JP6987494B2 - Method for Producing Catalyst for Olefin Polymerization and Ethylene Polymer - Google Patents

Description

The present invention relates to a catalyst for olefin polymerization and a method for producing an ethylene polymer.

Olefin polymers are molded by various molding methods and are used in various applications. For example, an extrusion-molded ethylene-based polymer is used for films and sheets used for packaging foods, liquids, daily miscellaneous goods, and the like.

The properties required for the olefin polymer differ depending on the molding method and application, but for example, when T-die molding is performed, stable molding is possible even at high speed (having high-speed film forming processability). That is, it is required to have processing performance such as a small neck-in. Further, when performing inflation molding, it is required to have processing performance such as excellent bubble stability.

On the other hand, the ethylene-based polymer obtained by using a Ziegler catalyst or a metallocene catalyst has a linear molecular structure and is excellent in mechanical strength, but has a small melt tension and is a low-density polyethylene produced by high-pressure radical polymerization. It has a problem that the molding processability is lower than that of (LDPE). As a method for solving the problem, [1] a method of blending LDPE with an ethylene-based polymer obtained by using a Cheegler catalyst or a metallocene catalyst (Patent Document 1), and [2] a method of expanding the molecular weight distribution by multistage polymerization. (Patent Document 2), [3] A method for producing a long-chain branched ethylene-based polymer using a chromium catalyst, and [4] Producing a long-chain branched ethylene-based polymer using a specific metallocene catalyst. Method (Patent Document 3), [5] Method for producing a long-chain branched ethylene polymer by copolymerizing a macromonomer using a specific metallocene catalyst (Patent Document 4), [6] Using a specific metallocene catalyst. A method for producing a long-chain branched ethylene-based polymer by copolymerizing ethylene and diene using the polymer (Patent Documents 5 and 6) has been proposed. However, these methods still have problems in industrial implementation, such as significant cost increase, insufficient molding processability, and gel generation during molding.

Further, in recent years, a method for producing an ethylene polymer having a wide molecular weight distribution and a long chain branch by an adjacent double crosslinked metallocene complex (Patent Documents 7 and 8) has been disclosed.

International Publication No. 99/46325 Japanese Unexamined Patent Publication No. 2-53811 Japanese Unexamined Patent Publication No. 4-213306 Japanese Patent Publication No. 8-502303 Special Table 1-501633 Gazette Special Table No. 4-506372 Gazette Japanese Patent Application Laid-Open No. 2003-105016 Japanese Unexamined Patent Publication No. 8-20605

However, the methods described in Patent Documents 7 and 8 have not obtained sufficient molding processability and polymerization activity, and further improvement is desired. An object of the present invention is to provide a catalyst for olefin polymerization capable of producing an olefin-based polymer having high polymerization activity and excellent molding processability.

The present invention is the following [1] to [7].

[1] A catalyst for olefin polymerization containing the following component (A), the following component (B), and the following component (C).

Component (A); Cross-linked metallocene compound represented by the following formula (I)

(In formula (I), R ^{1 to} R ⁸ are monovalent groups, each independently a hydrogen atom or a hydrocarbon group , which may be the same or different from each other, but at least R ^{1 to} R ⁸ one is a hydrocarbon group having 3 to 8 carbon atoms, .Q ¹ remainder is a hydrocarbon group or a hydrogen atom is a divalent group, a hydrocarbon group, a halogen-containing group having 1 to 20 carbon atoms, a silicon It is a containing group, a germanium-containing group or a tin-containing group. X is a monovalent group and independently contains a hydrogen atom, a halogen atom, a hydrocarbon group, a halogen-containing group, a silicon-containing group, an oxygen-containing group and a sulfur-containing group. A group, a nitrogen-containing group or a phosphorus-containing group, which may be the same or different from each other. M is a titanium atom, a zirconium atom or a hafnium atom.)
Component (B); Double crosslinked metallocene compound represented by the following formula (II)

In formula (II), R ⁹ to R ¹² and R ¹⁴ are monovalent groups, each independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R ¹³ is a monovalent group. There, a hydrogen atom or an alkyl group having 4 to 8 carbon atoms, it may also be the same or different ^bur, all R 9 ^{to R 11} are not simultaneously hydrogen ^atoms, all R 12 ^{to R 14} simultaneously Adjacent groups of R ^{9 to} R ¹¹ may be bonded to each other to form a ring instead of a hydrogen atom. ^{Q 2} and Q ³ are divalent groups and are independently silicon-containing groups . , They may be the same or different from each other, or they may be bonded to each other to form a ring. X is a monovalent group, and each of them independently has a hydrogen atom, a halogen atom, a hydrocarbon group, and an anion ligand. , Or a neutral ligand that can be coordinated with an isolated electron pair. The anionic ligand is a halogen-containing group, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a phosphorus-containing group, or boron. It is a containing group, an aluminum-containing group or a conjugated diene-based divalent derivative group. X may be the same as or different from each other. M is a titanium atom, a zirconium atom or a hafnium atom.)
Component (C); (c-1) an organometallic compound represented by the following formula (III), (IV) or (V), (c-2) organoaluminum oxy compound, and (c-3) the component (c-3). a) or the component (B) at least one compound reacted with a compound to form an ion pair is selected from the group consisting of _{^{R a m Al (oR b)}} n H p X q (III)
(In formula (III), ^Ra and R ^b represent hydrocarbon groups having 1 to 15 carbon atoms, which may be the same or different from each other. X represents a halogen atom. M is 0 <m ≦ 3, n satisfies 0 ≦ n <3, p satisfies 0 ≦ p <3, q satisfies 0 ≦ q <3, and m + n + p + q = 3).
M ^a AlR ^a ₄ (IV)
(In the formula (IV), ^{M a} is Li, .R ^a indicating the Na or K represents a hydrogen atom or a hydrocarbon group having 1 to 15 carbon atoms.)
R ^a _r M ^b R ^b _s X _t (V)
(In the formula (V), ^Ra and R ^b represent hydrocarbon groups having 1 to 15 carbon atoms, which may be the same or different from each other. M ^b is Mg, Zn or Cd. X is a halogen. Indicates an atom. R is 0 <r ≦ 2, s is 0 ≦ s ≦ 1, t is 0 ≦ t ≦ 1, and r + s + t = 2).

[2] The catalyst for olefin polymerization according to [1], which further comprises a solid carrier (S).

[3] The catalyst for olefin polymerization according to [2], wherein the component (A), the component (B) and the component (C) contain a solid catalyst component supported on the solid carrier (S).

[4] The solid catalyst component in which the component (C) and the component (A) are supported on the solid carrier (S), and the solid carrier (S) in which the component (C) and the component (B) are supported. ), The catalyst for olefin polymerization according to [2].

[5] The catalyst for olefin polymerization according to any one of [2] to [4], wherein the solid carrier (S) is a porous oxide.

[6] The catalyst for olefin polymerization according to any one of [1] to [5], wherein the component (C) is the organoaluminum oxy compound (c-2).

