a siamil (1,2-dimethylpropyl) group, a benzyl group, and a phenyl group. Group, trill (methylphenyl) group, xsilyl (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, and for example, a fluoromethyl group, a trifluoromethyl group, a trichloromethyl group, a pentafluoroethyl group, 2,2,2-trifluoro Examples thereof include ethyl group, fluorophenyl group, difluorophenyl group, trifluorophenyl group, tetrafluorophenyl group, pentafluorophenyl group, trifluoromethylphenyl group, bistrifluoromethylphenyl group, hexachloroantimonate anion and the like.

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, and for example, a trimethylsilyl group, a triethylsilyl group, a tri-iso-propylsilyl group, a diphenylmethylsilyl group, and a tert-butyldimethylsilyl group. , Tert-butyldiphenylsilyl group, triphenylsilyl group, tris (trimethylsilyl) silyl group, trimethylsilylmethyl group and the like.

Among the silicon-containing groups, a trimethylsilylmethyl group is preferable.
The oxygen-containing group (O1) is not particularly limited as long as the effects of the present invention are exhibited, and 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-Butyloxy group, 2,4,6-trimethylphenoxy group, 2,4,6-tri-iso-propylphenoxy group, acetoxy group, pivaloyloxy group, benzoyloxy group, trifluoroacetoxy group, perchlorate anion, Examples thereof include periodate anion.

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 are exhibited, and for example, a mesyl (methanesulfonyl) group, a phenylsulfonyl group, a tosyl (p-toluenesulfonyl) group, and a triflate (trifluoromethanesulfonyl). Group, nonaflate (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 are exhibited, and for example, an amino group, a cyano group, a methylamino group, a dimethylamino group, an ethylamino group, a diethylamino group, an allylamino group, and a diallylamino group. Examples thereof include a group, a benzylamino group, a dibenzylamino group, a pyrrolidinyl group, a piperidinyl group, a morpholic group, a pyrrolyl group, a 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.
The phosphorus-containing group (P) is not particularly limited as long as the effects of the present invention are exhibited, and examples thereof include hexafluorophosphate anions.

The boron-containing group (B) is not particularly limited as long as the effects of the present invention are exhibited, and for example, tetrafluoroborate anion, tetrakis (pentafluorophenyl) borate anion, (methyl) (tris (pentafluorophenyl)). ) Boron anion, (benzyl) (Tris (pentafluorophenyl)) borate anion, tetrakis ((3,5-bistrifluoromethyl) phenyl) borate anion, BR ₄ (R is hydrogen, alkyl group, substituent) (Indicating an aryl group, a halogen atom, etc., which may have) can be mentioned.

The aluminum-containing group (Al) is not particularly limited as long as the effect of the present invention is exhibited, and is, for example, a (M-halogen atom-aluminum atom-hydrocarbon group) four-membered ring or (M-hydrocarbon group-aluminum). _{Atom-hydrocarbon group) AlR 4} (R represents a hydrogen, an alkyl group, an aryl group which may have a substituent, 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 are exhibited, and for example, 1,3-butadienyl group, isoprenyl (2-methyl-1,3-butadienyl) group, piperylenyl. Examples thereof include a metallocyclopentene group such as a (1,3-pentadienyl) group, a 2,4-hexadienyl group, a 1,4-diphenyl-1,3-pentadienyl group and a cyclopentadienyl group.

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

R ^{1 to} R ¹⁰ independently contain 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), and a nitrogen. It is a group (N2) or a sulfur-containing hydrocarbon group (S2), and may be the same or different from each other.

The hydrocarbon groups (G2) having 1 to 40 carbon atoms are preferably hydrocarbon groups having 1 to 20 carbon atoms (excluding aromatic hydrocarbon groups) and aromatic groups 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. Hydrocarbon groups having 1 to 20 carbon atoms also include substituents having an aromatic structure such as arylalkyl groups.

The hydrocarbon group (G2) having 1 to 40 carbon atoms is not particularly limited as long as the effects of the present invention are exhibited, and for example, a methyl group, an ethyl group, a 1-propyl group, a 1-butyl group, and a 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 (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, tert-pentyl (1,1-dimethylpropyl) group, sheamil (1,2-dimethylpropyl) group, pentan-3-yl group, 2-methyl Pentyl group, 3-methylpentyl group, iso-hexyl (4-methylpentyl) group, 1,1-dimethylbutyl (2-methylpentane-2-yl) group, 3-methylpentane-2-yl group, 4- Methylpentane-2-yl group, 2,2-dimethylbutyl group, 2,3-dimethylbutyl group, 3,3-dimethylbutyl group, texyl (2,3-dimethylbut-2-yl) group, 3-methyl Pentan-3-yl group, 3,3-dimethylbut-2-yl group, hexane-3-yl group, 2-methylpentane-3-yl group, heptan-4-yl group, 2,4-dimethylpentane- 3-yl group, 3-ethylpentane-3-yl group, 4,4-dimethylpentyl group, 4-methylheptan-4-yl group, 4-propylheptan-4-yl group, 2,3,3-trimethyl A linear or branched alkyl group having 1 to 20 carbon atoms such as a butyl-2-yl group and a 2,3,4-trimethylpentane-3-yl group;
Vinyl group, allyl group, propenyl group (propa-1-ene-1-yl group), iso-propenyl group (propa-1-en-2-yl group), allenyl (propa-1,2-diene-1-yl) Il group) group, buta-3-en-1-yl group, crotyl (but-2-en-1-yl) group, buta-3-en-2-yl group, metalryl (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-) Methylbuta-3-ene-1-yl) group, 2-methylbut-3-en-1-yl group, penta-4-en-2-yl group, prenyl (3-methyl-but-2-en-1-yl) Il) group, 2-methyl-but-2-ene-1-yl group, penta-3-en-2-yl group, 2-methyl-but-3-en-2-yl group, penta-1-ene -3-yl group, penta-2,4-dien-1-yl group, penta-1,3-dien-1-yl group, penta-1,4-dien-3-yl group, iso-prenyl (2) -Methyl-buta-1,3-dien-1-yl) group, penta-2,4-dien-2-yl group, hexa-5-ene-1-yl group, hexa-4-en-1-yl Group, Hexa-3-en-1-yl group, Hexa-2-en-1-yl group, 4-Methyl-penta-4-ene-1-yl group, 3-Methyl-penta-4-en-1 -Il group, 2-methyl-penta-4-ene-1-yl group, hexa-5-en-2-yl group, 4-methyl-penta-3-ene-1-yl group, 3-methyl-penta -3-en-1-yl group, 2,3-dimethyl-but-2-ene-1-yl group, 2-methylpenta-4-en-2-yl group, 3-ethylpenta-1-en-3-yl group Il group, hexa-3,5-diene-1-yl group, hexa-2,4-dien-1-yl group, 4-methylpenta-1,3-dien-1-yl group, 2,3-dimethyl- Buta-1,3-diene-1-yl group, hexa-1,3,5-triene-1-yl group, 2- (cyclopentadienyl) propan-2-yl group, 2- (cyclopentadienyl) ) A linear or branched alkenyl group or unsaturated double bond-containing group having 2 to 40 carbon atoms such as an ethyl group;
Ethynyl group, propa-2-in-1-yl group, propargyl (propa-1-in-1-yl) group, porcine-1-in-1-yl group, porcine-2-in-1-yl group, Buta-3-in-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-buta-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-buta-1-in-1-yl group, 2-methyl-penta-3-in-2-yl group, A linear chain having 2 to 40 carbon atoms such as a 2,2-dimethyl-but-3-in-1-yl group, a hexa-4-in-1-yl group, and a hexa-5-in-1-yl group. Deformal or branched alkynyl group or unsaturated triple bond-containing group;
Benzyl group, 2-methylbenzyl group, 4-methylbenzyl group, 2,4,6-trimethylbenzyl group, 3,5-dimethylbenzyl group, Kuminyl (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, Kumil (2-phenylpropan-2-) Il) group, 2- (4-methylphenyl) propan-2-yl group, 2- (3,5-dimethylphenyl) propan-2-yl group, 2- (4-tert-butylphenyl) propan-2-yl Il group, 2- (3,5-di-tert-butylphenyl) propan-2-yl group, 3-phenylpentane-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-3-ene-1-yl group, 1, 1,2-Triphenylethyl group, trityl (triphenylmethyl) group, tri- (4-methylphenyl) methyl group, 2-phenylethyl group, styryl (2-phenylvinyl) group, 2- (2-methylphenyl) ) Ethyl group, 2- (4-methylphenyl) ethyl group, 2- (2,4,6-trimethylphenyl) ethyl group, 2- (3,5-dimethylphenyl) ethyl group, 2- (2,4) 6-Tri-iso-propylphenyl) ethyl group, 2- (4-tert-butylphenyl) ethyl group, 2- (3,5-di-tert-butylphenyl) ethyl group, 2-methyl-1-phenylpropane -2-yl group, 3-phenylpropyl group, 2-cinnamyl (3-phenylallyl) group, neofil (2-methyl-2-phenylpropyl) group, 3-methyl-3-phenylbutyl group, 2-methyl- 4-Phenylbutane-2-yl group, cyclopentadienyldiphenylmethyl group, 2- (1-indenyl) propan-2-yl group, (1-indenyl) diphenylmethyl group, 2- (1-indenyl) ethyl group , 2- (Tetrahydro-1-indacenyl) propan-2-yl group, (Tetrahydro-1-indacenyl) diphenylmethyl group, 2- (Tetrahydro-1-indacenyl) ethyl group, 2- (1-benzoindenyl) propane -2-yl group, (1-benzoindenyl) diphenylmethyl group, 2- (1-benzoindeni) Le) Ethyl group, 2- (9-fluorenyl) propan-2-yl group, (9-fluorenyl) diphenylmethyl group, 2- (9-fluorenyl) ethyl group, 2- (1-azulenyl) propan-2-yl Aromatic-containing linear or branched alkyl groups having 7 to 40 carbon atoms and unsaturated double bond-containing groups such as groups, (1-azulenyl) diphenylmethyl groups, and 2- (1-azulenyl) ethyl groups. ;
Cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclopentenyl group, cyclopentadienyl group, dimethylcyclopentadienyl group, n-butylcyclopentadienyl group, n-butyl-methylcyclopentadienyl group, tetramethylcyclo Pentazienyl group, 1-methylcyclopentyl group, 1-allylcyclopentyl group, 1-benzylcyclopentyl group, cyclohexyl group, cyclohexenyl group, cyclohexadienyl group, 1-methylcyclohexyl group, 1-allylcyclohexyl group, 1-benzyl Cyclohexyl group, cycloheptyl group, cycloheptenyl group, cycloheptatrienyl group, 1-methylcycloheptyl group, 1-allylcycloheptyl group, 1-benzylcycloheptyl group, cyclooctyl group, cyclooctenyl group, cyclooctadienyl group, Cyclooctatrienyl group, 1-methylcyclooctyl group, 1-allylcyclooctyl group, 1-benzylcyclooctyl group, 4-cyclohexyl-tert-butyl group, norbornyl group, norbornenyl group, norbornadienyl group, 2- Methylbicyclo [2.2.1] heptane-2-yl group, 7-methylbicyclo [2.2.1] heptane-7-yl group, bicyclo [2.2.2] octane-1-yl group, bicyclo [2.2.2] Octane-2-yl group, 1-adamantyl group, 2-adamantyl group, 1- (2-methyladamantyl), 1- (3-methyladamantyl), 1- (4-methyladamantyl) , 1- (2-phenyladamantyl), 1- (3-phenyladamantyl), 1- (4-phenyladamantyl), 1- (3,5-dimethyladamantyl), 1- (3,5,7-trimethyladamantyl) ), 1- (3,5,7-triphenyladamantyl), pentarenyl group, indenyl group, fluorenyl group, indasenyl group, tetrahydroindacenyl group, benzoindenyl group, azulenyl group, etc. Cyclic saturated and unsaturated hydrocarbon groups;
Phenyl group, trill (methylphenyl) group, xsilyl (dimethylphenyl) group, mesityl (2,4,6-trimethylphenyl) group, cumenyl (iso-propylphenyl) group, juryl (2,3,5,6-tetra) Methylphenyl) group, 2,6-di-iso-propylphenyl group, 2,4,6-tri-iso-propylphenyl group, 4-tert-butylphenyl group, 3,5-di-tert-butylphenyl group , Allylphenyl group, (but-3-en-1-yl) phenyl group, (but-2-en-1-yl) phenyl group, metallicylphenyl 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, ferrosenyl group, etc. Aryl) group; and the like.

Among the linear or branched alkyl groups having 1 to 40 carbon atoms, preferably a methyl group, an ethyl group, a 1-propyl group, a 1-butyl group, a 1-pentyl group, a 1-hexyl group, and the like. 1-Heptyl group, 1-octyl group, iso-propyl group, sec-butyl (butane-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-) group Methylpentyl) group, 1,1-dimethylbutyl (2-methylpentane-2-yl) group, 3,3-dimethylbutyl group, texyl (2,3-dimethylbut-2-yl) group, 3-methylpentane -3-yl group, heptan-4-yl group, 2,4-dimethylpentane-3-yl group, 3-ethylpentane-3-yl group, 4,4-dimethylpentyl group, 4-methylheptan-4- Il group, 4-propylheptan-4-yl group and the like can be mentioned, and more preferably, methyl group, ethyl group, 1-propyl group, 1-butyl group, 1-pentyl group, 1-hexyl group and 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, vinyl group, allyl group, buta-3-ene-1-yl group and crotyl are preferable. (Buta-2-en-1-yl) group, metalryl (2-methylallyl) group, penta-4-en-1-yl group, prenyl (3-methyl-but-2-en-1-yl) group, Penta-1,4-diene-3-yl group, hexa-5-ene-1-yl group, 2-methylpenta-4-en-2-yl group, 2- (cyclopentadienyl) propan-2-yl Examples thereof include a group, a 2- (cyclopentadienyl) ethyl group and the like, and more preferably, a vinyl group, an allyl group, a porcine-3-ene-1-yl group, a penta-4-en-1-yl group and the like. , Plenyl (3-methyl-but-2-ene-1-yl) group, hexa-5-ene-1-yl group.