[7] A method for producing an ethylene-based polymer in which ethylene alone or ethylene and an olefin having 3 to 20 carbon atoms are polymerized in the presence of the catalyst for olefin polymerization according to any one of [1] to [6].

According to the present invention, it is possible to provide a catalyst for olefin polymerization capable of producing an olefin-based polymer having high polymerization activity and excellent molding processability.

[Catalyst for olefin polymerization]
The catalyst for olefin polymerization according to the present invention contains the component (A), the component (B), and the component (C). Since the olefin polymerization catalyst according to the present invention contains the components (A) to (C), an olefin polymer having a large number of long-chain branches with high catalytic activity, particularly an ethylene-based polymer, is efficiently used in the polymerization of olefins. It is presumed that it can be manufactured well. The olefin polymer having many long-chain branches has high fluidity and excellent molding processability. When the catalyst for olefin polymerization does not contain the component (A), the number of long-chain branches of the obtained olefin polymer is reduced. On the other hand, when the catalyst for olefin polymerization does not contain the component (B), the catalytic activity is lowered.

In the present invention, the term "polymerization" may be used to include not only homopolymerization of olefins but also copolymerization of two or more kinds of olefins. Further, the term "polymer" may be used to include not only a homopolymer but also a copolymer.

(Ingredient (A))
The component (A) is a crosslinked metallocene compound represented by the following formula (I).

In the formula (I), R ^{1 to} R ⁸ are monovalent groups, and each of them independently has a hydrogen atom, a hydrocarbon group, a halogen-containing group, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, and a sulfur-containing group. They are phosphorus-containing groups, silicon-containing groups, germanium-containing groups or tin-containing groups, which may be the same or different from each other, but they are not all hydrogen atoms at the same time, and adjacent groups are bonded to each other to form a ring. May be good.

The monovalent hydrocarbon group includes an alkyl group consisting of carbon and hydrogen having 1 to 20 carbon atoms, a cycloalkyl group consisting of carbon and hydrogen having 3 to 20 carbon atoms, and an alkenyl consisting of carbon and hydrogen having 2 to 20 carbon atoms. A group, an aryl group composed of carbon and hydrogen having 6 to 20 carbon atoms, and an arylalkyl group composed of carbon and hydrogen having 7 to 20 carbon atoms are preferable. Examples of the alkyl group composed of carbon having 1 to 20 carbon atoms and hydrogen include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, an s-butyl group and a t-butyl group. , N-pentyl group, neopentyl group, n-hexyl group, n-octyl group, nonyl group, dodecyl group, icosyl (icosyl) group and the like. Examples of the cycloalkyl group composed of carbon having 3 to 20 carbon atoms and hydrogen include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a norbornyl group, and an adamantyl group. Examples of the alkenyl group composed of carbon having 2 to 20 carbon atoms and hydrogen include a vinyl group, a propenyl group, a cyclohexenyl group and the like. Examples of the aryl group composed of carbon and hydrogen having 6 to 20 carbon atoms include a phenyl group, a trill group, a dimethylphenyl group, a trimethylphenyl group, an ethylphenyl group, a propylphenyl group, a biphenyl group, α- or β-naphthyl. Examples thereof include a group, a methylnaphthyl group, an anthrasenyl group, a phenanthryl group, a benzylphenyl group, a pyrenyl group, an acenaphthyl group, a phenalenyl group, an aceanthrylenyl group, a tetrahydronaphthyl group, an indanyl group and a biphenylyl group. Examples of the arylalkyl group composed of carbon having 7 to 20 carbon atoms and hydrogen include a benzyl group, a phenylethyl group, and a phenylpropyl group. Among these, an alkyl group composed of carbon and hydrogen having 3 to 20 carbon atoms is preferable, and an alkyl group composed of carbon and hydrogen having 3 to 8 carbon atoms is more preferable.

Examples of the monovalent halogen-containing group include a halogen atom and a group in which one or more hydrogen atoms in the monovalent hydrocarbon group are substituted with a halogen atom, for example, a trifluoromethyl group.

Examples of the monovalent oxygen-containing group include a methoxy group and an ethoxy group.

Examples of the monovalent nitrogen-containing group include a dimethylamino group.

Examples of the monovalent boron-containing group include a bolangyl group, a bolantriyl group, and a diboranyl group.

Examples of the monovalent sulfur-containing group include a thiol group and a sulfonic acid group.

Examples of the monovalent phosphorus-containing group include a phenylphosphine group.

The monovalent silicon-containing group includes a silyl group, a methylsilyl group, a dimethylsilyl group, a diisopropylsilyl group, a methyl-t-butylsilyl group, a dicyclohexylsilyl group, a methylcyclohexylsilyl group, a methylphenylsilyl group, a diphenylsilyl group, and a methylnaphthyl. Examples thereof include a silyl group, a dinaphthyl silyl group, a cyclodimethylene silyl group, a cyclotrimethylene silyl group, a cyclotetramethylene silyl group, a cyclopentamethylene silyl group, a cyclohexamethylene silyl group and a cycloheptamethylene silyl group.

Examples of the monovalent germanium-containing group and the monovalent tin-containing group include a group obtained by converting silicon into germanium or tin in the monovalent silicon-containing group.

Examples of cases where adjacent groups are bonded to each other to form a ring include a tetrahydroindenyl group, a 2-methyltetrahydroindenyl group, a 2,2,4-trimethyltetrahydroindenyl group and a 4-phenyltetrahydroindenyl group. , 4-Cyclohexyltetrahydroindenyl group, 2-methyl-4-phenyltetrahydroindenyl group, 2-methyl-4-cyclohexyltetrahydroindenyl group and the like. The ring can be an aliphatic ring.

R ^{1 to} R ⁸ are preferably hydrogen atoms, hydrocarbon groups or halogen-containing groups, more preferably ^{at least one of R 1 to} R ⁸ is a hydrocarbon group, and even more preferably R ¹ to R 8. At ^{least one of R 8} is a hydrocarbon group having 1 to 15 carbon atoms, the rest is a hydrocarbon group or a hydrogen atom, and most preferably ^{at least one of R 1 to} R ⁸ is a hydrocarbon having 3 to 8 carbon atoms. It is a group and the rest are hydrocarbon groups or hydrogen atoms. As the hydrocarbon group, an alkyl group is preferable, and a linear alkyl group is more preferable.

In the formula (I), Q ¹ is a divalent group, which is a hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing group, a silicon-containing group, a germanium-containing group or a tin-containing group.

Examples of the divalent hydrocarbon group having 1 to 20 carbon atoms include an alkylene group having 1 to 20 carbon atoms, a substituted alkylene group, a cycloalkylene group and an alkylidene group. Examples of the alkylene group having 1 to 20 carbon atoms include a methylene group, an ethylene group, a propylene group and a butylene group. Substituted alkylene groups having 1 to 20 carbon atoms include isopropyridene group, dimethylmethylene group, diethylmethylene group, dipropylmethylene group, diisopropylmethylene group, dibutylmethylene group, methylethylmethylene group, methylbutylmethylene group, and methyl-t. -Butylmethylene group, dihexylmethylene group, dicyclohexylmethylene group, methylcyclohexylmethylene group, methylphenylmethylene group, diphenylmethylene group, ditrilmethylene group, methylnaphthylmethylene group, dinaphthylmethylene group, 1-methylethylene group, 1, Examples thereof include 2-dimethylethylene group and 1-ethyl-2-methylethylene group. Examples of the cycloalkylene group having 1 to 20 carbon atoms include a cyclopropyridene group, a cyclobutylidene group, a cyclopentylidene group, a cyclohexylidene group, a cycloheptylidene group, a bicyclo [33.1] nonylidene group, and a norbornylidene. Examples thereof include a group, an adamantylidene group, a tetrahydronaphthylidene group, a dihydroindanylidene group and the like. Examples of the alkylidene group having 1 to 20 carbon atoms include an ethylidene group, a propylidene group, and a butylidene group.

Examples of the divalent silicon-containing group include a sylylene group, a methylsylylene group, a dimethylsylylene group, a diisopropylsylylene group, a dibutylsylylene group, a methylbutylsylylene group, a methyl-t-butylsylylene group, a dicyclohexylsilylene group and a methylcyclohexylsilylene group. Methylphenylsilylene group, diphenylcyrylene group, ditrilcilylene group, methylnaphthyltylylene group, dinaphthyltylylene group, cyclodimethylenecyrylene group, cyclotrimethylenecyrylene group, cyclotetramethylenecilylene group, cyclopentamethylenetylylene group, cyclohexa Examples thereof include a methylene silylene group and a cycloheptamethylene silylene group. Preferably, it is a dimethylsilylene group, a dibutylcilylene group, or a diphenylcilylene group.

Examples of the divalent halogen-containing group include a divalent hydrocarbon group and a group in which one or more hydrogen atoms in the divalent silicon-containing group are substituted with a halogen atom. For example, a bis (trifluoromethyl) methylene group, a 4,4,4-trifluorobutylmethyl methylene group, a bis (trifluoromethyl) silylene group, a 4,4,4-trifluorobutylmethylcilylene group and the like can be mentioned.

Examples of the divalent germanium-containing group and the divalent tin-containing group include a group obtained by converting silicon into germanium or tin in the divalent silicon-containing group.

The Q ^1, preferably, an alkylene group having 1 to 20 carbon atoms, a substituted alkylene group, a cycloalkylene group, an alkylidene group, a halogen-containing alkylene groups, halogen-containing substituted alkylene groups, halogen-containing cycloalkylene group, a halogen-containing alkylidene groups, It is a silicon-containing group or a halogen-containing silicon-containing group, more preferably a silicon-containing group or a halogen-containing silicon-containing group, still more preferably a silicon-containing group, and particularly preferably a dialkylsilylene group.

In formula (I), X is a monovalent group, which is independently a hydrogen atom, a halogen atom, a hydrocarbon group, a halogen-containing group, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group or phosphorus. It is a containing group and may be the same or different from each other.

Examples of the halogen atom include fluorine, chlorine, bromine and iodine. The hydrocarbon group, halogen-containing group, silicon-containing group, oxygen-containing group, sulfur-containing group, nitrogen-containing group and phosphorus-containing group are the same as those exemplified as ^{R 1 to} R ^{8 of the above formula (I).} Can be mentioned. X is preferably a halogen atom or a hydrocarbon group, and more preferably a halogen atom.

In formula (I), M is a titanium atom, a zirconium atom or a hafnium atom, preferably a zirconium atom.

The method for producing the crosslinked metallocene compound represented by the formula (I) is not particularly limited, and is described in, for example, JP-A-2006-233208, JP-A-2009-143901, JP-A-2009-144148 and the like. There are several methods.

In the present invention, the crosslinked metallocene compound represented by the formula (I) may be used alone, or two or more kinds of the crosslinked metallocene compound represented by the formula (I) having different chemical structures may be used. .. Further, the optical isomers having the same chemical structure may be used alone, or an optical isomer mixture having the same chemical structure (for example, a meso-form mixture or a racemic mixture) may be used.

(Component (B))
The component (B) is a double crosslinked metallocene compound represented by the following formula (II).

In formula (II), R ^{9 to} R ¹⁴ are monovalent groups, which are independently hydrogen atoms or hydrocarbon groups having 1 to 20 carbon atoms, and may be the same or different from each other, and are adjacent groups. May be coupled to each other to form a ring.

The monovalent hydrocarbon group having 1 to 20 carbon atoms includes an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, and an aryl having 6 to 20 carbon atoms. Examples thereof include an arylalkyl group having 7 to 20 carbon atoms.

Examples of the alkyl group having 1 to 20 carbon atoms include 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 a 1-octyl group. 1-nonyl group, 1-decanyl group, 1-undecanyl group, 1-dodecanyl group, 1-eicosanyl, iso-propyl group, sec-butyl group (butane-2-yl group), tert-butyl group (2-methyl) Propyl-2-yl group), iso-butyl group (2-methylpropyl group), pentan-2-yl group, 2-methylbutyl group, iso-pentyl group (3-methylbutyl), neopentyl group (2,2-dimethyl) Propyl group), tert-pentyl group (1,1-dimethylpropyl group), siamil group (1,2-dimethylpropyl group), pentan-3-yl group, 2-methylpentyl group, 3-methylpentyl group, iso -Hexyl group (4-methylpentyl group), 1,1-dimethylbutyl group (2-methylpentane-2-yl), 3-methylpentane-2-yl group, 4-methylpentane-2-yl group, 2 , 2-dimethylbutyl group, 2,3-dimethylbutyl group, 3,3-dimethylbutyl group, texyl group (2,3-dimethylbut-2-yl group), 3-methylpentane-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-ethyl Pentan-3-yl group, 4,4-dimethylpentyl group, 4-methylheptan-4-yl group, 4-propylheptan-4-yl group, 2,3,3-trimethylbutane-2-yl group, 2 , 3,4-trimethylpentane-3-yl group and the like.

Examples of the cycloalkyl group having 3 to 20 carbon atoms include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclopentenyl group, a cyclopentadienyl group, a dimethylcyclopentadienyl group and an n-butylcyclopentadienyl group. , N-butyl-methylcyclopentadienyl group, tetramethylcyclopentadienyl group, 1-methylcyclopentyl group, 1-allylcyclopentyl group, 1-benzylcyclopentyl group, cyclohexyl group, cyclohexenyl group, cyclohexadienyl 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, 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-Methyl adamantyl), 1- (4-methyl adamantyl), 1- (2-phenyl adamantyl), 1- (3-phenyl adamantyl), 1- (4-phenyl adamantyl), 1- (3,5-) Dimethyladamantyl), 1- (3,5,7-trimethyladamantyl), pentarenyl group, indenyl group, fluorenyl group, indasenyl group, tetrahydroindasenyl group, benzoindenyl group, azulenyl group and the like.