Among the linear or branched alkynyl groups or unsaturated triple bond-containing groups having 2 to 40 carbon atoms, the ethynyl group, propa-2-in-1-yl group and propargyl (propa-1) are preferable. −In-1-yl) group, porcine-2-in-1-yl group, porcine-3-in-1-yl group, penta-3-in-1-yl group, penta-4-in-1-yl Il group, 3-methyl-buta-1-in-1-yl group, 3,3-dimethyl-but-1-in-1-yl group, hexa-4-in-1-yl group, hexa-5- Examples thereof include an in-1-yl group, and more preferably, a propa-2-in-1-yl group, a propargyl (propa-1-in-1-yl) group, a buta-2-in-1-yl group and the like. It is an yl group and a porcine-3-in-1-yl group.

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

Among the cyclic saturated and unsaturated hydrocarbon groups having 3 to 40 carbon atoms, preferably 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] Heptane-2-yl group, bicyclo [2.2.2] octane-1-yl group, 1-adamantyl group, 2-adamantyl group, pentarenyl group, indenyl group, fluorenyl group and the like. Of these, 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 are more preferable.

Among the aromatic substituted (aryl) groups having 6 to 40 carbon atoms, preferably, a phenyl group, a tolyl (methylphenyl) group, a xsilyl (dimethylphenyl) group, and a 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 -Tart-butylphenyl group, allylphenyl group, prenylphenyl group, 4-adamantylphenyl group, naphthyl group, biphenyl group, ter-phenyl group, binaphthyl group, phenanthryl group, anthracenyl group, ferrosenyl group and the like. More preferably, a phenyl group, a trill (methylphenyl) group, a xsilyl (dimethylphenyl) group, a mesityl (2,4,6-trimethylphenyl) group, a cumenyl (iso-propylphenyl) group, a 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, anthracenyl group.

The halogen-containing group (H2) is not particularly limited as long as the effects of the present invention are exhibited, and 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, Tri Fluoromethoxyphenyl group, bistrifluoromethoxyphenyl group, trifluoromethylthiophenyl group, bistrifluoromethylthiophenyl group, fluorobiphenyl group, difluorobiphenyl group, trifluorobiphenyl group, tetrafluorobiphenyl group, pentafluorobiphenyl group, di-tert- Butyl-fluorobiphenyl group, trifluoromethylbiphenyl group, bistrifluoromethylbiphenyl group, trifluoromethoxybiphenyl group, bistrifluoromethoxybiphenyl group, trifluoromethyldimethylsilyl group, trifluoromethoxy group, pentafluoroethoxy group, fluorophenoxy group , Difluorophenoxy group, trifluorophenoxy group, pentafluorophenoxy group, di-tert-butyl-fluorophenoxy group, trifluoromethylphenoxy group, bistrifluoromethylphenoxy group, trifluoromethoxyphenoxy group, bistrifluoromethoxyphenoxy group, difluoro Examples thereof include a methylenedioxyphenyl group, a bistrifluoromethylphenyliminomethyl group, and a trifluoromethylthio group.

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

The silicon-containing group (Si2) is not particularly limited as long as the effects of the present invention are exhibited, and for example, a trimethylsilyl group, a triethylsilyl group, a tri-iso-propylsilyl group, a diphenylmethylsilyl group, and a tert-butyldimethylsilyl group. , Tert-Butyldiphenylsilyl group, triphenylsilyl group, tris (trimethylsilyl) silyl group, 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 group, 4-triethylsilylphenyl group, 4-tri-iso-propylsilylphenyl group, 4-tert-butyldiphenylsilylphenyl group, 4-triphenylsilylphenyl group, 4-tris (trimethylsilyl) silylphenyl group, etc. Can be mentioned.

Among the silicon-containing groups, trimethylsilyl group, triethylsilyl group, tri-iso-propylsilyl group, tert-butyldimethylsilyl group, triphenylsilyl group, cyclopentadienyldimethylsilyl group, cyclopentadienyldiphenylsilyl group are preferable. Group, indenyldimethylsilyl group, indenyldiphenylsilyl group, fluorenyldimethylsilyl group, fluorenyldiphenylsilyl group, 4-trimethylsilylphenyl group, 4-triethylsilylphenyl group, 4-tri-iso-propylsilylphenyl Examples thereof include a group and a 4-triphenylsilylphenyl group, more preferably a trimethylsilyl group, a triethylsilyl group, a tert-butyldimethylsilyl group, a 4-trimethylsilylphenyl group, a 4-triethylsilylphenyl group and a 4-tri. -Iso-propylsilylphenyl group.

The oxygen-containing group (O2) is not particularly limited as long as the effects of the present invention are exhibited, and for example, methoxy group, ethoxy group, n-propoxy group, iso-propoxy group, allyloxy group, n-butoxy group, sec- Butoxy group, iso-butoxy group, tert-butoxy group, metalryloxy group, prenyloxy group, benzyloxy group, methoxymethoxy group, methoxyethoxy group, phenoxy group, naphthoxy group, toluyloxy group, iso-propylphenoxy group, allylphenoxy Group, tert-butylphenoxy group, methoxyphenoxy group, iso-propoxyphenoxy group, allyloxyphenoxy group, biphenyloxy group, binaphthyloxy group, methoxymethyl group, allyloxymethyl group, benzyloxymethyl group, phenoxymethyl group, methoxy Ethyl group, allyloxyethyl group, benzyloxyethyl group, phenoxyethyl group, methoxypropyl group, allyloxypropyl group, benzyloxypropyl group, phenoxypropyl group, methoxyvinyl group, allyloxyvinyl group, benzyloxyvinyl group, phenoxy Vinyl group, methoxyallyl group, allyloxyallyl group, benzyloxyallyl group, phenoxyallyl group, dimethoxymethyl group, di-iso-propoxymethyl group, dioxolanyl group, tetramethyldioxolanyl group, dioxanyl group, methoxyphenyl group, iso-propoxyphenyl group, allyloxyphenyl group, phenoxyphenyl group, methylenedioxyphenyl group, 3,5-di-tert-butyl-4-methoxyphenyl group, frill group, methylfuryl group, tetrahydrofuryl group, pyranyl group , Tetrahydropyranyl group, flofuryl group, benzofuryl group, dibenzofuryl group and the like.

Among the oxygen-containing groups, preferably, a methoxy group, an ethoxy group, an iso-propoxy group, an allyloxy group, an n-butoxy group, a tert-butoxy group, a prenyloxy group, a benzyloxy group, a phenoxy group, a naphthoxy group and a toluyloxy group. , Iso-propylphenoxy group, allylphenoxy group, tert-butylphenoxy group, methoxyphenoxy group, biphenyloxy group, binaphthyloxy group, allyloxymethyl group, benzyloxymethyl group, phenoxymethyl group, methoxyethyl group, methoxyallyl group , Benzyloxyallyl group, phenoxyallyl group, dimethoxymethyl group, dioxolanyl group, tetramethyldioxolanyl group, dioxanyl group, dimethyldioxanyl group, methoxyphenyl group, iso-propoxyphenyl group, allyloxyphenyl group, phenoxyphenyl Group, methylenedioxyphenyl group, 3,5-di-tert-butyl-4-methoxyphenyl group, frill group, methyl frill group, tetrahydropyranyl group, flofuryl group, benzofuryl group, dibenzofuryl group and the like. , More preferably, methoxy group, iso-propoxy group, tert-butoxy group, allyloxy group, phenoxy group, dimethoxymethyl group, dioxolanyl group, methoxyphenyl group, iso-propoxyphenyl group, allyloxyphenyl group, phenoxyphenyl. Group, 3,5-di-tert-butyl-4-methoxyphenyl group, frill group, methyl frill group, benzofuryl group, dibenzofuryl group.

The nitrogen-containing group (N2) is not particularly limited as long as the effect of the present invention is exhibited, and for example, an amino group, a dimethylamino group, a diethylamino group, an allylamino group, a diallylamino group, a didecylamino group, a benzylamino group, or a dibenzyl. Amino group, pyrrolidinyl group, piperidinyl group, molyphoryl group, azepinyl group, dimethylaminomethyl group, dibenzylaminomethyl group, pyrrolidinylmethyl group, dimethylaminoethyl group, benzylaminomethyl group, benzylaminoethyl group, pyrrolidinyl Ethyl group, dimethylaminovinyl group, benzylaminovinyl group, pyrrolidinyl vinyl group, dimethylaminopropyl group, benzylaminopropyl group, pyrrolidinylpropyl group, dimethylaminoallyl group, benzylaminoallyl group, pyrrolidinylallyl group , Aminophenyl group, dimethylaminophenyl group, pyrrolidinylphenyl group, pyrrolylphenyl group, pyridylphenyl group, quinolylphenyl group, isoquinolylphenyl group, indolinylphenyl group, indolylphenyl group, carbazolylphenyl Group, di-tert-butylcarbazolylphenyl group, pyrrolyl group, methylpyrrrolyl group, phenylpyrrolill group, pyridyl group, quinolyl group, tetrahydroquinolyl group, iso-quinolyl group, tetrahydro-iso-quinolyl group, indolyl group, Examples thereof include an indolinyl group, a carbazolyl group, a di-tert-butylcarbazolyl group, an imidazolyl group, a dimethylimidazolidinyl group, a benzoimidazolyl group, an oxazolyl group, an oxazolidinyl group and a benzoxazolyl group.

Among the nitrogen-containing groups, preferably amino group, dimethylamino group, diethylamino group, allylamino group, benzylamino group, dibenzylamino group, pyrrolidinyl group, piperidinyl group, morpholyl group, dimethylaminomethyl group, benzylaminomethyl group, Pyrrolidinylmethyl group, dimethylaminoethyl group, pyrrolidinylethyl group, dimethylaminopropyl group, pyrrolidinylpropyl group, dimethylaminoallyl group, pyrrolidinylallyl group, aminophenyl group, dimethylaminophenyl group, pyrrolidini Ruphenyl group, 3,5-di-iso-propyl-4-dimethylaminophenyl group, durolidinyl group, pyrrolylphenyl group, carbazolylphenyl group, di-tert-butylcarbazolylphenyl group, pyrrolyl 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, Examples thereof include benzoimidazolyl group, oxazolyl group, oxazolidinyl group, benzoxazolyl group and the like, and more preferably, amino group, dimethylamino group, diethylamino group, pyrrolidinyl group, dimethylaminophenyl group and pyrrolidinylphenyl. Group, 3,5-di-iso-propyl-4-dimethylaminophenyl group, durolidinyl group, pyrrolyl group, pyridyl group, carbazolyl group, imidazolyl group.

The sulfur-containing group (S2) is not particularly limited as long as the effects of the present invention are exhibited, and for example, a methylthio group, an ethylthio group, a benzylthio group, a phenylthio group, a naphthylthio group, a methylthiomethyl group, a benzylthiomethyl group, and a phenylthio. Methyl group, naphthylthiomethyl group, methylthioethyl group, benzylthioethyl group, phenylthioethyl group, naphthylthioethyl group, methylthiovinyl group, benzylthiovinyl group, phenylthiovinyl group, naphthylthiovinyl group, methylthiopropyl group, Benzylthiopropyl group, phenylthiopropyl group, naphthylthiopropyl group, methylthioallyl group, benzylthioallyl group, phenylthioallyl group, naphthylthioallyl group, mercaptophenyl group, methylthiophenyl group, thienylphenyl group, methylthienylphenyl group , Benzothienyl phenyl group, dibenzothienylphenyl group, benzodithienylphenyl group, thienyl group, tetrahydrothienyl group, methylthienyl group, thienovryl group, thienotienyl group, benzothienyl group, dibenzothienyl group, thienobenzofuryl group Examples thereof include a 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 thienofryl group, a thienotienyl group, a benzothienyl group, a dibenzothienyl group, a thienobenzofuryl group, a benzodithienyl group, a thiazolyl group and a benzothiazolyl group are preferable.

Adjacent substituents R ^{1 to} R ⁵ and R ^{6 to} R ¹⁰ may be bonded to each other to form a ring, and may be the same or different from each other when a plurality of the rings are present.
Of R ^{1 to} R ⁵ and R ^{6 to} R ¹⁰ , when adjacent substituents are bonded to each other to form a ring, the 5- to 8-membered ring fused to the cyclopentadienyl ring moiety is saturated or unsaturated. Saturated hydrocarbon groups and heterocycles may be formed and are not particularly limited as long as the effects of the present invention are exhibited, but are preferably 5- or 6-membered rings, in which case they are combined with the cyclopentadienyl moiety of the mother nucleus. As the structure, for example, a substituted cyclopentapyrrole ring, a substituted cyclopentaindole ring, a substituted cyclopentatiophene ring, a substituted cyclopentabenzothiophene ring, a substituted inden ring, a substituted benzoinden ring, a substituted tetrahydroinden ring, a substituted azulene ring, a substituted azulene ring. Examples thereof include a dihydroazulene ring, a substituted tetrahydroazulene ring, a substituted hexahydroazulene ring, and a substituted fluorene ring, and a substituted inden ring, a substituted tetrahydroinden ring, and a substituted fluorene ring are preferable.

R ^{1 to} R ¹⁰ each independently contain a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms among the hydrocarbon groups (G2) having 1 to 40 carbon atoms, a silicon-containing group, an oxygen-containing group, or a nitrogen-containing group. It is preferably a group, more preferably a hydrogen atom or a hydrocarbon group having 1 to 20 carbon 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 in the hydrocarbon group having 1 to 40 carbon atoms (G2). Preferably, it is a hydrocarbon group selected from an aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms. Hydrocarbon groups having 1 to 20 carbon atoms also include substituents having an aromatic structure such as arylalkyl groups.