Examples of the alkenyl group having 2 to 20 carbon atoms include a vinyl group, an allyl group, a propenyl group (propa-1-en-1-yl group), an iso-propenyl group (propa-1-en-2-yl group), and the like. Allenyl group (proper-1,2-diene-1-yl group), porcine-3-en-1-yl group, crotyl group (but-2-en-1-yl group), porcine-3-en-2 -Il group, metalryl group (2-methylallyl group), erythrenyl group (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 group (3-methylbut-3-en-1-yl group), 2-methylbut-3-en-1-yl group, penta-4-en-2-yl Group, prenyl group (3-methyl-but-2-en-1-yl group), 2-methyl-but-2-en-1-yl group, penta-3-en-2-yl group, 2-methyl -Puta-3-en-2-yl group, penta-1-en-3-yl group, penta-2,4-dien-1-yl group, penta-1,3-dien-1-yl group, penta -1,4-dien-3-yl group, iso-prenyl group (2-methyl-buta-1,3-dien-1-yl group), penta-2,4-dien-2-yl group, hexa- 5-en-1-yl group, hexa-4-en-1-yl group, hexa-3-en-1-yl group, hexa-2-en-1-yl group, 4-methyl-penta-4- En-1-yl group, 3-methyl-penta-4-en-1-yl group, 2-methyl-penta-4-en-1-yl group, hexa-5-en-2-yl group, 4- Methyl-penta-3-ene-1-yl group, 3-methyl-pent-3-en-1-yl group, 2,3-dimethyl-but-2-en-1-yl group, 2-methylpenta-4 -En-2-yl group, 3-ethylpenta-1-ene-3-yl group, hexa-3,5-diene-1-yl group, hexa-2,4-dien-1-yl group, 4-methylpenta -1,3-diene-1-yl group, 2,3-dimethyl-buta-1,3-dien-1-yl group, hexa-1,3,5-triene-1-yl group, 2- (cyclo) Examples thereof include a pentadienyl) propan-2-yl group and a 2- (cyclopentadienyl) ethyl group.

The aryl group having 6 to 20 carbon atoms includes a phenyl group, a trill group (methylphenyl group), a xsilyl group (dimethylphenyl), a mesityl group (2,4,6-trimethylphenyl group), and a cumenyl group (iso-propyl). Phenyl group), Julyl group (2,3,5,6-tetramethylphenyl 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, meta Examples thereof include a rylphenyl group, a prenylphenyl group, a 4-adamantylphenyl group, a naphthyl group, a biphenyl group, a ter-phenyl group, a binaphthyl group, an acenaphthalenyl group, a phenanthryl group, an anthrasenyl group, a pyrenyl group and a ferrosenyl group.

Examples of the arylalkyl group having 7 to 20 carbon atoms include a benzyl group, a 2-methylbenzyl group, a 4-methylbenzyl group, a 2,4,6-trimethylbenzyl group, a 3,5-dimethylbenzyl group and a cumill group (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 group (Diphenylmethyl group), Kumil group (2-phenylpropan-2-yl group), 2- (4-methylphenyl) propan-2-yl group, 2- (3,5-dimethylphenyl) propan-2-yl Group, 2- (4-tert-butylphenyl) propan-2-yl group, 2- (3,5-di-tert-butylphenyl) propan-2-yl group, 3-phenylpentane-3-yl group, 4-Phenylhepta-1,6-dien-4-yl group, 1,1-diphenylethyl group, 1,1-diphenylpropyl group, 1,1-diphenyl-3-ene-1-yl group, 1 , 1,2-triphenylethyl group, trityl group (triphenylmethyl group), 2-phenylethyl group, styryl group (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-phenylpropan-2-yl group, 3- Phenylpropyl group, 2-cinnamyl group (3-phenylallyl group), neophil group (2-methyl-2-phenylpropyl group), 3-methyl-3-phenylbutyl group, 2-methyl-4-phenylbutane-2 -Il group, cyclopentadienyldiphenylmethyl group, 2- (1-indenyl) propan-2-yl group, 2- (1-indenyl) ethyl group, 2- (tetrahydro-1-indacenyl) propan-2-yl Group, 2- (tetrahydro-1-indacenyl) ethyl group, 2- (1-benzoindenyl) propan-2-yl group, 2- (1-benzoindenyl) ethyl group, 2- (9-fluorenyl) propane -2-yl group, 2- (9-fluorenyl) ethyl group, 2- (1-azurenyl) propan-2-yl group, 2- (1-azurenyl) ) Ethyl group and the like.

Among the alkyl 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 a 1-octyl group. , Iso-propyl group, sec-butyl group (butane-2-yl group), tert-butyl group (2-methylpropan-2-yl group), iso-butyl group (2-methylpropyl group), iso-pentyl Group (3-methylbutyl group), neopentyl group (2,2-dimethylpropyl group), tert-pentyl group (1,1-dimethylpropyl group), pentan-3-yl group, iso-hexyl group (4-methylpentyl group) Group), 1,1-dimethylbutyl group (2-methylpentane-2-yl group), 3,3-dimethylbutyl group, texyl group (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, more preferably methyl group, ethyl group, 1-propyl group, 1-butyl group, 1-pentyl group, 1-hexyl group, iso-propyl group, It is a tert-butyl (2-methylpropan-2-yl) group. The alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms.

Among the cycloalkyl groups having 3 to 20 carbon atoms, preferably, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclopentenyl group, a cyclopentadienyl group, a 1-methylcyclopentyl group, a 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, more preferably cyclopentyl group, cyclo It is a pentenyl group, a 1-methylcyclopentyl group, a cyclohexyl group, a cyclohexenyl group, a 1-methylcyclohexyl group and a 1-adamantyl group.

Among the alkenyl groups having 2 to 20 carbon atoms, preferable are a vinyl group, an allyl group, a but-3-en-1-yl group, a crotyl group (but-2-en-1-yl group), and a methallyl group (. 2-Methylallyl group), penta-4-en-1-yl group, prenyl group (3-methyl-but-2-en-1-yl group), penta-1,4-dien-3-yl group, hexa -5-En-1-yl group, 2-methylpenta-4-en-2-yl group, 2- (cyclopentadienyl) propan-2-yl group, 2- (cyclopentadienyl) ethyl group. , More preferably, a vinyl group, an allyl group, a buta-3-en-1-yl group, a penta-4-en-1-yl group, a prenyl group (3-methyl-but-2-en-1-yl group). ), Hexa-5-ene-1-yl group.

Among the aryl groups having 6 to 20 carbon atoms, phenyl group, trill group (methylphenyl group), xsilyl group (dimethylphenyl group), mesityl group (2,4,6-trimethylphenyl group) and cumenyl 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- Phenyl group, allylphenyl group, prenylphenyl group, 4-adamantylphenyl group, naphthyl group, biphenyl group, ter-phenyl group, binaphthyl group, phenanthryl group, anthrasenyl group, ferrosenyl group, more preferably phenyl group, Trill group (methylphenyl group), xsilyl group (dimethylphenyl group), mesityl group (2,4,6-trimethylphenyl group), cumenyl group (iso-propylphenyl group), 2,6-di-iso-propylphenyl Group, 2,4,6-tri-iso-propylphenyl group, 4-tert-butylphenyl group, 3,5-di-tert-butylphenyl group, allylphenyl group, 4-adamantylphenyl group, naphthyl group, biphenyl Group, phenyl group, anthrasenyl group.

Among the arylalkyl groups having 7 to 20 carbon atoms, benzyl group, 2-methylbenzyl group, 4-methylbenzyl group, 2,4,6-trimethylbenzyl group, 3,5-dimethylbenzyl group and cuminyl are preferable. Group (4-iso-propylbenzyl group), 2,4,6-tri-iso-propylbenzyl group, 4-tert-butylbenzyl group, 3,5-di-tert-butylbenzyl group, benzhydryl group (diphenylmethyl) Group), cumyl group (2-phenylpropan-2-yl group), 1,1-diphenylethyl group, trityl group (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 group (2-phenylvinyl group), 2-methyl-1-phenylpropan-2-yl Group, 3-phenylpropyl group, 2-cinnamyl group (3-phenylallyl group), neophil group (2-methyl-2-phenylpropyl group), cyclopentadienyldiphenylmethyl group, 2- (1-indenyl) propane -2-yl group, 2- (1-indenyl) ethyl group, 2- (9-fluorenyl) propan-2-yl group, 2- (9-fluorenyl) ethyl group, more preferably benzyl group, benzhydryl. Group (diphenylmethyl group), cumyl group (2-phenylpropan-2-yl group), 1,1-diphenylethyl group, trityl group (triphenylmethyl group), 2-phenylethyl group, 3-phenylpropyl group, It is a 2-cinnamyl group (3-phenylallyl group).

Of R ^{9 to} R ¹⁴ , when adjacent substituents are bonded to each other to form a ring, a saturated or unsaturated hydrocarbon group having a 5- to 8-membered ring fused to the cyclopentadienyl ring moiety and a saturated or unsaturated hydrocarbon group. A heterocycle may be formed. The ring is preferably a 5- or 6-membered ring. As a structure combined with the cyclopentadienyl moiety of the mother nucleus, for example, a substituted cyclopentapilol ring, a substituted cyclopentaindole ring, a substituted cyclopentathiophene ring, a substituted cyclopentabenzothiophene ring, a substituted inden ring, a substituted benzoinden ring, Examples thereof include a substituted tetrahydroindene ring, a substituted azulene ring, a substituted dihydroazulene ring, a substituted tetrahydroazulene ring, a substituted hexahydroazulene ring and the like, and a substituted inden ring and a substituted tetrahydroindene ring are preferable.

In formula (II), Q ² and Q ³ are divalent groups, which are independently hydrocarbon groups having 1 to 20 carbon atoms, halogen-containing groups, silicon-containing groups, germanium-containing groups or tin-containing groups. , They may be the same or different from each other, or they may be bonded to each other to form a ring.

Examples of the divalent hydrocarbon group having 1 to 20 carbon atoms include an alkylene group, a substituted alkylene group, a cycloalkylene group and an alkylidene group. Examples of the alkylene group include a methylene group, an ethylene group, a propylene group, a butylene group and the like. Substituted alkylene groups include isopropyridene group, dimethylmethylene group, diethylmethylene group, dipropylmethylene group, diisopropylmethylene group, dibutylmethylene group, methylethylmethylene group, methylbutylmethylene group, methylbuta-3-emethylene group, and methyl-. t-butylmethylene group, dihexylmethylene group, dicyclohexylmethylene group, methylcyclohexylmethylene group, methylphenylmethylene group, phenylmethylene group, phenylbut-3-emethylene group, diphenylmethylene group, ditrilmethylene group, methylnaphthylmethylene group, Examples thereof include dinaphthylmethylene group, benzylphenylmethylene group, dibenzylmethylene group, 1-methylethylene group, 1,2-dimethylethylene group and 1-ethyl-2-methylethylene group. Examples of the cycloalkylene group include a cyclopropanolene group, a cyclobutylidene group, a cyclopentylidene group, a cyclohexylidene group, a cycloheptylidene group, a bicyclo [3.3.1] nonylidene group, a norbornylidene group, and an adamantylidene group. , Tetrahydronaphthylidene group, dihydroindanylidene group and the like. Examples of the alkylidene group include an ethylidene group, a propylidene group and a butylidene group.

The divalent silicon-containing group includes a silylene group, a methylsilylene group, a dimethylsilylene group, a diethylsilylene group, a diisopropylsilylene group, a dibutylsilylene group, a methylbutylsilylene group, a methyl-t-butylsilylene group, a dicyclohexylsilylene group, and a methyl. Cyclohexylcyrrylene group, methylphenylcilylene group, diphenylcyrylene group, ditrilcilylene group, methylnaphthylcilylene group, dinaphthyltylylene group, cyclodimethylenecyrylene group, cyclotrimethylenetylylene group, cyclotetramethylenecyrylene group, cyclopentamethylenetylylene Examples thereof include a group, a cyclohexamethylene silylene group, a cycloheptamethylene silylene group, a tetramethyldisylylene group and the like. Preferred are a dimethylsilylene group, a dibutylcyrylene group, a diphenylcyrylene group, a cyclodimethylenetylylene group, a cyclotrimethylenecilylene group, a cyclotetramethylenecilylene group, a cyclopentamethylenesilylene group and a tetramethyldisylylene group.

Examples of the divalent halogen-containing group include the alkylene group, the substituted alkylene group, the cycloalkylene group, the alkylidene group, and a group in which one or more hydrogen atoms in the silicon-containing group are substituted with a halogen atom. .. For example, a bis (trifluoromethyl) methylene group, a 4,4,4-trifluorobutylmethyl methylene group, a bis (trifluoromethyl) silylene group, a 4,4,4-trifluorobutylmethylcilylene group and the like can be mentioned.

Examples of the divalent germanium-containing group and the divalent tin-containing group include a group obtained by converting silicon into germanium or tin in the silicon-containing group.

Q ² is ^{coupled with R 9} and R ¹² and Q ³ is ^{coupled with R 11} and R ¹⁴ to independently form ^{a saturated 5-membered ring containing Q 2} or Q ³ , or a bicyclic saturated 5-membered ring, respectively. When a plurality of the rings are present, the rings may be the same or different from each other. Examples of the structure in this case include a cyclopentane ring matrix, an octahydroindene ring matrix, and an octahydropentane ring matrix.