At ^{least one of R 1 to} R ¹⁰ is a substituent represented by the general formula [3].
In the general formula [3], R ¹¹ and R ¹² are independently hydrogen atoms or hydrocarbon groups having 1 to 20 carbon atoms, which may be the same or different, and both may be hydrogen atoms. preferable. Examples of the hydrocarbon group having 1 to 20 carbon atoms include those having 1 to 20 carbon atoms among the hydrocarbon groups exemplified in the hydrocarbon group having 1 to 40 carbon atoms (G2). Preferably, it is a hydrocarbon group selected from an aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms. Hydrocarbon groups having 1 to 20 carbon atoms also include substituents having an aromatic structure such as arylalkyl groups.

In the general formula [3], R ¹³ and R ¹⁴ are independently hydrocarbon groups having 1 to 20 carbon atoms, aromatic hydrocarbon groups having 6 to 40 carbon atoms, or silicon-containing groups, and they may be the same. It may be different. The hydrocarbon group having 1 to 20 carbon atoms and the aromatic hydrocarbon group having 6 to 40 carbon atoms are, for example, among the hydrocarbon groups exemplified in the hydrocarbon group having 1 to 40 carbon atoms (G2), respectively. Hydrocarbon groups having 1 to 20 carbon atoms and aromatic hydrocarbon groups having 6 to 40 carbon atoms can be mentioned. Further, as the silicon-containing group, for example, the silicon-containing group exemplified in the silicon-containing group (Si2) can be mentioned.

Examples of the hydrocarbon group having 1 to 20 carbon atoms include the above-mentioned 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. Alkyl groups (allylkyl groups) are mentioned as preferred groups. As the hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 10 carbon atoms is more preferable.

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

Among the aromatic hydrocarbon groups having 6 to 40 carbon atoms, phenyl group, tolyl (methylphenyl) group, xsilyl (dimethylphenyl) group, mesityl (2,4,6-trimethylphenyl) group and cumenyl (2,4,6-trimethylphenyl) group are preferable. iso-propylphenyl) group, 2,6-di-iso-propylphenyl group, 2,4,6-tri-iso-propylphenyl group, 4-tert-butylphenyl group, 3,5-di-tert-butyl Phenyl group, 4-adamantylphenyl group, naphthyl group, biphenyl group, ter-phenyl group, binaphthyl group, phenanthryl group, anthracenyl group, ferrosenyl 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 ¹³ and R ¹¹ and R ¹⁴ and R ¹² may be combined with each other to form a ring. The ring formed in this case preferably forms a ring as a saturated or unsaturated hydrocarbon group of a 5- to 8-membered ring fused to the aromatic ring portion. When a plurality of rings exist, they may be the same or different from each other. The ring is not particularly limited as long as the effect of the present invention is exhibited, but is preferably a 5- or 6-membered ring. , Substituted tetrahydronaphthalene and the like.
It is preferable that R ¹³ and R ¹⁴ are each independently a hydrocarbon group having 1 to 10 carbon atoms.

In the general formula [3], Z is an atom selected from nitrogen, oxygen or sulfur, and is preferably nitrogen or oxygen.
m is an integer of 1 or 2 that satisfies the valence of Z, and when m is 2, R ¹⁵ may be the same or different.

R ¹⁵ 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 (G2) having 1 to 40 carbon atoms, preferably 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. , 1-octyl group, iso-propyl group, sec-butyl (butane-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 Propyl group, cyclooctyl group, cyclooctenyl group, norbornyl group, bicyclo [2.2.2] octane-1-yl group, 1-adamantyl group, 2-adamantyl group, benzyl group, benzhydryl (diphenylmethyl) group, cumyl ( 2-Phenylpropan-2-yl) group, 1,1-diphenylethyl group, trityl (triphenylmethyl) group, 2-phenylethyl group, 3-phenylpropyl group, 2-cinnamyl (3-phenylallyl) group, Phenyl group, trill (methylphenyl) group, xsilyl (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, ferrosenyl group, more preferably methyl group, ethyl group, 1-propyl group, 1-butyl group, iso-propyl group, sec-butyl (butane-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, trill It is a (methylphenyl) group, a xsilyl (dimethylphenyl) group, a mesityl (2,4,6-trimethylphenyl) group, a naphthyl group, a biphenyl group, and a ter-phenyl group.

The ether bond-containing hydrocarbon group is not particularly limited as long as the effect of the present invention is exhibited, and examples thereof include 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 exhibited, and for example, an N-dimethylamino group, an N-diethylamino group, an N-diallylamino group, an N-dibenzylamino group, and the like. N-Methylethylamino group, N-pyrrolidinyl group, N-piperidinyl group, N-morpholyl group, N-methyl-N-piperazinyl group, N-pyrrrolyl group, N-indolinyl group, N-indrill 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 The group and the like can be mentioned.

R ¹⁵ may ^{be attached to at least one selected from R 13} and R ¹⁴ to form a ring which may have a substituent. The ring formed in this case may form a ring as a saturated or unsaturated hydrocarbon group of a 5- to 8-membered ring which may have a substituent which is condensed in the aromatic ring portion. R ¹⁵ is preferably a saturated ring when coupled with at least one selected from ^{R 13} and R ^{14 to form a ring structure.} When a plurality of rings are present, they may be the same or different from each other. Although not particularly limited as long as the effects of the present invention are exhibited, it is preferably a 5- or 6-membered ring, and 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 Il group, 4-methyldibenzo [b, d] thiophen-2-yl group, 1,7-dimethylindole-5-yl group, 1,7-dimethylindolin-5-yl group, 1,9-dimethylcarbazole- Examples thereof include a 3-yl group and a 9-duroridinyl (2,3,6,7-tetrahydro-1H, 5H-benzo [ij] quinolidine-9-yl) group, preferably 1,7-dimethylindrin-5. -Il group, 9-duroridinyl (2,3,6,7-tetrahydro-1H, 5H-benzo [ij] quinolidine-9-yl) group.

R ¹⁵ may be the same or different when m is 2, that is, when Z is a nitrogen atom. Further, R ^15s may be bonded to each other to form a saturated or unsaturated hydrocarbon group having a ring having a substituent, for example, a 5- to 8-membered ring. When R ^15s are bonded to each other to form a ring structure, a saturated ring is preferable. The ring is not particularly limited as long as the effect of the present invention is exhibited, but is preferably a 5- or 6-membered ring. In this case, the structure combined with the nitrogen atom portion of the mother nucleus is, for example, an N-pyrrolidinyl group, an N-piperidinyl group, or N. -Morholic group, N-methyl-N-piperazinyl group, N-pyrrrolyl group, N-indolinyl group, N-indrill group, N-carbazolyl group, N-di-tert-butylcarbazolyl group, N-imidazolyl group, Examples thereof include N-dimethylimidazolidinyl group, N-benzoimidazolyl group, N-oxazolyl group, N-oxazolidinyl group, N-benzoxazolyl group and the like, preferably N-pyrrolidinyl group and N-piperidinyl group. , N-morpholyl group, N-methyl-N-piperazinyl group.

The substituent represented by Z- (R ¹⁵ ) _m is particularly preferably an alkoxy group, a dialkylamino group or a pyrrolidinyl group.
Among the alkoxy groups, preferably, a methoxy group, an ethoxy group, a 1-propoxy group, a 1-butoxy group, an iso-propoxy group, a sec-butoxy group, a tert-butoxy group, an iso-butoxy group, an allyloxy group and a cyclopentyloxy group. The group is a cyclohexyloxy group, a 1-adamantyloxy group, a benzyloxy group, and the methoxy group, an ethoxy group, a 1-propoxy group, an iso-propoxy group, and a tert-butoxy group are most preferable.

Particularly preferred examples of the general formula [3] are 3,5-dimethyl-4-methoxyphenyl group, 3,5-di-iso-propyl-4-methoxyphenyl group, and 3,5-di-tert-butyl. -4-methoxyphenyl group, 3,5-dimethyl-4-dimethylaminophenyl group, 3,5-di-iso-propyl-4-dimethylaminophenyl group, 3,5-dimethyl-4-pyrrolidinylphenyl group , 3,5-di-iso-propyl-4-pyrrolidinylphenyl group.

The wavy line of the general formula [3] indicates the binding site with the cyclopentadienyl ring.
In the general formula [2], Q is a divalent group that binds two ligands, and specifically, Q is a divalent hydrocarbon group, a divalent silicon-containing group, or a divalent germanium. It is a 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, the substituted alkylene group, the cycloalkylene group and the alkylidene group include alkylene groups such as methylene, ethylene, propylene and butylene;
Isopropyridene, dimethylmethylene, diethylmethylene, dipropylmethylene, diisopropylmethylene, dibutylmethylene, methylethylmethylene, methylbutylmethylene, methylbuta-3-emethylene, methyl-t-butylmethylene, dihexylmethylene, dicyclohexylmethylene, methylcyclohexylmethylene, Methylphenylmethylene, phenylmethylene, phenylbut-3-emethylene, diphenylmethylene, ditrilmethylene, methylnaphthylmethylene, dinaphthylmethylene, benzylphenylmethylene, dibenzylmethylene, 1-methylethylene, 1,2-dimethylethylene, 1 -Substituted alkylene groups such as ethyl-2-methylethylene;
Cycloalkylene groups such as cyclopropylidene, cyclobutylidene, cyclopentylidene, cyclohexylidene, cycloheptilidene, bicyclo [33.1] nonylidene, norbornylidene, adamantylidene, tetrahydronaphthylidene, dihydroindalilidene, etc. ;
Examples thereof include an alkylidene group such as ethylidene, propylidene and butylidene.

Examples of the divalent silicon-containing group include silylene, methylsilylene, dimethylsilylene, diethylsilylene, diisopropylsilylene, dibutylsilylene, methylbutylsilylene, methyl-t-butylcilylene, dicyclohexylsilylene, methylcyclohexylcilylene, methylphenylcilylene, and diphenylcilylene. , Ditrilcilylene, methylnaphthylsilylene, dinaphthylcilylene, cyclodimethylenesilylene, cyclotrimethylenecilylene, cyclotetramethylenesilylene, cyclopentamethylenesilylene, cyclohexamethylenecilylene, cycloheptamethylenecilylene, tetramethyldisylylene, etc. These are preferably dimethylsilylene, dibutylsilylene, diphenylcilylene, cyclodimethylenecilylene, cyclotrimethylenecilylene, cyclotetramethylenecilylene, cyclopentamethylenecilylene and tetramethyldisylylene.

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

Q may ^{be attached to at least one selected from R 1} , R ⁴ , R ⁶ and R ⁹ to form a ring which may have a substituent independently of each other. As the ring, a saturated 5-membered ring or a bicyclic saturated 5-membered ring may be formed. When a plurality of the rings are present, they may be the same or different from each other, and examples of the structure in this case include a cyclopentane ring matrix, an octahydroindene ring matrix, and an octahydropentane ring matrix.
In the general formula [2], it is preferable that the substitution position of the substituent represented by the general formula [3] is at least one selected from ^{R 2} , R ³ , R ⁷ and R ^8.

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

First, known methods are used for the starting material, a 3,4,5-substituted aromatic compound having a heteroatom-containing electron-donating substituent at the 4-position and a substituent introduced at the nearby 3,5-position. It can be manufactured by, and 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. 2013." 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.

Further, the substituted cyclopentenone compound, which is the other starting material, can be produced by a known method, and the production method is not particularly limited. As known production methods, for example, JP-A-63-222179, "J. Am. Chem. Soc. 1991, 113, 2537.", "J. Org. Chem. 1991, 56, 735.", WO 1998 / 040331, WO1998 / 046547, "J. Organomet. Chem. 1999, 577, 211.", "J. Organomet. Chem. 1999, 590, 169.", "J. Am. Chem. Soc. 2000." , 122, 6977. ”, Japanese Patent Application Laid-Open No. 2002-535339, WO 2002/016374,“ J. Organomet. Chem. 2003, 677, 133. ”, JP-A-2004-2259,“ Organometallics 2006, 25, 1217. ”, US Pat. No. 7,910,783, Japanese Patent Application Laid-Open No. 2011-500800,“ Organometallics 2011,30,5744. ”,“ Chem.Eur.J.2012,18,4174. ”,“ Organometallics 2012,31,4962. , Japanese Patent Application Laid-Open No. 2014-201519, Japanese Patent Application Laid-Open No. 7-286005 by the Applicant, and the like.

Further, the aromatic-substituted cyclopentadiene compound can be produced by a known method using the 3,4,5-substituted aromatic compound and the substituted cyclopentenone compound as raw materials, and the production method is particularly limited. is not it. As known production methods, for example, in addition to those mentioned as the methods for producing the 3,4,5-substituted aromatic compound and the substituted cyclopentenone compound, JP-A-5-214827, JP-A-11-279189, Japanese Patent Application Laid-Open No. 2000-136195 and the like can be mentioned. Other methods that do not use the substituted cyclopentenone compound as a raw material include "JAm. Chem. Soc. 1981, 103, 7753.".

Further, among the transition metal compounds [A], the precursor compound (ligand) for obtaining the crosslinked transition metal compound represented by the general formula [2] is made from the aromatic-substituted cyclopentadiene compound as a raw material. It can be produced by a known method, 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 substituted cyclopentadiene compound, "J. Organomet. Chem. 1997, 530, 75.", "J. Organomet. Chem. 2001, 619, 280. , Japanese Patent Application Laid-Open No. 2001-11089, Japanese Patent Application Laid-Open No. 2002-535339, Japanese Patent Application Laid-Open No. 2003-201259, "J. Organomet. Chem. 2005, 690, 952.", Japanese Patent Application Laid-Open No. 2011-144157, Japanese Patent Application Laid-Open No. Japanese Patent Publication No. 2014-193846 and the like can be mentioned.

Further, the target transition metal compound [A] can be produced by a known method using the aromatic-substituted cyclopentadiene compound or the crosslinked precursor compound (ligand), and in particular, a production method. Is not limited. As known production methods, for example, in addition to those mentioned as the method for producing the precursor compound (ligand), US Pat. No. 5,972822, JP-A-10-109996, "J. Organomet. Chem. 1997, 527". , 297. ”, JP-A-2002-88092,“ Organometallics 2012, 31, 4340. ”, WO 2004/029062 by the present applicant, and the like.