The Q ² and Q ^3, preferably, an alkylene group having 1 to 20 carbon atoms, a substituted alkylene group, a cycloalkylene group, a silicon-containing group, more preferably a silicon-containing group, more preferably, dialkylsilylene It is the basis. Further, it is preferable that ^{Q 2} and Q ^{3 are the same.}

In formula (II), X is a monovalent group, which is a neutral ligand that can be coordinated independently with a hydrogen atom, a halogen atom, a hydrocarbon group, an anionic ligand, or a lone electron pair. .. The anion ligand is a halogen-containing group, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a phosphorus-containing group, a boron-containing group, an aluminum-containing group or a conjugated diene-based divalent derivative group. X may be the same or different from each other.

In X, examples of the halogen atom include fluorine, chlorine, bromine, iodine and the like, preferably chlorine or bromine.

In X, the monovalent hydrocarbon group includes, for example, 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, a 1-octyl group, and the like. iso-propyl group, sec-butyl group (butane-2-yl group), tert-butyl group (2-methylpropan-2-yl group), iso-butyl group (2-methylpropyl group), pentan-2- Il group, 2-methylbutyl group, iso-pentyl group (3-methylbutyl group), neopentyl group (2,2-dimethylpropyl group), siamil group (1,2-dimethylpropyl group), iso-hexyl group (4- Methylpentyl group), 2,2-dimethylbutyl group, 2,3-dimethylbutyl group, 3,3-dimethylbutyl group, texyl group (2,3-dimethylbut-2-yl group), 4,4-dimethyl Linear or branched alkyl groups such as pentyl groups;
Vinyl group, allyl group, propenyl group (propa-1-en-1-yl group), iso-propenyl group (propa-1-en-2-yl group), allenyl group (propa-1,2-diene-1) -Il group), porcine-3-en-1-yl group, crotyl group (but-2-en-1-yl group), porcine-3-en-2-yl group, methallyl group (2-methylallyl group) , Erythrenyl group (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 Group (3-methylbut-3-en-1-yl group), 2-methylbut-3-en-1-yl group, penta-4-en-2-yl group, prenyl group (3-methylbut-2-ene) A linear or branched alkenyl group such as -1-yl group) or an unsaturated double bond-containing group;
A linear or branched alkynyl group or unsaturated triple bond-containing group such as an ethynyl group, a propa-2-in-1-yl group, a propargyl group (propa-1-in-1-yl group);
Benzyl group, 2-methylbenzyl group, 4-methylbenzyl group, 2,4,6-trimethylbenzyl group, 3,5-dimethylbenzyl group, Kuminyl group (4-iso-propylbenzyl group), 2,4,6 -Aroma-containing linear chain such as tri-iso-propylbenzyl group, 4-tert-butylbenzyl group, 3,5-di-tert-butylbenzyl group, 1-phenylethyl group, benzhydryl group (diphenylmethyl group) Or a branched alkyl group or 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 group (methylphenyl group), xylyl group (dimethylphenyl group), mesityl group (2,4,6-trimethylphenyl group), cumenyl group (iso-propylphenyl group), juryl group (2,3) 5,6-Tetramethylphenyl group), 2,6-di-iso-propylphenyl group, 2,4,6-tri-iso-propylphenyl group, 4-tert-butylphenyl group, 3,5-di- Examples thereof include aromatic substituted (aryl) groups such as tert-butylphenyl group, naphthyl group, biphenyl group, ter-phenyl group, binaphthyl group, acenaphthalenyl group, phenanthryl group, anthrasenyl group, pyrenyl group and ferrosenyl group. ..

Among the above-mentioned hydrocarbon groups, a methyl group, an iso-butyl group (2-methylpropyl group), a neopentyl group (2,2-dimethylpropyl group), a siamil group (1,2-dimethylpropyl group), and a benzyl group are preferable. Group, phenyl group, trill group (methylphenyl group), xsilyl group (dimethylphenyl group), mesityl group (2,4,6-trimethylphenyl group), cumenyl group (iso-propylphenyl group).

In X, examples of the monovalent halogen-containing group include a fluoromethyl group, a trifluoromethyl group, a trichloromethyl group, a pentafluoroethyl group, a 2,2,2-trifluoroethyl group, a fluorophenyl group and a 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.

In X, examples of the monovalent silicon-containing group include trimethylsilyl group, triethylsilyl group, tri-iso-propylsilyl group, diphenylmethylsilyl group, tert-butyldimethylsilyl group, tert-butyldiphenylsilyl group and triphenyl. Examples thereof include a silyl group, a tris (trimethylsilyl) silyl group, and a trimethylsilylmethyl group. Among the silicon-containing groups, a trimethylsilylmethyl group is preferable.

In X, examples of the monovalent oxygen-containing group include methoxy group, ethoxy group, n-propoxy group, iso-propoxy group, allyloxy group, n-butoxy group, sec-butoxy group, iso-butoxy group and tert-. Butoxy group, benzyloxy group, methoxymethoxy group, phenoxy group, 2,6-dimethylphenoxy group, 2,6-di-iso-propylphenoxy group, 2,6-di-tert-butylphenoxy group, 2,4 Examples thereof include 6-trimethylphenoxy group, 2,4,6-tri-iso-propylphenoxy group, acetoxy group, pivaloyloxy group, benzoyloxy group, trifluoroacetoxy group, perchlorate anion, periodate anion and the like. .. Among the oxygen-containing groups, a methoxy group, an ethoxy group, an iso-propoxy group, and a tert-butoxy group are preferable.

In X, examples of the monovalent sulfur-containing group include a mesyl group (methanesulphonyl group), a phenylsulfonyl group, a tosyl group (p-toluenesulfonyl group), a trifuryl group (trifluoromethanesulfonyl group), and a nonaflate group (nonafluoro). Butane sulfonyl group), mesylate group (methanesulfonate group), tosylate group (p-toluenesulfonate group), trifurate group (trifluoromethanesulfonate group), nonaflate group (nonafluorobutanesulfonate group) and the like. can. Among the sulfur-containing groups, a triflate group (trifluoromethanesulfonate group) is preferable.

In X, examples of the monovalent nitrogen-containing group include an amino group, a cyano group, a methylamino group, a dimethylamino group, an ethylamino group, a diethylamino group, an allylamino group, a diallylamino group, a benzylamino group and a dibenzylamino group. , Pyrrolidinyl group, Piperidinyl group, Morphoryl group, Pyrrolyl group, Bistrifurylimide group and the like. Among the nitrogen-containing groups, a dimethylamino group, a diethylamino group, a pyrrolidinyl group, a pyrrolyl group, and a bistrifurylimide group are preferable.

In X, examples of the monovalent phosphorus-containing group include hexafluorophosphate anion and the like.

In X, examples of the monovalent boron-containing group include tetrafluoroborate anion, tetrakis (pentafluorophenyl) borate anion, (methyl) (tris (pentafluorophenyl)) borate anion, and (benzyl) (tris). (Pentafluorophenyl)) borate anion, tetrakis ((3,5-bistrifluoromethyl) phenyl) borate anion, BR ₄ (R is a hydrogen atom, an alkyl group, or an aryl group which may have a substituent or a substituent or (Indicating a halogen atom) can be mentioned.

In X, as the monovalent aluminum-containing group, for example, a (M-halogen atom-aluminum atom-hydrocarbon group) four-membered ring or (M-hydrocarbon group-aluminum atom-hydrocarbon group) four-membered ring is used. _{Examples thereof include AlR 4 which} can be formed (R indicates an aryl group or a halogen atom which may have a hydrogen atom, an alkyl group, or a substituent).

In X, examples of the monovalent conjugated diene-based divalent derivative group include a 1,3-butadienyl group, an isoprenyl group (2-methyl-1,3-butadienyl group), and a piperylenyl group (1,3-pentadienyl group). , 2,4-Hexadienyl group, 1,4-diphenyl-1,3-pentadienyl group, cyclopentadienyl group and the like, and metallocyclopentene groups can be mentioned.

In X, examples of the neutral ligand (L1) capable of coordinating with a lone electron pair include ethers such as diethyl ether, tetrahydrofuran, dioxane and 1,2-dimethoxyethane, amines such as triethylamine and diethylamine, and the like. Examples thereof include heterocyclic compounds such as pyridine, picolin, lutidine, oxazoline, oxazole, thiazole, imidazole and thiophene, and organic phosphorus compounds such as triphenylphosphine, tricyclohexylphosphine and tri-tert-butylphosphine.

X is preferably a hydrogen atom, a halogen atom, a hydrocarbon group or an oxygen-containing group, and more preferably a halogen atom.

In formula (II), M is a titanium atom, a zirconium atom or a hafnium atom, preferably a zirconium atom.

The method for producing the double crosslinked metallocene compound represented by the formula (II) is not particularly limited, and it can be produced by a known method. An example of a typical synthetic route is shown below, but the embodiment of the present invention is not limited thereto.

First, the compound in which the substituted cyclopentadiene compound, which is the starting material, is crosslinked can be produced by a known method using the substituted cyclopentadiene compound as a raw material. For example, "Organometallics 1991, 10, 3739.", International Publication No. 2004/066689, JP-A-2009-143901, JP-A-2002-308893, International Publication No. 2012/077289, International Publication No. 2013/031779. The method described in the issue etc. can be mentioned.

The precursor compound (ligand) in which the substituted cyclopentadiene compound is doubly crosslinked at the adjacent position can be produced by a known method using the compound in which the substituted cyclopentadiene compound is crosslinked as a raw material. For example, in addition to the method described as a method for producing a compound in which the substituted cyclopentadiene compound is crosslinked, described in "Organometallics 1991, 10, 1787.", International Publication No. 1995/009172, JP-A-11-322774 and the like. The method that was done is mentioned.

The target double crosslinked metallocene compound represented by the formula (II) can be produced by a known method using the precursor compound (ligand). For example, in addition to the methods mentioned as the method for producing the precursor compound (ligand), "Organometallics 1993, 12, 1931.", "Organometallics 2001, 20, 3035.", US Pat. No. 5,972822, JP-A-10. -109996A, "J. Organomet. Chem. 1997, 527, 297.", JP-A-2002-88092, "Organometallics 2012, 31, 4340.", International Publication No. 2004/029062, etc. The method can be mentioned.

The double crosslinked metallocene compound represented by the formula (II) and its precursor compound (ligand) have a cyclopentadienyl ring moiety surface that is bonded to the central metal with the crosslinked moiety in two directions (2 directions). Front and back). Therefore, there is no intramolecular symmetric mirror image plane on one cyclopentadienyl ring. When the two cyclopentadienyl ring moieties bonded to the central metal across the crosslinked moiety are the same, there are two types of structural isomers, racemic and meso. On the other hand, when the two cyclopentadienyl ring moieties are different from each other, there are two types of structural isomers, a pseudo-racemic and a pseudo-meso-form. Further, when the ^{two cross-linked moieties represented by Q 2} and Q ³ in the formula (II) are different from each other, or when Q ² and Q ³ do not have symmetry as a cross-linked substituent, the structural isomer can be obtained. exist.

Purification of these structural isomer mixtures, fractionation of racemates and pseudo-racemates, and selective production of racemates and pseudo-racemates can be carried out by known methods. For example, the method mentioned as a method for producing a double crosslinked metallocene compound represented by the formula (II) can be mentioned.

Hereinafter, specific examples of the double crosslinked metallocene compound represented by the formula (II) will be shown, but this does not limit the scope of the present invention. The double crosslinked metallocene compound represented by the formula (II) may be used alone or in combination of two or more. Further, a racemate or a pseudo-racemic mixture may be used, a structural isomer mixture may be used, or a combination thereof may be used.

For convenience, the ligand structure of the double crosslinked metallocene compound represented by the formula (II) _{excluding MX 2} (metal moiety) is a cyclopentadienyl ring moiety, a cyclopentadienyl ring moiety substituent (Y), and a cyclo. It is divided into five groups: a pentadienyl ring partial substituent (W), a cyclopentadienyl ring partial substituent (V), and a crosslinked moiety structure.

The abbreviation for the cyclopentadienyl ring moiety is α, the abbreviation for the cyclopentadienyl ring partial substituent (Y) is β, the abbreviation for the cyclopentadienyl ring partial substituent (W) is γ, and the cyclopentadienyl ring partial substituent is substituted. Specific examples are shown below, with the abbreviation of the group (V) being δ and the abbreviation of the crosslinked portion being ε.

At α-10, α-11 and α-12, Cp indicates that the other cyclopentadienyl ring is bound, at positions adjacent to the binding site, α-10, α-11 and It represents that it is bound by the cross-linking site shown in α-12.

Specific examples of the metal portion MX _{2 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.

For example, the cyclopentadienyl ring moiety is α-4, the cyclopentadienyl ring partial substituent (Y ³ ) is β-23, the cyclopentadienyl ring partial substituent (W) is γ-1, and the crosslinked moiety is ε. -27, When the metal portion MX ₂ is ZrMe ₂ , the component (B) has a structure represented by the following formula [VI].

Further, the two substituted cyclopentadienyl ring moieties bonded to the metal moiety MX ₂ and the crosslinked structure are not the same, but may be different from each other. For example, one cyclopentadienyl ring moiety is α-1, the cyclopentadienyl ring partial substituents (Y ¹ ) to (Y ³ ) are β-1, and the other cyclopentadienyl ring moiety is α-1. , Cyclopentadienyl ring partial substituents (Y ¹ ) and (Y ³ ) are β-5, cyclopentadienyl ring partial substituents (Y ² ) are β-1, one crosslinked moiety is ε-31, and the other. When one of the crosslinked portions is ε-2 and the metal portion MX ₂ is Hf (NMe ₂ ) ₂ , the component (B) has a structure represented by the following formula [VII].