In the transition metal compound [A] of the present invention, the surface of the cyclopentadienyl ring portion bonded to the central metal exists in two directions (front surface and back surface). Therefore, if there is no intramolecular symmetric mirror image plane on one cyclopentadienyl ring and the two cyclopentadienyl ring portions bonded to the central metal are the same, the racemate and the meso form 2 There are two types of structural isomers, a pseudo-racemic and a pseudo-meso-form, when the two cyclopentadienyl ring moieties are different from each other. As an example of the transition metal compound [A] represented by the general formula [1], 1-aryl-3-methylcyclopentadiene has a cyclopentadienyl structure, and the racemate and the pseudo-racemic form have the following general formula [4a]. The meso-form and the pseudo-meso-form are shown in the following general formula [4b].

同様に、前記一般式［２］で示される遷移金属化合物［Ａ］の一例として、３−アリール−２−メチルシクロペンタジエンをシクロペンタジエニル構造とし、ラセミ体および疑似ラセミ体を下記一般式［５ａ］、メソ体および疑似メソ体を下記一般式［５ｂ］に示す。

Similarly, as an example of the transition metal compound [A] represented by the general formula [2], 3-aryl-2-methylcyclopentadienyl has a cyclopentadienyl structure, and the racemate and the pseudo-racemic form have the following general formula [ 5a], the meso-form and the pseudo-meso-form are shown in the following general formula [5b].

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 pseudo-racemates, or selective production of racemates and pseudo-racemates is possible by known methods, and the production method is not particularly limited. .. As a known production method, the method for producing the transition metal compound [A] is mentioned.

Specific examples of the transition metal compound [A] of the present invention are shown below, but the scope of the present invention is not particularly limited by this. In the present invention, the transition metal compound [A] may be used alone, in combination of two or more, racemic and pseudo-racemic, and a mixture of structural isomers. Alternatively, it may be used in the above-mentioned combination.

For convenience, the ligand structure of the transition metal compound [A] of the present invention _{excluding MX n} (metal moiety) is a cyclopentadienyl ring moiety, a cyclopentadienyl ring partial substituent (Y), and a cyclopentadienyl ring moiety. Aromatic substituents (Ar), substituents at positions 3 and 5 of the cyclopentadienyl ring partial aromatic substituents (T), and substituents at the 4-position of the cyclopentadienyl ring partial aromatic substituents (J), It is divided into seven structures: cyclopentadienyl ring partial substituent (V), cyclopentadienyl ring partial substituent (W), and crosslinked moiety.

The abbreviation for the cyclopentadienyl ring moiety is α, the abbreviation for the combined structure of the cyclopentadienyl ring and the crosslinked moiety is β, and the abbreviation for the cyclopentadienyl ring partial substituent (Y ^{1 to Y 5} ) is γ, cyclopentadi. The abbreviation of the partial aromatic substituent (Ar) of the enyl ring is δ, the abbreviation of the substituents (T ¹ and T ² ) at the 3rd and 5th positions of the cyclopentadienyl ring partial aromatic substituent is ε, and the cyclopentadienyl ring. The abbreviation of the 4-position substituent (J) among the partial aromatic substituents is ζ, the abbreviation of the cyclopentadienyl ring partial substituents (V ^{1 to} V ⁴ ) is η, and the cyclopentadienyl ring partial substituent (W). The abbreviation for is θ, the abbreviation for the structure of the crosslinked portion is ι, and the abbreviations for each substituent are shown in [Table 1] to [Table 9].

When the transition metal compound [A] has a cross-linked structure represented by the general formula [2], Y ⁵ of α-1 to α-14 in [Table 1] is a cross-linked structure represented by [Table 9]. It is a part.
Further, only when the transition metal compound [A] has a non-crosslinked structure represented by the general formula [1], α-15 and α-16 in [Table 1] are applied, and α-15 and α Y ⁵ of -16 may be a cyclopentadienyl ring partial aromatic substituent (Ar) shown in [Table 4].

When the transition metal compound [A] is a combination of different substituted cyclopentadienyl type ligands and the substituent represented by the general formula [3] is present in only one of them, [Table 1] And the cyclopentadienyl ring partial aromatic substituent (Ar) in [Table 2] may be the cyclopentadienyl ring partial substituent (Y) shown in [Table 3].

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 (OMe) ₂ , Ti (OiPr) ₂ , Ti (NMe ₂ ) ₂ , Ti (OMs) ₂ , Ti (OTs) 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 (eta 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 (OMe) ₂ , Zr (OiPr) ₂ , Zr (NMe ₂ ) ₂ , Zr (OMs) ₂ , Zr (OTs) ₂ , Zr (OTf) 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 (eta ⁴ -1,3-pentadienyl), Hf (η ⁴ -2,4- hexadienyl), Hf (η ⁴ -1,4- _{diphenyl-1,3-pentadienyl), Hf (CH 2 -Si (} Me) ₃ ) ₂ , Hf (OMe) ₂ , Hf (OiPr) ₂ , Hf (NMe ₂ ) ₂ , Hf (OMs) ₂ , Hf (OTs) ₂ , Hf (OTf) _{2, and the} like. Me is a methyl group, Bn is a benzyl group, tBu is a tert-butyl group, Si (Me) ₃ is a trimethylsilyl group, OMe is a methoxy group, OiPr is an iso-propoxy group, NMe ₂ is a dimethylamino group, and OMs is a methanesulfonate. The group, OTs is a p-toluenesulfonate group, and OTf is a trifluoromethanesulfonate group.

According to the above notation, the cyclopentadienyl ring moiety is α-3 in [Table 1], and the cyclopentadienyl ring partial substituents Y ² and Y ⁵ are γ-1, cyclopenta in [Table 3]. The dienyl ring partial aromatic substituent (Ar) is δ-1 in [Table 4], and the cyclopentadienyl ring partial aromatic substituents (T ¹ ) and (T ² ) are the substituents at the 3rd and 5th positions. When ε-1, the substituent (J) at the 4-position of the cyclopentadienyl ring partial aromatic substituent is composed of a combination of ζ-8 and the MX _{n of} the metal moiety is HfMe ₂ , the following compound [6] Is illustrated.

The cyclopentadienyl ring moiety is α-2 in [Table 1], and the cyclopentadienyl ring partial substituent Y ¹ is γ-2, Y ² and Y ⁴ in [Table 3] [Table 3]. Γ-1, Y ⁵ in the cross-linked moiety, cyclopentadienyl ring partial aromatic substituent (Ar) in δ-1, cyclopentadienyl ring partial aromatic substituent (Ar) in [Table 4] 3,5 The substituents (T ¹ ) and (T ² ) at the positions are ε-8, the substituent (J) at the 4-position of the cyclopentadienyl ring partial aromatic substituent is ζ-2, and the crosslinked part is in [Table 9]. _{When the MX n of} the metal part is ZrCl ₂ , it is composed of the combination of ι-32, and the following compound [7] is exemplified.

If the two substituted cyclopentadienyl ring moieties bonded to the metal moiety MX _n are not the same, but are different, then one cyclopentadienyl ring moiety is α-2, cyclo in [Table 1]. Pentazienyl ring partial substituent Y ¹ is γ-6, Y ² , Y ⁴ and Y ⁵ in [Table 3] γ-1, cyclopentadienyl ring partial aromatic substituent (Table 3) Ar) is δ-8 in [Table 4], the other cyclopentadienyl ring moiety is α-15 in [Table 1], and the cyclopentadienyl ring partial substituent Y ⁵ is [Table 2]. Γ-1, cyclopentadienyl ring partial substituents (V ¹ ) to (V ⁴ ) are composed of a combination of η-2 in [Table 7], and MX _{n of} the metal part is Zr (NMe ₂ ). _{In the case of 2,} the following compound [8] is exemplified.

The combination structure of the cyclopentadienyl ring and the crosslinked portion is β-3 in [Table 2], and the cyclopentadienyl ring partial aromatic substituent (Ar) is δ-1 in [Table 4], cyclopenta. ^{Substituents (T 1} ) and (T ² ) at the 3rd and 5th positions of the dienyl ring partial aromatic substituent are ε-10, and the substituent (J) at the 4th position of the cyclopentadienyl ring partial aromatic substituent is. ζ-26, and the other cyclopentadienyl ring moiety is α-8 in [Table 1], and the cyclopentadienyl ring partial substituent Y ¹ is γ-21, Y ^{5 in [Table 3].} bridging moiety, Ar is gamma-1, cyclopentadienyl ring moiety substituent (W) is formed by a combination of theta-9 in Table 8], MX _n of the metal portion is Ti (η ⁴ -1,3 In the case of −pentadienyl), the following compound [9] is exemplified.

The reason why the above transition metal compounds exhibit peculiar performance is not clear at present, but the inventor of the present application speculates as follows.
The transition metal compound of the present invention has a heteroatom in any of the five carbon atoms forming the cyclopentadienyl skeleton of (i) the metallocene compound in the transition metal compound [A] represented by the general formula [1]. It is characterized by having an electron-donating aromatic substituent. It is thought that this gives the potential to increase the activity, which is thought to be due to the inflow of electrons to the vicinity of the central metal via the conjugated system, and to improve the reactivity with α-olefins, especially higher α-olefins with a large number of carbon atoms. Be done. On the other hand, the substituent near the (ii) hetero element is considered to reduce the interaction between the hetero atom and a Lewis acidic compound such as an organic metal compound described later, or the central metal of the transition metal compound. It is considered that only the performance improvement effect due to the introduction can be selectively exhibited.

((B-1) Organometallic compound)
Specific examples of the organometallic compound (B-1) used in the present invention are Group 1, 2, 12, and 13 of the periodic table represented by the following general formulas (B-1a) to (B-1c). Compounds containing at least one atom of:
R ^a _p Al (OR ^b ) _q H _r Y _s・ ・ ・ (B-1a)
(In the general formula (B-1a), ^Ra and R ^b may be the same or different from each other, and represent hydrocarbon groups having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, and Y is a halogen atom. , P is 0 <p ≦ 3, q is 0 ≦ q <3, r is 0 ≦ r <3, s is 0 ≦ s <3, and m + n + p + q = 3). Organic aluminum compound;
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 and aluminum of Group 1 of the Periodic Table;
R ^d R ^e M ⁴ ... (B-1c)
(In the general formula (B-1c), R ^d and R ^e may be the same or different from each other, and represent hydrocarbon groups having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, and M ⁴ is Mg. , Zn or Cd.) A dialkyl compound with an alkaline earth metal of Group 2 or a metal of Group 12 of the periodic table.

Examples of the organoaluminum compound belonging to the general formula (B-1a) include the following compounds.
R ^a _p Al (OR ^b ) _3-p ... (B-1a-1)
(In the formula (B-1a-1), ^Ra and R ^b may be the same or different from each other, and represent hydrocarbon groups having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, and p is preferable. 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 preferably 0 <p <3. The organic aluminum 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 of 2 ≦ p <3). Represented organoaluminum compound,
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 represent hydrocarbon groups having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, and Y is a halogen. An organic aluminum compound representing an atom, where p is 0 <p ≦ 3, q is 0 ≦ q <3, s is a number of 0 ≦ s <3, and p + q + s = 3).

More specifically, as the organoaluminum compound belonging to the general formula (B-1a), trimethylaluminum, triethylaluminum, trin-butylaluminum, tripropylaluminum, tripentylaluminum, trihexylaluminum, trioctylaluminum, and tridecylaluminum. Tri-n-alkylaluminum such as;
Triisopropylaluminum, triisobutylaluminum, trisec-butylaluminum, tritert-butylaluminum, tri2-methylbutylaluminum, tri3-methylbutylaluminum, tri2-methylpentylaluminum, tri3-methylpentylaluminum, tri4 -Tri-branched alkylaluminum such as methylpentylaluminum, tri2-methylhexylaluminum, tri3-methylhexylaluminum, tri2-ethylhexylaluminum;
Tricycloalkylaluminum such as tricyclohexylaluminum and tricyclooctylaluminum;
Triarylaluminum such as triphenylaluminum and tritrylaluminum;
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;
Alkoxides such as isobutylaluminum methoxydo, isobutylaluminum ethoxide, isobutylaluminum isopropoxide;
Dialkylaluminum alkoxides such as dimethylaluminum methoxyde, diethylaluminum ethoxide, dibutylaluminum butoxide;
Alkylaluminum sesquialkoxides such as ethylaluminum sesquiethoxydo and butylaluminum sesquibutoxide;
Partially alkoxylated alkylaluminum with an average composition represented by R ^a _2.5 Al (OR ^b ) _0.5 ^{(in the formula, R a} and R ^b may be the same or different from each other and have a number of carbon atoms. Shows 1-15, preferably 1-4 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) and isobutylaluminum bis (2,6-di-t-butyl-4-methylphenoxide);
Dialkylaluminum halides such as dimethylaluminum chloride, diethylaluminum chloride, dibutylaluminum chloride, diethylaluminum bromide, diisobutylaluminum chloride;
Alkylaluminum sesquihalides such as ethylaluminum sesquichloride, butylaluminum sesquichloride, ethylaluminum sesquibromid;
Partially halogenated alkylaluminum such as alkylaluminum dihalide such as ethylaluminum dichloride, propylaluminum dichloride, butylaluminum dibromid;
Dialkylaluminum hydrides such as diethylaluminum hydride and dibutylaluminum hydride;
Other partially hydrogenated alkylaluminum such as ethylaluminum dihydride, alkylaluminum dihydride such as propylaluminum dihydride;
Examples thereof include partially alkoxylated and halogenated alkylaluminum such as ethylaluminum ethoxychloride, butylaluminum butoxycyclolide, ethylaluminum ethoxybromid and the like.

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

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

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

Further, a compound such that the organoaluminum compound is formed in the polymerization system, for example, a combination of aluminum halide and alkyllithium, a combination of aluminum halide and alkylmagnesium, and the like can be used as the organometallic compound (B-1). Can also be used as.

Among the organometallic compounds (B-1), organoaluminum compounds are preferable from the viewpoint of catalytic activity.
The above-mentioned organometallic compound (B-1) is used alone or in combination of two or more.

((B-2) Organoaluminium oxy compound)
The organoaluminum oxy compound (B-2) used in the present invention may be a conventionally known aluminoxane, or is a benzene-insoluble organoaluminum oxy compound as exemplified in JP-A-2-78687. You may.

Conventionally known aluminoxane can be produced, for example, by the following method, and is usually 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 in which an organic aluminum compound such as trialkylaluminum is added to the hydrocarbon medium suspension of the above, and adsorbed water or water of crystallization is reacted with the organic aluminum compound.

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

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

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

Specific examples of the organoaluminum compound used when preparing alminoxane 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-mentioned organoaluminum compounds are used alone or in combination of two or more.

Examples of the solvent used for the preparation of alminoxane include aromatic hydrocarbons such as benzene, toluene, xylene, cumene and simen, aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, hexadecane and octadecane, and cyclopentane. , Cyclohexane, cyclooctane, alicyclic hydrocarbons such as methylcyclopentane, petroleum distillates such as gasoline, kerosene, light oil or halides of the above aromatic hydrocarbons, aliphatic hydrocarbons, alicyclic hydrocarbons, especially chlorine Examples thereof include hydrocarbon solvents such as isomers and bromines. Further, ethers such as ethyl ether and tetrahydrofuran can 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 a following general formula (B-2c). Examples thereof include aluminoxane selected from at least one aluminoxane having a repeating unit and a repeating unit represented by the following general formula (B-2d) as a structure.

In the general formula, ^Re is independently a hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms, and specifically, a methyl group, an ethyl group, a propyl group, an isopropyl group, and an isopropenyl group. , N-butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, octyl group, decyl group, dodecyl group, tridecyl group, tetradecyl group, hexadecyl group, octadecyl group, eicosyl group, cyclohexyl group, cyclo A hydrocarbon group such as an octyl group, a phenyl group, a tolyl group, and an ethylphenyl group can be exemplified. 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 The part may be substituted with a halogen atom such as chlorine or bromine, and the halogen content may be 40% by weight or less. A straight line in (B-2c) and (B-2d) in which one 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 in the range of 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.

Aluminoxane having a repeating unit represented by the general formula (B-2c) and a repeating unit represented by the general formula (B-2d) has a molecular weight in the range of 200 to 2000 as measured by the freezing point depression method of benzene. It is preferably inside.

Further, in the benzene-insoluble organic aluminum oxy compound used in the present invention, the Al component dissolved in benzene at 60 ° C. is 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 sparingly soluble in benzene. )

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

（一般式（Ｂ−２ｅ）中、Ｒ^fは炭素原子数が１〜１０の炭化水素基を示し、４つのＲ^g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 ^f represents a hydrocarbon group having 1 to 10 carbon atoms, and the four R ^g may be the same or different from each other, and each of them independently has a hydrogen atom and a halogen. Indicates a hydrocarbon group having 1 to 10 atoms or carbon atoms.)

The organoaluminum oxy compound containing boron represented by the general formula (B-2e) contains an alkylboronic acid represented by the following general formula (B-2f) and an organoaluminum compound in an inert gas atmosphere. It can be produced by reacting in an inert solvent at a temperature of −80 ° C. to room temperature for 1 minute to 24 hours.
R ^f −B (OH) ₂ ... (B-2f)
(In the general formula (B-2f), R ^f represents the same group as ^{R f} in the general formula (B-2e).)

Specific examples of the alkylboronic acid represented by the general formula (B-2f) include methylboronic acid, ethylboronic acid, isopropylboronic acid, n-propylboronic acid, n-butylboronic acid, isobutylboronic acid, and n-. Examples thereof include hexylboronic acid, cyclohexylboronic acid, phenylboronic acid, 3,5-difluoroboronic acid, pentafluorophenylboronic acid, and 3,5-bis (trifluoromethyl) phenylboronic acid. Among these, methylboronic acid, n-butylboronic acid, isobutylboronic acid, 3,5-difluorophenylboronic acid, and pentafluorophenylboronic acid are preferable. These are used alone or in combination of two or more.

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

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

When an organoaluminum oxy compound (B-2) such as methylaluminoxane as a co-catalyst component is used in combination with the transition metal compound [A], it exhibits extremely high polymerization activity for an olefin compound.
The above-mentioned organoaluminum oxy compound (B-2) is used alone or in combination of two or more.

((B-3) A compound that reacts with the transition metal compound [A] to form an ion pair)
As the compound (B-3) (hereinafter, referred to as “ionized ionic compound”) used in the present invention that reacts with the transition metal compound [A] to form an ion pair, Japanese Patent Application Laid-Open No. 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. Further, 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 a fluorine, a methyl group or a trifluoromethyl group) is used. For example, trifluoroborone, triphenylboron, tris (4-fluorophenyl) boron, tris (3,5-difluorophenyl) boron, tris (4-fluoromethylphenyl) boron, tris (pentafluorophenyl) boron, etc. Tris (p-tolyl) boron, tris (o-tolyl) boron, tris (3,5-dimethylphenyl) boron and the like.

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

（一般式［Ｂ−３ａ］中、Ｒ^h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、Ｒⁱ〜Ｒ^l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 ^h is H ^+, carbonium cation, ferrocenium cation having oxonium cation, ammonium cation, phosphonium cation, a cycloheptyltrienyl cation or a transition metal, R ⁱ ~ R ^l 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 triphenyl carbonium cation, tri (methylphenyl) carbonium cation, and tri (dimethylphenyl) carbonium cation.

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

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

As R ^h , carbonium cations and ammonium cations are preferable, and triphenylcarbonium cations, N, N-dimethylanilinium cations, and N, N-diethylanilinium cations are particularly preferable.

Further, as the ionic compound, a trialkyl-substituted ammonium salt, an N, N-dialkylanilinium salt, a dialkylammonium salt, a triarylphosphonium salt and the like can also be mentioned.

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-ditrifluoromethylphenyl) 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 Di (octadecyl) methylammonium such as (octadecyl) methylammonium tetrakis (4-trifluoromethylphenyl) boron, di (octadecyl) methylammonium tetrakis (3,5-ditrifluoromethylphenyl) boron Alkylammonium salts can be exemplified.

Specifically, as the N, N-dialkylanilinium salt, for example, N, N-dimethylanilinium tetra (phenyl) boron, N, N-diethylanilinium tetra (phenyl) boron, N, N, 2,4. 6-Pentamethylanilinium tetra (phenyl) boron and the like can be mentioned.

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, ferrosenium tetra (pentafluorophenyl) borate, triphenylcarbenium pentaphenyl Cyclopentadienyl complex, N, N-diethylanilinium pentaphenylcyclopentadienyl complex, boron compound represented by the following formula (B-3b) or (B-3c) and the like can also be mentioned.

（式（Ｂ−３ｂ）中、Ｅｔはエチル基を示す。）

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

（式（Ｂ−３ｃ）中、Ｅｔはエチル基を示す。）

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

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] nonabolate, bis [tri (n-butyl) ammonium] decaborate, bis [tri (n-butyl) ammonium] undecaborate, bis [tri (n-butyl) ammonium] dodecaborate , Anionic salts such as bis [tri (n-butyl) ammonium] decachlorodecaborate, bis [tri (n-butyl) ammonium] dodecachloro dodecaborate;
Metal borane anions such as tri (n-butyl) ammonium bis (dodecahydride dodecaborate) cobaltate (III), bis [tri (n-butyl) ammonium] bis (dodecahydride dodecaborate) nickelate (III) Examples include salt.

Specific examples of the carborane compound, which is an example of an ionized ionic compound, include 4-carbanonaborane, 1,3-dicarbanoborane, 6,9-dicarbadecaborane, and dodecahydride-1-phenyl-1,3-. Dicarbanonaborane, dodecahydride-1-methyl-1,3-dicarbanonaborane, undecahydride-1,3-dimethyl-1,3-dicarbanonaborane, 7,8-dicarbanonaborane, 2, , 7-Dicarbaundecaborane, Undecahydride-7,8-dimethyl-7,8-dicarbaundecaborane, Dodecahydride-11-methyl-2,7-dicarbundecaborane, Tri (n-butyl) ammonium 1-carbadecaborate, tri (n-butyl) ammonium 1-carbundecaborate, tri (n-butyl) ammonium 1-carbadodecaborate, tri (n-butyl) ammonium 1-trimethylsilyl-1-carbadecaborate, Tri (n-butyl) ammonium bromo-1-carbadodecaborate, tri (n-butyl) ammonium 6-carbadecaborate, tri (n-butyl) ammonium 6-carbadecaboleate, tri (n-butyl) ammonium 7- Carbaundecaborate, tri (n-butyl) ammonium 7,8-dicarbaundecaborate, tri (n-butyl) ammonium 2,9-dicarbundecaborate, tri (n-butyl) ammonium dodecahydride-8-methyl -7,9-dicarbaundecaborate, tri (n-butyl) ammonium undecahydride-8-ethyl-7,9-dicarbaundecaborate, tri (n-butyl) ammonium undecahydride-8-butyl-7 , 9-Dicarbaundecaborate, tri (n-butyl) ammonium undecahydride-8-allyl-7,9-dicarbaundecaborate, tri (n-butyl) ammonium undecahydride-9-trimethylsilyl-7,8 -Dicarbundecaborate, tri (n-butyl) ammonium undecahydride-4,6-dibromo-7-carbundecaborate and other anion salts;
Tri (n-butyl) ammonium bis (nonahydride-1,3-dicarbanonabolate) cobaltate (III), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarbaundecaborate) Telate (III), Tri (n-Butyl) Ammonium Bis (Undeca Hydlide-7,8-Dicarba Undecaborate) Cobalate (III), Tri (n-Butyl) Ammonium Bis (Undeca Hydride-7) , 8-dicarbundecaborate) Niklate (III), Tri (n-butyl) Ammonium Bis (Undeca Hydlide-7,8-dicarbundecaborate) Copper Acidate (III), Tri (n-butyl) Ammonium Bis (Undeca Hydlide-7,8-Dicarba Undecaborate) Hydrochloride (III), Tri (n-Butyl) Ammonium Bis (Nona Hydride-7,8-Dimethyl-7,8-Dicarba Undecaborate) Tetrate (III), Tri (n-Butyl) Ammonium Bis (Nonahydrate-7,8-Dimethyl-7,8-Dicarbundecaborate) Chromate (III), Tri (n-Butyl) Ammonium Bis (N-butyl) Tribromooctahydride-7,8-dicarbaundecaborate) cobaltate (III), tris [tri (n-butyl) ammonium] bis (undecahydride-7-carbaundecaborate) chromate (III) , Bis [Tri (n-butyl) Ammonium] Bis (Undeca Hydlide-7-Carbaundecaborate) Manganate (IV), Bis [Tri (n-Butyl) Ammonium] Bis (Undeca Hydlide-7-Cal) Bound decaborate) cobaltate (III), bis [tri (n-butyl) ammonium] bis (undecahydride-7-carbundecaborate) nickelate (IV) and other metal carborane anion salts. Be done.

Heteropoly compounds, which are examples of ionized ionic compounds, include atoms selected from silicon, phosphorus, titanium, germanium, arsenic and tin, and one or more atoms selected from vanadium, niobium, molybdenum and tungsten. It is a compound. Specifically, limvanadic acid, germanovanadic acid, arsenic vanadic acid, linniobic acid, germanoniobic acid, siliconomolybdic acid, phosphomolybdic acid, tungstic acid, germanomolybdic acid, arsenic molybdic acid, tungstic acid, phosphorus Tungstic acid, germanotungstic acid, tin tungstic acid, phosphoribdovanadic acid, lintangustvanadic acid, germanotangstvanadic acid, lymmolibed tongue tungstic acid, germanomoribed tongue tungstic acid, phosphoribdotungstic acid , Tungstic acid, and salts of these acids, but not limited to. The salt may be an alkali metal of Group 1 or an alkaline earth metal of Group 2 of the periodic table of the acid, specifically, lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium. , Salts with cesium, barium and the like, and organic salts such as triphenylethyl salt and the like.

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

The above-mentioned ionized ionic compound (compound (B-3) that reacts with the transition metal compound [A] to form an ion pair) is used alone or in combination of two or more.
The catalyst for olefin polymerization according to the present invention includes the above-mentioned transition metal compound [A], an organometallic compound (B-1), an organoaluminum oxy compound (B-2), and an ionized ionic compound (B-3). The following carrier [C] may be contained, if necessary, together with 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 solid in the form of granules or fine particles. By supporting the transition metal compound [A] and the compound [B] on the carrier [C], a polymer having good morphology can be obtained.

As the inorganic compound, a porous oxide, a solid aluminoxane compound, an inorganic halide, clay, a clay mineral or an ion-exchange layered compound is 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 the} like, or a composite or mixture containing these. It can also be used, for example natural or synthetic zeolite, 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, as the porous oxide, those containing SiO ₂ and / or Al ₂ O ₃ as main components are preferable.

The above-mentioned porous oxides are a small amount of Na ₂ CO ₃ , K ₂ CO ₃ , CaCO ₃ , Mg _{CO 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.

The properties of such a porous oxide differ depending on the type and manufacturing method, but the porous oxide preferably used in the present invention has a particle size of 10 to 300 μm, preferably 20 to 200 μm, and a specific surface area. It is desirable that the pore volume is in the range of 50 to 1000 m ² / g, preferably 100 to 700 m ² / g, and the pore volume is in ^{the range of 0.3 to 3.0 cm 3 / g.} Such a porous oxide is used by firing 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 shown in (B-2a) to (B-2d).
Unlike conventionally known carriers for olefin polymerization catalysts, the solid aluminoxane used in the present invention does not contain inorganic solid components such as silica and alumina and organic polymer components such as polyethylene and polystyrene, and mainly contains alkylaluminum compounds. The solidified product is shown as. The meaning of "solid state" 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 the component [A] and the component [B] are brought into contact with each other to prepare a solid catalyst component for olefin polymerization as described later, an inert hydrocarbon solvent such as hexane or toluene used in the reaction is used. Medium, it indicates that the component [B] is in a solid state under a specific temperature / pressure environment. Further, for example, when suspension polymerization is carried out using a solid catalyst component for olefin polymerization prepared by using the component [B] as described later, a specific temperature and pressure are used 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 carried out in a liquefied monomer instead of a solvent, and vapor phase polymerization in which polymerization is carried out in a monomer gas.

Whether or not the component [B] is in a solid state under the above environment is the easiest method to visually confirm, but it is often difficult to visually confirm, for example, during polymerization. In that case, for example, it is possible to judge from the properties of the polymer powder obtained after the polymerization and the state of adhesion to the reactor. On the contrary, if the properties of the polymer powder are good and the adhesion to the reactor is small, even if a part of the component [B] is eluted in the polymerization environment, the gist of the present invention is not deviated. Examples of the index for determining the properties of the polymer powder include bulk density, particle shape, surface shape, and the degree of abundance of the amorphous polymer, but the polymer bulk density is preferable from the viewpoint of quantitativeness. The bulk density in the present invention is usually 0.01 to 0.9, preferably in the range of 0.05 to 0.6, more preferably 0.1 to 0.5.

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

The dissolution ratio of the solid aluminoxane used in the present invention to n-hexane was determined by adding 2 g of the solid aluminoxane carrier to 50 ml of n-hexane maintained at 25 ° C., stirring for 2 hours, and then G-4 glass. The solution part was separated using a filter made by the manufacturer, and the concentration of aluminum in this 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 aluminoxane used.

As the solid aluminoxane according to the present invention, known solid aluminoxane can be used endlessly. As known manufacturing methods, for example, JP-A-7-42301, JP-A-6-220126, JP-A-6-220128, JP-A-11-140113, JP-A-11-310607, JP-A-2000. Examples thereof include Japanese Patent Application Laid-Open No. -38410, Japanese Patent Application Laid-Open No. 2000-95810, and WO201055652.

The average particle size of the solid aluminoxane according to the present invention is generally in the range of 0.01 to 50,000 μm, preferably 1 to 1000 μm, and particularly preferably 1 to 200 μm.
The average particle size of solid aluminoxane is determined by observing the particles with a scanning electron microscope, measuring the particle size of 100 or more particles, and averaging the weight. For the particle size of solid aluminoxane, the maximum length of the Pythagoras method was measured from a particle image. That is, the length of the particle image sandwiched between two parallel lines is measured in each of the horizontal direction and the vertical direction, and the calculation is performed using the following formula.
Particle size = ((horizontal length) ² + (vertical length) ² ) ^0.5
The weight average particle size of the solid aluminoxane is calculated by the following formula using the particle size 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 and the} like are used. The inorganic halide may be used as it is, or may be used after being pulverized by a ball mill or a vibration mill. Further, it is also possible to use a product obtained by dissolving an inorganic halide in a solvent such as alcohol and then precipitating it in the form of fine particles with a precipitant.

The clay is usually composed mainly of clay minerals. Further, the ion-exchangeable layered compound is a compound having a crystal structure in which surfaces formed by ionic bonds and the like are stacked in parallel with each other with a weak bonding force, and the contained ions can be exchanged. Most clay minerals are ion-exchange layered compounds. Further, as these clays, clay minerals, and ion-exchange layered compounds, not only naturally produced ones but also artificial synthetic compounds can be used.

Further, as the clay, clay mineral or ion-exchangeable layered compound, an ionic crystalline compound having a layered crystal structure such _{as hexagonal fine packing type, antimony type, CdCl 2} type and CdI _{2 type can be exemplified.}

Furthermore, as clays and clay minerals, kaolin, bentonite, wood knot clay, gailome clay, allophane, hisingel stone, pyrophyllite, ummo group, montmorillonite group, vermiculite, ryokudei stone group, parigolskite, kaolinite, nacrite, dicite, etc. Halloysite etc.
The ion-exchange layered _{compounds, 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 include crystalline acid salts of polyvalent metals such as NH ₄ PO ₄ ) ₂ and H _{2 O.}

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

It is also preferable to chemically treat the clay and clay mineral used in the present invention. As the chemical treatment, any of a surface treatment for removing impurities adhering to the surface, a treatment for affecting the crystal structure of clay, and the like can be used. Specific examples of the chemical treatment include acid treatment, alkali treatment, salt treatment, and organic substance treatment. The acid treatment removes impurities on the surface and increases the surface area by eluting cations such as Al, Fe, and Mg in the crystal structure. Alkaline treatment destroys the crystal structure of the clay, resulting in a change in the structure of the clay. Further, in the salt treatment and the organic substance treatment, an ion complex, a molecular complex, an organic derivative and the like can be formed, and the surface area and the interlayer distance can be changed.

The ion-exchangeable layered compound used in the present invention may be a layered compound in a state in which the layers are expanded by utilizing the ion exchange property and exchanging the exchangeable ions between the layers with another large bulky ion. .. Such bulky ions play a supporting role in supporting the layered structure, and are usually called pillars. Further, the introduction of another substance between the layers of the layered compound in this way is called intercalation. Guest compounds to be intercalated include cationic inorganic compounds such as _{TiCl 4} , ZrCl _4, and metal alkoxides such as _{Ti (OR) 4} , Zr (OR) ₄ , PO (OR) ₃ , and B (OR) _3. R is a hydrocarbon group, etc.), [Al ₁₃ O ₄ (OH) ₂₄ ] ⁷⁺ , [Zr ₄ (OH) ₁₄ ] ²⁺ , [Fe ₃ O (OCOCH ₃ ) ₆ ] ⁺ and other metal hydroxide ions And so on. These compounds are used alone or in combination of two or more. Further, when these compounds are intercalated _{, metal alkoxides such as Si (OR) 4} , Al (OR) ₃ , and Ge (OR) ₄ (R indicates a hydrocarbon group or the like) are hydrolyzed. The obtained polymer, a colloidal inorganic compound such as _{SiO 2 can coexist.} Further, examples of the pillars include oxides produced by intercalating the metal hydroxide ions between layers and then heating and dehydrating them.

The clay, clay mineral, and ion-exchange layered compound used in the present invention may be used as they are, or may be used after being subjected to a treatment such as ball milling or sieving. Further, it may be used after newly adding and adsorbing water or heat dehydration treatment. Further, it may be used alone or in combination of two or more.

Of these, preferred are clays or clay minerals, with particular preference being 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 fine particle 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. The polymers produced as, and their variants can be exemplified.

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

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

As the alcohols and the phenolic compound, ^{those represented by R m-} OH are usually used, where R ^m 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 the number of carbon atoms is 1 to 50 (in the case of phenols, the number of carbon atoms is 6 to 50).

As the alcohols, ^{those having R m} of a halogenated hydrocarbon group are preferable. Further, as the phenolic compound, those in which the α and α'-positions of the hydroxyl groups are substituted with hydrocarbons having 1 to 20 carbon atoms are preferable.

As the carboxylic acid, one represented by ^{R n − COOH is usually used.} R ⁿ 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—H bond, P—OR, phosphate having a P = O bond, and a phosphine oxide compound are preferably used.
Examples of the sulfonate include those represented by the following general formula (DA).

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

(In the general formula (D-a), M ⁵ is a Periodic Table 1-14 atom of Group, R ^o is hydrogen, halogen or a hydrocarbon group having 1 to 20 carbon atoms having 1 to 20 carbon atoms It is a hydrocarbon group, T is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group having 1 to 20 carbon atoms, and t is an integer of 1 to 7. U is an integer of 1 to 7, and tu ≧ 1.)

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

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

An olefin is reserved for 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, or the catalyst component may be further supported on the pre-polymerized solid catalyst component.

In the present invention, the polymerization (homopolymerization or copolymerization) can be carried out by any of a liquid phase polymerization method such as dissolution polymerization and suspension polymerization or a gas phase polymerization method. Specific examples of the inert hydrocarbon medium used in the liquid phase polymerization method are 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 like, and the olefins themselves to be subjected to polymerization. Can also be used as a solvent.

When polymerizing an olefin using the above catalyst for olefin polymerization, the transition metal compound [A] is usually 10 ^-12 to ^10-2 mol, preferably 10 ^-10 to 10 mol, per liter of the reaction volume. It is used in an amount such that it becomes ^{-3 mol.}

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

The molar ratio [[D] / (B-1)] of the organic compound component [D] to the organometallic compound (B-1) is usually 0.01 to 10, preferably 0.1 to 5. Used in large amounts. The molar ratio [[D] / (B-2)] of the organic compound component [D] to the organoaluminum oxy compound (B-2) is usually 0.001 to 2, preferably 0.005 to 1. It is used in such an amount. 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. It is used in such an amount.

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 under normal pressure to 100 kg / cm ^2- G, preferably normal pressure to 50 kg / cm ^2- G, and the polymerization reaction can be carried out in any of batch, semi-continuous and continuous methods. Can also be done. Further, it is also possible to carry out the polymerization in two or more stages having different reaction conditions.

The molecular weight of the obtained polyolefin can be adjusted by the presence of hydrogen in the polymerization system or by changing the polymerization temperature. Furthermore, it can be adjusted according to the amount of compound [B] used.

The olefin that can be polymerized by the olefin polymerization catalyst of the present invention is not particularly limited as long as it has a polymerizable double bond, but has a carbon atom number of 2 to 30, preferably 2 to 20, more preferably. 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 with 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 can be used for homopolymerization of ethylene or copolymerization of ethylene with an α-olefin having 3 to 20 carbon atoms, preferably a linear or branched α-olefin having 3 to 10 carbon atoms. It is more preferable to use it. The α-olefin may be used alone or in combination of two or more.

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

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

The catalyst for olefin polymerization of the present invention may polymerize a chain unsaturated hydrocarbon having a polar group (for example, a carbonyl group, a hydroxyl group, an ether bond group, etc.), and specifically, the unsaturated hydrocarbon may be polymerized. , For example acrylic acid, 3-butenoic acid, 4-pentenoic acid, 5-hexenoic acid, 6-heptenoic acid, 7-octenoic acid, 8-nonenic 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-eicocenoic acid, 20-henkocenoic acid, 21-dococenoic acid, 22-tricocenoic acid, methacrylic acid, 2-methylpentenoic acid, 2,2-dimethyl-3-butenoic acid, 2,2-dimethyl-4-pentenic acid, 3-vinylbenzoic acid, 4-vinylbenzoic acid, 2, 6-Heptadylic acid, 2- (4-isopropylbenzylidene) -4-pentenoic acid, allylmalonic acid, 2- (10-undecenyl) malonic acid, fumaric acid, itaconic acid, bicyclo [2.2.1] -5-heptene -2-Carboxylic acid, unsaturated carboxylic acids such as bicyclo [2.2.1] -5-heptene-2,3-dicarboxylic acid, and their sodium, potassium, lithium, zinc and magnesium salts, Unsaturated metal salts such as calcium salts, and methyl esters, ethyl esters, n-propyl esters, isopropyl esters, n-butyl esters, isobutyl esters, (5-norbornen-2-yl) esters and the like of these unsaturated carboxylic acids. Carboxylic acid esters (which may be monoesters or diesters when the unsaturated carboxylic acid is a dicarboxylic acid), and amides, N, N-dimethylamides, etc. of these unsaturated carboxylic acids. Saturated carboxylic acid amides (may be monoamides or diamides if the unsaturated carboxylic acid is a dicarboxylic acid);
Maleic anhydride, itaconic anhydride, allyl succinic anhydride, isobutenyl succinic anhydride, (2,7-octadien-1-yl) succinic anhydride, tetrahydrophthalic anhydride, bicyclo [2.2.1] ] -Saturated carboxylic acid anhydrides such as 5-heptene-2,3-dicarboxylic acid anhydrides;
Vinyl esters such as vinyl acetate, vinyl propionate, vinyl caproate, vinyl caproate, 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;
Cyrilized olefins such as allyltrimethylsilane, diallyldimethylsilane, 3-butenyltrimethylsilane, allyltriisopropylsilane, and 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-nonenor, 9-decenol, 10-undecenol, 11-dodecenol, 12-tridecenol. , And these unsaturated esters such as acetate, benzoic acid ester, propionic acid ester, caproic acid ester, capric acid ester, lauric acid ester, stearic acid ester;
Substituted phenols such as vinylphenol and allylphenol, and unsaturated esters such as acetic acid ester, benzoic acid ester, propionic acid ester, caproic acid ester, capric acid ester, lauric acid ester and stearic acid ester;
Substituted benzyl alcohols such as vinylbenzyl alcohol and allylbenzyl alcohol, and unsaturated esters such as acetic acid esters, benzoic acid esters, propionic acid esters, caproic acid esters, capric acid esters, lauric acid esters and stearic acid esters;
Unsaturated ethers such as methyl vinyl ether, ethyl vinyl ether, allyl methyl ether, allyl propyl ether, allyl butyl ether, allyl metallic ether, methoxystyrene, ethoxystyrene, allyl anisole;
Unsaturated epoxides such as butadiene monooxide, 1,2-epoxy-7-octene, 3-vinyl7-oxabicyclo [4.1.0] heptane;
Unsaturated aldehydes such as acrolein and undecenal, and unsaturated acetals such as these dimethyl acetals and diethyl acetals;
Unsaturated ketones such as methyl vinyl ketone, ethyl vinyl ketone, allyl methyl ketone, allyl ethyl ketone, allyl propyl ketone, allyl butyl ketone, allyl benzyl ketone, and unsaturated acetals such as these dimethyl acetals and diethyl acetals;
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 allylphenyl sulfoxide;
Unsaturated sulfones such as allylphenyl sulfone;
Unsaturated phosphines such as allyldiphenylphosphine;
Examples include unsaturated phosphine oxides such as allyldiphenylphosphine oxide.

Further, unsaturated hydrocarbons having two or more of the above-mentioned polar groups, such as vinyl trifluoroacetate, allyl trifluoroacetate, methyl 4- (3-butenyloxy) benzoate, glycidyl acrylate, allyl glycidyl ether, (2H-Perfluoropropyl) -2-propenyl ether, linalol oxide, 3-allyloxy-1,2-propanediol, 2- (allyloxy) ethanol, N-allylmorpholin, 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.

Further, the catalyst for olefin polymerization 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, 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-octadien, 1,5-octadien, 1,6-octadien, 1,7-octadien, etylidene norbornene, vinyl norbornene, dicyclopentadiene;
7-Methyl-1,6-octadien, 4-ethylidene-8-methyl-1,7-nonadien, 5,9-dimethyl-1,4,8-decatorien;
Further, mono or poly such as aromatic vinyl compounds such as styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, o, p-dimethylstyrene, o-ethylstyrene, m-ethylstyrene and p-ethylstyrene. Alkylstyrene;
Functional group-containing styrene derivatives such as methoxystyrene, ethoxystyrene, vinylbenzoic acid, methyl vinylbenzoate, vinylbenzylacetate, hydroxystyrene, o-chlorostyrene, p-chlorostyrene, divinylbenzene;
And 3-phenylpropylene, 4-phenylpropylene, α-methylstyrene and the like.

The transition metal compound [A] of the present invention has a novel structure in which a specific aromatic substituent is directly introduced into the cyclopentadienyl moiety of the metallocene skeleton as described above, and contains the compound [A]. The olefin polymerization catalyst of the present invention has a particularly excellent α-olefin copolymerizability as compared with a transition metal compound having a conventional metallocene skeleton (which does not have a specific aromatic substituent at the cyclopentadienyl moiety). It is possible to produce a low-density ethylene-based copolymer having a sufficient molecular weight with good olefin polymerization activity.

The effect is the effect of introducing a heteroatom-containing electron-donating aromatic substituent into the cyclopentadienyl moiety of the (i) metallocene compound in the transition metal compound [A] represented by the general formula [1] or [2]. It is considered that this is due to the remarkable improvement of α-olefin copolymerization and the effect of (ii) inhibiting the activity decrease phenomenon due to the introduction of heteroatoms by the effect of introducing a substituent into the vicinity.

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

As one aspect of the olefin polymer of the present invention, an ethylene-based weight containing an ethylene-derived structural unit in the range of preferably 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 structural units derived from the olefin A in the range of 0 to 10 mol% in total, more preferably 0 to 8 mol%, and further 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 olefin A is 100 mol%. The ethylene-based polymer whose structural unit derived from olefin A is in the above range is excellent in moldability. In addition, other structural units may be included as long as the gist of the present invention is not deviated. These contents can be measured by nuclear magnetic resonance spectroscopy, infrared spectroscopy when there is a reference substance, or the like.

Among these polymers, ethylene homopolymer, ethylene / propylene copolymer, ethylene / 1-butene copolymer, ethylene / propylene / 1-butene copolymer, ethylene / 1-octene polymer, ethylene / 1 −Hexen 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 preferable. Further, it may be a so-called block copolymer (impact copolymer) obtained by mixing or continuously producing two or more kinds selected from these polymers.

Among the polymers having the structural units described above, the ethylene-based polymer of the present invention is preferably an α-olefin polymer consisting of only structural units derived from α-olefins having 2 to 20 carbon atoms. By "substantially", it means that the ratio of the constituent units derived from α-olefin having 2 to 20 carbon atoms to all the constituent units is 95% by weight or more.

In the olefin polymer of the present invention, the weight average molecular weight measured by the gel permeation chromatography (GPC) method is not particularly limited, but is preferably 10,000 to 5,000,000, more preferably 10,000. ~ 2,000,000, particularly preferably 20,000-1,000,000. The molecular weight distribution (Mw / Mn), which is the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn), is not particularly limited, but is preferably 1 to 10, more preferably 1 to 7, and particularly preferably 1 to 1. It is 5.5. The molecular weight distribution can also be adjusted by producing polymers having different molecular weights by a multi-stage polymerization method or the like, or by a method such as solvent separation.

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

In the olefin 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 olefin polymer of the present invention, the ultimate 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. It is 10 dl / g.

In the olefin polymer of the present invention, the melt mass flow rate (MFR; unit is g / 10 minutes) measured under the conditions of 190 ° C. and 2.16 kg load according to ASTM D1238-89 is not particularly limited, but is preferably 0. 0.01 g / 10 minutes or more and 300 g / 10 minutes or less, more preferably 0.001 g / 10 minutes or more and 200 g / 10 minutes or less.

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

The present invention will be described in more detail with reference to the following examples. The present invention is not limited to the description of the following examples.
The transition metal compounds are ^{270 MHz, 1} H-NMR (JEOL; GSH-270), gas chromatograph mass spectrometer (GC-MS) (Shimadzu; GCMS-QP5050A and Shimadzu; GCMS-QP2010Ultra), FD-mass. It was identified using analysis (JEOL SX-102A).
Further, a method for measuring the physical characteristics and properties of a polymer obtained by polymerization of an olefin in the presence of a catalyst containing a transition metal compound of the present invention is described below.

・ Density (kg / m ³ )
Using a hydraulic heat press machine manufactured by Shinto Kinzoku Kogyo Co., Ltd. set at 190 ° C. ^{, a 0.5 mm thick sheet was formed at a pressure of 100 kg / cm 2} (spacer shape: 240 x 240 x 0.5 (mm) thick plate. 45 x 45 x 0.5 (mm), take 9 pieces), cool by compressing at a pressure of ^{100 kg / cm 2} using another hydraulic heat press machine manufactured by Shinto Kinzoku Kogyo Co., Ltd. set at 20 ° C. A sample for measurement was prepared. A 5 mm thick SUS plate was used as the hot plate.
This press sheet was heat-treated at 120 ° C. for 1 hour, slowly cooled linearly 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 the number average molecular weight (Mn) of the olefin polymer were determined by gel permeation chromatography (GPC). It was calculated from the molecular weight distribution curve obtained by Waters' Alliance GPC 2000 gel permeation chromatograph (high temperature size exclusion chromatograph), and the operating conditions are as follows:

[Devices used and conditions]
Measuring device: Gel permeation chromatograph alliance GPC2000 type (Waters)
Analysis software; Chromatography data system Emper (trademark, Waters)
Column; TSKgel GMH6-HT x 2 + TSKgel GMH6-HT x 2 (inner diameter 7.5 mm x length 30 cm, Tosoh)
Mobile phase; o-dichlorobenzene [= ODCB] (Wako Pure Chemical Industries, Ltd. special grade reagent)
Detector; differential refractometer (built-in device)
Column temperature; 140 ° C
Flow velocity; 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) / Molecular weight 495 to 20.6 million Molecular weight distribution and various average molecular weights are described in J.M. Polym. Sci. 1967, B5, 753. Calculated as polyethylene molecular weight conversion according to the general-purpose calibration procedure described in.

-Comonomer content The copolymer content of the copolymer was measured by FT-IR (FT-IR410 type infrared spectrophotometer manufactured by Nippon Kogaku Co., Ltd.). For FT-IR, a film obtained by dissolving and stretching the copolymer-forming polymer obtained in Examples in a hot press heated to 135 ° C. and then pressurizing and cooling at room temperature was used as a measurement sample, and a light source was used. The measurement was performed at a wavelength of 5000 cm ^{-1 to} 400 cm ^-1. The hexene content uses hexene-based C-CH ₂ CH ₂ CH ₂ CH ₃ skeletal vibration (1378 cm ^-1 ) as the key band, and the absorbance of the key band (D1378) and the internal standard band (4321 cm ^-1 : CH expansion and contraction vibration). It was determined by the ratio [D1378 / D4321] with the absorbance (D4321) of methylene and methyl variable vibration vibration.

A calibration curve that specifies the relationship between the comonomer content and the above [D1378 / D4321] is used to determine the comonomer content. The calibration curve is prepared in advance by FT-IR measurement of ethylene-based copolymers having various compositions whose comonomer content has been specified by ^{13 C NMR by the above method and the result of the above [D1378 / D4321].}

<(1) Synthesis of transition metal compounds>
[Example 1]
(Example 1-1) Synthesis of compound (1a) 0.54 g (22.3 mmol) of magnesium pieces was charged into a 300 mL reactor sufficiently dried and substituted with argon, and the mixture was vigorously stirred 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, Euro. J. Org. Chem. 2006, 2727. And a 25 mL diluted solution of 4-bromo-2,6-di-iso-propyl-N, N-dimethylaniline 5.69 g (20.0 mmol) synthesized by the method described in WO2007 / 034975 was slowly added. It was heated to reflux in an oil bath for 1 hour. After cooling the reaction solution to −78 ° C., 2.20 mL (22.2 mmol) of 3-methylcyclopentene-1-one was slowly added, and stirring was continued for 19 hours while slowly returning to room temperature. 2.00 mL of concentrated hydrochloric acid was added, and the mixture was stirred at room temperature for 1 hour, and then neutralized by adding a saturated aqueous sodium hydrogen carbonate solution under ice-cooling. Solubles were extracted with ethyl acetate, the resulting fraction was washed with water and saturated brine, and dried over anhydrous magnesium sulfate. After filtering magnesium sulfate, the filtrate was distilled off and the obtained residue was purified by silica gel column chromatography to find 1.35 g (hereinafter referred to as compound (1a)) of the target product represented by the following formula (1a) (hereinafter referred to as compound (1a)). Yield 24%) was obtained.
^{1 1} H NMR (270 MHz, CDCl ₃ ) δ 7.20 (2H, s, Ar-H), 6.72-6.64 (1H, m, -CH = C-), 6.02-5.90 ( 1H, m, -CH = C-), 3.45-3.04 (4H, m, -CH _2- & -CH (CH ₃ ) ₂ ), 2.84 (6H, s, -NC (CH ₃₎ ) ₂ ), 2.20-1.95 (3H, m, C-CH ₃ ), 1.23 (12H, d, J = 6.9Hz, -CH (CH ₃ ) ₂ ) ppm

(Example 1-2) Synthesis of metallocene compound (1) 0.35 g (1.22 mmol) of the compound (1a) obtained in Example 1-1, diethyl 10 mL of ether was charged and stirred. 0.75 mL of an n-butyllithium solution (hexane solution, 1.63 M, 1.22 mmol) was added to this solution under ice-cooling, and then stirring was continued at room temperature for 3 hours. The solution was cooled to 0 ° C., 0.14 g (0.61 mmol) of zirconium tetrachloride was added, and stirring was continued at room temperature for 19 hours. After distilling off the solvent of the reaction solution, dichloromethane was added to the obtained solid to prepare a suspension, and the insoluble matter was removed with a membrane syringe filter. The obtained solution was concentrated under reduced pressure, the suspension was prepared by adding n-hexane, and the insoluble material was filtered off by a glass filter. After distilling off the solvent of the obtained solution, n-hexane was added and the mixture was allowed to stand for 72 hours under cooling at 0 ° C. The crystallized crystals are separated by filtration, and the residue is dried under reduced pressure to obtain a white powdery compound bis (1- (3,5-di-iso-propyl-N, N-dimethyl) represented by the following formula (16). Aminophenyl) -3-methylcyclopentadienyl) zirconium dichloride (hereinafter referred to as metallocene compound (1)) 0.01 g (1% yield, racemic / meso or meso / racemic ratio = 2/1) Obtained.
^{1 1} H NMR (270 MHz, CDCl ₃ ) δ 7.26 (4H, d, J = 2.0 Hz, Ar-H), 6.54 (0.66 H, t, J = 2.9 Hz, Cp-H), 6.48 (1.33H, t, J = 2.9Hz, Cp-H), 6.40 (1.33H, t, J = 2.4Hz, Cp-H), 6.34 (0.66H, t, J = 2.4Hz, Cp-H), 5.79 (0.66H, t, J = 2.6Hz, Cp-H), 5.59 (1.33H, t, J = 2.8Hz, Cp-H), 3.43 (4H, sep, J = 6.8Hz, -CH (CH ₃ ) ₂ ), 2.84 (12H, s, -NC (CH ₃ ) ₂ ), 1.87 (2H) , S, Cp-CH ₃ ), 1.79 (4H, s, Cp-CH ₃ ), 1.23 (24H, dd, J = 1.4and 6.9Hz, -CH (CH ₃ ) ₂ ) ppm
FD-Mass Spectrometry (M ⁺ ): 726

[Comparative Example 1]
Bis (2-methyl-4-phenylcyclopentadienyl) zirconium dichloride (metallocene compound (2)) was synthesized by the method described in JP-A-2000-136195.

[Example 2]
(Example 2-1) Synthesis of compound (3a) 1.34 g (4.74 mmol) of compound (1a) obtained in Example 1-1 and 15 mL of tetrahydrofuran were placed in a 100 mL reactor sufficiently dried and substituted with argon. Was charged and stirred. To this solution under ice cooling, 2.92 mL of n-butyllithium solution (hexane solution, 1.63M, 4.76 mmol) was added to this solution, and the mixture was stirred at room temperature for 2 hours. After adding 0.45 mL (4.79 mmol) of 1,3-dimethyl-2-imidazolidinone to this solution, cool to -30 ° C, add 0.29 mL (2.43 mmol) of dichlorodimethylsilane, and slowly bring it to room temperature. Stirring was continued for 20 hours while returning to. A saturated aqueous solution of ammonium chloride was added, the soluble component was extracted with n-hexane, and the obtained fraction was washed with saturated brine and dried over anhydrous magnesium sulfate. After filtering magnesium sulfate, the filtrate was distilled off and the obtained residue was purified by silica gel column chromatography to find 0.59 g (hereinafter referred to as compound (3a)) of the target product represented by the following formula (3a) (hereinafter referred to as compound (3a)). It was obtained as a mixture of isomers (yield 40%).
^{1 1} H NMR (270 MHz, CDCl ₃ ) δ 7.41-5.86 (8H, m, Ar-H & -CH = C-), 3.80-3.01 (6H, m, -CH _2- &-) CH (CH ₃ ) ₂ ), 3.00-2.70 (12H, m, -NC (CH ₃ ) ₂ ), 2.35-1.76 (6H, m, C-CH ₃ ), 1.64 -1.40 (3H, m, Si-CH ₃ ), 1.38-1.05 (24H, d, J = 6.9Hz, -CH (CH ₃ ) ₂ ), 0.50-0.80 (3H, m, Si-CH ₃ ) ppm

(Example 2-2) Synthesis of metallocene compound (3) 0.58 g (0.93 mmol) of the compound (3a) obtained in Example 2-1 and toluene were placed in a 100 mL reactor sufficiently dried and substituted with argon. 10 mL and 0.2 mL of tetrahydrofuran were charged and stirred. To this solution, 1.20 mL of an n-butyllithium solution (hexane solution, 1.63 M, 1.96 mmol) was added at room temperature, and then stirring was continued for 3 hours in an oil bath at 40 ° C. After distilling off the solvent of the reaction solution, 10 mL of diethyl ether was added to the obtained solid. The solution was cooled to 0 ° C., 0.21 g (0.92 mmol) of zirconium tetrachloride was added, and stirring was continued at room temperature for 17 hours. After distilling off the solvent of the reaction solution, dichloromethane was added to the obtained solid to prepare a suspension, and the insoluble matter was removed with a membrane syringe filter. The obtained solution was concentrated under reduced pressure, the suspension was prepared by adding n-hexane, and the insoluble material was filtered off by a glass filter.

By drying the residue under reduced pressure, the white powdery compound dimethylsilylenebis (4- (3,5-di-iso-propyl-N, N-dimethylaminophenyl) -2-methyl represented by the following formula (3)) is obtained. 0.05 g (yield 6%, meso-form purity 87%) of cyclopentadienyl) zirconium dichloride (hereinafter referred to as metallocene compound (3)) was obtained (the obtained metallocene compound (3) is hereinafter referred to as metallocene compound (3 m)). ).

After the filtrate is concentrated under reduced pressure, the suspension is prepared by adding n-hexane, the insoluble material is filtered off with a glass filter, and the residue is dried under reduced pressure to obtain 0.01 g of the metallocene compound (3). (Yield 2%, racemic purity 85%) was obtained (the obtained metallocene compound (3) is hereinafter referred to as metallocene compound (3r)).
^{1 1} H NMR (270 MHz, CDCl ₃ ) [meso-] δ 6.90 (4H, d, J = 2.1 Hz, Ar-H), 6.67 (2H, d, J = 2.3 Hz, Cp-H) ), 5.82 (2H, d, J = 2.4Hz, Cp-H), 3.27 (4H, sep, J = 6.9Hz, -CH (CH ₃ ) ₂ ), 2.79 (12H, 12H, s, -NC (CH ₃ ) ₂ ), 2.31 (6H, s, Cp-CH ₃ ), 1.16 (24H, dd, J = 4.8 and 6.9Hz, -CH (CH ₃ ) ₂ ), 0.97 (3H, s, Si-CH ₃ ), 0.85 (3H, s, Si-CH ₃ ) ppm, [rac-] δ 7.26 (4H, s, Ar-H), 6.90 (2H, d, J = 2.3Hz, Cp-H), 5.76 (2H, d, J = 2.4Hz, Cp-H), 3.32 (4H, sep, J = 6.9Hz,- CH (CH ₃ ) ₂ ), 2.83 (12H, s, -NC (CH ₃ ) ₂ ), 2.22 (6H, s, Cp-CH ₃ ), 1.21 (24H, t, J = 6) .8Hz, -CH (CH ₃ ) ₂ ), 0.89 (6H, s, Si-CH ₃ ) ppm
FD-Mass Spectrometry (M ⁺ ): 782

[Comparative Example 2]
Dimethylsilylenebis (2,4-dimethylcyclopentadienyl) zirconium dichloride (metallocene compound (4)) was synthesized by the method described in JP-A-03-012406.

[Example 3]
<(2) Preparation of solid carrier>
Using a reactor with an internal volume of 270 L, silica gel (manufactured by Fuji Silysia Chemical Ltd .: cumulative 50% particle size 70 μm, specific surface area 340 m2 / g, pore volume 1) .3 cm3 / g, dried at 250 ° C. for 10 hours) 10 kg was suspended in 77 L of toluene and then cooled to 0-5 ° C. To this suspension, 19.4 liters of a toluene solution of methylaluminoxane (3.5 mol / L in terms of Al atoms) was added dropwise over 30 minutes. At this time, the temperature inside the system was kept at 0 to 5 ° C.

Then, after contacting at 0 to 5 ° C. for 30 minutes, the temperature inside the system was raised to 95 ° C. over 1.5 hours, and then contacting was continued at 95 ° C. for 4 hours. Then, the temperature was lowered to room temperature, the supernatant was removed by decantation, and the mixture was washed twice with toluene to prepare a toluene slurry of a solid carrier having a total volume of 115 liters.
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>
30 mL of toluene and 8.2 mL of the above solid-state carrier slurry (solid weight: 1.0 g) were charged into a reactor with a stirrer having an internal volume of 200 mL that was sufficiently nitrogen-substituted. Next, a 0.025 mmol toluene solution of the metallocene compound (1) obtained in Example 1-2 was added, and the mixture was contacted at an in-system temperature of 20 to 25 ° C. for 1 hour, and then the supernatant was removed by decantation. After washing twice with heptane, a total volume of 50 ml of the solid catalyst component slurry (I) for olefin polymerization was prepared.

[Comparative Example 3]
A solid catalyst component slurry (II) for olefin polymerization was prepared in the same manner as in Example 3 except that the metallocene compound (2) obtained in Comparative Example 1 was added instead of the metallocene compound (1).

[Example 4]
A solid catalyst component slurry (III) for olefin polymerization was prepared in the same manner as in Example 3 except that the metallocene compound (3r) obtained in Example 2-2 was added in place of the metallocene compound (1). ..

[Example 5]
A solid catalyst component slurry (IV) for olefin polymerization was prepared in the same manner as in Example 3 except that the metallocene compound (3 m) obtained in Example 2-2 was added in place of the metallocene compound (1). ..

[Comparative Example 4]
A solid catalyst component slurry (V) for olefin polymerization was prepared in the same manner as in Example 3 except that the metallocene compound (4) obtained in Comparative Example 2 was added instead of the metallocene compound (1).

<(4) Olefin polymerization>
[Example 6]
After charging 500 mL of heptane into a fully nitrogen-substituted stainless autoclave having an internal volume of 1 L and replacing the inside of the system with ethylene, 20 mL of 1-hexene, 0.375 mmol of triisobutylaluminum and the solid obtained in Example 3 above. 90 mg of the catalyst component slurry (I) was added as a solid content, and the temperature in the system was raised to 80 ° C. Next, by continuously introducing ethylene, a polymerization reaction was carried out under the conditions of a total pressure of 0.8 MPaG and 80 ° C. for 20 minutes. The polymer was recovered by filtration and dried at 80 ° C. for 10 hours under reduced pressure to obtain 50.2 g of an ethylene polymer. The polymerization activity was 68687.2 g-PE / mmol-Zr. It was h.

The density of the obtained polymer was 910 kg / m ³ , the 1-hexene content was 2.1 mol%, the weight average molecular weight (Mw) was 537,300, and the number average molecular weight (Mn) was 123,100. It was.

[Comparative Example 5]
The polymerization reaction was carried out in the same manner as in Example 6 except that 40 mg of the solid catalyst component slurry (II) obtained in Comparative Example 3 was added instead of the solid catalyst component slurry (I). The obtained ethylene polymer weighed 87.8 g, and the polymerization activity was 59775.1 g-PE / mmol-Zr. It was h.

The density of the obtained polymer was 912 kg / m ³ , the 1-hexene content was 1.6 mol%, the weight average molecular weight (Mw) was 424,300, and the number average molecular weight (Mn) was 170,300. It was.

[Example 7]
Instead of the solid catalyst component slurry (I), 80 mg of the solid catalyst component slurry (III) obtained in Example 4 was added as a solid content, and 10 mL of 1-hexene was added, in the same manner as in Example 6. A polymerization reaction was carried out. The obtained ethylene polymer weighed 59.6 g, and the polymerization activity was 20432.0 g-PE / mmol-Zr. It was h.

The density of the obtained polymer was 910 kg / m ³ , the 1-hexene content was 5.1 mol%, the weight average molecular weight (Mw) was 125,400, and the number average molecular weight (Mn) was 38,800. It was.

[Example 8]
Instead of the solid catalyst component slurry (I), 160 mg of the solid catalyst component slurry (IV) obtained in Example 5 was added as a solid content, and 10 mL of 1-hexene was added, in the same manner as in Example 6. A polymerization reaction was carried out. The obtained ethylene polymer weighed 70.6 g and had a polymerization activity of 27213.7 g-PE / mmol-Zr. It was h.

The density of the obtained polymer was 919 kg / m ³ , the 1-hexene content was 3.9 mol%, the weight average molecular weight (Mw) was 92,900, and the number average molecular weight (Mn) was 18,400. It was.

[Comparative Example 6]
Instead of the solid catalyst component slurry (I), 20 mg of the solid catalyst component slurry (V) obtained in Comparative Example 4 was added as a solid content, and 10 mL of 1-hexene was added, in the same manner as in Example 6. A polymerization reaction was carried out. The obtained ethylene polymer weighed 33.6 g, and the polymerization activity was 733333.3 g-PE / mmol-Zr. It was h.

The density of the obtained polymer was 926 kg / m ³ , the 1-hexene content was 1.8 mol%, the weight average molecular weight (Mw) was 152,900, and the number average molecular weight (Mn) was 46,700. It was.
The above results of Examples 6 to 8 and Comparative Examples 5 and 6 are summarized in [Table 10].

Comparison with Comparative Example 5 using the known metallocene compound (2) described in Comparative Example 1 and implementation using the metallocene compound (1) described in Example 1-2, which is the scope of the present patent. In Example 6, an improvement in 1-hexene copolymerization was observed.

Further, in comparison with Comparative Example 6 using the known metallocene compound (4) described in Comparative Example 2, the metallocene compound (3) described in Example 2-2, which is the scope of the present patent, is used. In Examples 7 and 8 as well, improvement in 1-hexene copolymerization was observed. In particular, in Example 7 using the racemic excess metallocene compound (3r), the tendency was remarkable.

By using a catalyst for olefin polymerization containing a novel transition metal compound having a specific substituent according to the present invention, an olefin polymer having a sufficient molecular weight when copolymerization of ethylene and α-olefin is carried out. Can be produced and exhibits particularly excellent α-olefin copolymerizability. According to the present invention, it is expected that a polyolefin having an excellent balance of impact resistance, light weight and transparency, which makes the best use of these characteristics, can be provided with high productivity. Therefore, it can be said that the present invention has extremely high industrial value.

Claims (5)

Among the transition metal compounds represented by the following general formula [1] or general formula [2],
Bis (1- (3,5-di-lower alkyl-N, N-di lower alkylaminophenyl) -3-methylcyclopentadienyl) zirconium dihalide or di-lower alkyl silylenebis (4- (3,5-) Di-lower alkyl-N, N-di lower alkylaminophenyl) -2-methylcyclopentadienyl) zirconium dihalide,
The lower alkyl is a transition metal compound [A] selected from a methyl group, an ethyl group, a 1-propyl group, a 1-butyl group, an iso-propyl group, a sec-butyl group, a tert-butyl group and an iso-butyl group.

(In the general formulas [1] and [2],
M is a Group 4 transition metal atom of the periodic table.
n is an integer of 1 to 4 that satisfies the valence of M.
X is a neutral ligand capable of coordinating with a hydrogen atom, a halogen atom, a hydrocarbon group, an anion ligand or an isolated electron pair, and the anion ligand is a halogen-containing group, a silicon-containing group, or oxygen. It is a containing group, a sulfur-containing group, a nitrogen-containing group, a phosphorus-containing group, a boron-containing group, an aluminum-containing group or a conjugated diene-based divalent derivative group. They may be the same or different from each other, or they may be combined with each other to form a ring.
R ^{1 to} R ¹⁰ are independently hydrogen atoms, hydrocarbon groups having 1 to 40 carbon atoms, halogen-containing groups, silicon-containing groups, oxygen-containing groups, nitrogen-containing groups or sulfur-containing groups, and they are the same or different. Adjacent substituents R ^{1 to} R ⁵ and R ^{6 to} R ¹⁰ may be bonded to each other to form a ring, provided that at least one of ^{R 1 to} R ^{10 is} It is a substituent represented by the following general formula [3], and when there are a plurality of substituents, they may be the same or different.

(In the general formula [3],
R ¹¹ and R ¹² are independently hydrogen atoms or hydrocarbon groups having 1 to 20 carbon atoms, and may be the same or different from each other.
R ¹³ and R ¹⁴ are each independently a hydrocarbon group having 1 to 20 carbon atoms, an aromatic hydrocarbon group or a silicon-containing group having 6 to 40 carbon atoms which may each be the same or different, R ¹³ And R ¹¹ , R ¹⁴ and R ¹² may combine with each other to form a ring.
Z is an atom selected from nitrogen, oxygen or sulfur,
m is an integer of 1 or 2 that satisfies the valence of Z.
R ¹⁵ 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 is selected from ^{R 13} and R ^14. It may be bonded to at least one of the above to form a ring which may have a substituent, and when m is 2, they may be the same or different from ^{each other, and R 15s} may be bonded to each other to form a substituent. May form a ring which may have. )))
(In the general formula [2],
Q is a divalent hydrocarbon group, a divalent silicon-containing group or a divalent germanium-containing group, which is bonded to each other and at least one selected from ^{R 1} , R ⁴ , R ⁶ and R ^{9, respectively.} It may form a ring which may have a substituent independently. ) A catalyst for olefin polymerization, which comprises the transition metal compound [A] according to claim 1. Furthermore, [B] (B-1) organometallic compounds,
It is characterized by containing at least one compound selected from the group consisting of (B-2) an organoaluminum oxy compound and (B-3) a compound which reacts with a transition metal compound [A] to form an ion pair. The catalyst for olefin polymerization according to claim 2. A method for producing an olefin polymer, which comprises a step of polymerizing an olefin in the presence of the catalyst for olefin polymerization according to claim 2 or 3. The method for producing an olefin polymer according to claim 4, wherein the polymerization of the olefin is homopolymerization of ethylene or copolymerization of ethylene and an α-olefin having 3 or more and 20 or less carbon atoms.