In addition, one cyclopentadienyl ring moiety is α-10, the cyclopentadienyl ring partial substituent (Y ² ) is β-1, the cyclopentadienyl ring partial substituent (Y ³ ) is β-21, and the other. On the other hand, the cyclopentadienyl ring moiety is α-7, the cyclopentadienyl ring partial substituent (Y ³ ) is β-1, the cyclopentadienyl ring partial substituent (W) is γ-30, and cyclopentadienyl. If the ring moiety substituent ^{(V 3)} is [delta]-2, the crosslinking moiety is epsilon-21, metal parts MX ₂ is Ti (η ⁴ -1,3- pentadienyl), component (B) is of the formula [VIII] It has the structure shown by.

(Component (C))
The component (C) is (c-1) an organometallic compound represented by the following formula (III), (IV) or (V), (c-2) an organoaluminum oxy compound, and (c-3) the above-mentioned component. It is at least one compound selected from the group consisting of (A) or a compound that reacts with the component (B) to form an ion pair.

^{_{R a m Al (OR b)}} n H p X q (III)
In formula (III), ^Ra and R ^b represent hydrocarbon groups having 1 to 15 carbon atoms, which may be the same or different from each other. X represents a halogen atom. m satisfies 0 <m≤3, n satisfies 0≤n <3, p satisfies 0≤p <3, q satisfies 0≤q <3, and m + n + p + q = 3.

M ^a AlR ^a ₄ (IV)
Wherein (IV), ^{M a} represents a Li, Na or K. Ra represents ^a hydrogen atom or a hydrocarbon group having 1 to 15 carbon atoms.

R ^a _r M ^b R ^b _s X _t (V)
In formula (V), ^Ra and R ^b represent hydrocarbon groups having 1 to 15 carbon atoms, which may be the same or different from each other. M ^b is Mg, Zn or Cd. X represents a halogen atom. r satisfies 0 <r ≦ 2, s satisfies 0 ≦ s ≦ 1, t satisfies 0 ≦ t ≦ 1, and r + s + t = 2.

In the formula (III), ^Ra and R ^b represent a hydrocarbon group having 1 to 15 carbon atoms, preferably a hydrocarbon group having 1 to 8 carbon atoms, and preferably a hydrocarbon group having 1 to 6 carbon atoms. More preferred. Examples of R ^a and R ^b include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, pentyl group, hexyl group, octyl group, cyclopentyl group, cyclohexyl group, phenyl group and trill. The group etc. can be mentioned. R ^a and R ^b may be the same as or different from each other. Examples of X include fluorine, chlorine, bromine, iodine and the like. m preferably satisfies 0 <m ≦ 3, preferably 1 ≦ m ≦ 3, and more preferably 2 ≦ m ≦ 3. It is preferable that n satisfies 0 ≦ n <3, 0 ≦ n ≦ 2, and more preferably 0 ≦ n ≦ 1. It is preferable that p satisfies 0 ≦ p <3, 0 ≦ p ≦ 2, and more preferably 0 ≦ p ≦ 1. It is preferable that q satisfies 0 ≦ p <3, 0 ≦ q ≦ 2, and more preferably 0 ≦ q ≦ 1. In addition, m, n, p and q satisfy m + n + p + q = 3.

Specific examples of the organic metal compound represented by the formula (III) include trialkylaluminum such as trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, and tri2-ethylhexylaluminum, and dimethyl. Dialkylaluminum halides such as aluminum chloride, diethylaluminum chloride, diisopropylaluminum chloride, diisobutylaluminum chloride, dimethylaluminum bromide, methylaluminum sesquichloride, ethylaluminum sesquichloride, isopropylaluminum sesquichloride, butylaluminum sesquichloride, ethylaluminum sesquibromid, etc. Alkylaluminum dihalide such as alkylaluminum sesquihalide, methylaluminum dichloride, ethylaluminum dichloride, isopropylaluminum dichloride, ethylaluminum dibromid, dimethylaluminum hydride, diethylaluminum hydride, dihydrophenylaluminum hydride, diisopropylaluminum hydride, di-n-butyl Alkyl aluminum hydrides such as aluminum hydride, diisobutylaluminum hydride, diisohexyl aluminum hydride, diphenylaluminum hydride, dicyclohexyl aluminum hydride, di-sec-heptyl aluminum hydride, di-sec-nonyl aluminum hydride, dimethylaluminum ethoxide, diethylaluminum ethoki Examples thereof include dialkylaluminum alcokiside such as side, diisopropylaluminum methoxide, and diisobutylaluminum ethoxide.

In formula (IV), ^Ra represents a hydrogen atom or a hydrocarbon group having 1 to 15 carbon atoms, preferably a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, and preferably a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms. The hydrogen group of 6 is more preferable. ^{Examples of Ra} include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, pentyl group, hexyl group, octyl group, cyclopentyl group, cyclohexyl group, phenyl group, tolyl group and the like. Can be mentioned. Specific examples of the compound represented by the formula (IV) include lithium aluminum hydride and the like.

In the formula (V), ^Ra and R ^b represent a hydrocarbon group having 1 to 15 carbon atoms, preferably a hydrocarbon group having 1 to 8 carbon atoms, and preferably a hydrocarbon group having 1 to 6 carbon atoms. More preferred. Examples of R ^a and R ^b include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, pentyl group, hexyl group, octyl group, cyclopentyl group, cyclohexyl group, phenyl group and trill. The group etc. can be mentioned. R ^a and R ^b may be the same as or different from each other. Examples of X include fluorine, chlorine, bromine, iodine and the like. It is preferable that r satisfies 1 ≦ r ≦ 2, s satisfies 0 ≦ s ≦ 1, and t satisfies 0 ≦ t ≦ 1. Specific examples of the organometallic compound represented by the formula (V) include dialkylzinc compounds described in JP-A-2003-171412, which can also be used in combination with phenol compounds and the like.

Among these, as the organometallic compound (c-1), the organometallic compound represented by the formula (III) is preferable. (C-1) The organometallic compound may be used alone or in combination of two or more.

(C-2) As the organoaluminum oxy compound, an organoaluminum oxy compound prepared from trialkylaluminum or tricycloalkylaluminum is preferable, and aluminoxane prepared from trimethylaluminum or triisobutylaluminum is particularly preferable. Such organoaluminum oxy compounds can be used alone or in combination of two or more.

(C-3) Examples of the compound that reacts with the component (A) or the component (B) to form an ion pair include JP-A-1-501950, JP-A-1-502306, and JP-A-3-179005. Lewis acid, ionic compounds, borane compounds and carborane compounds described in JP-A-3-179006, JP-A-3-207703, JP-A-3-207704, US5321106 and the like, and further, heteropoly. Compounds, isopoly compounds and the like can be used.

In the olefin polymerization catalyst according to the present invention, when an organoaluminum oxy compound such as methylaluminoxane is used in combination as a co-catalyst component, not only the polymerization activity is very high with respect to the olefin compound, but also in the solid carrier (S). Since a solid carrier component containing a co-catalyst component can be easily prepared by reacting with active hydrogen, the component (C) is preferably an organoaluminum oxy compound (c-2).

(Solid carrier (S))
The catalyst for olefin polymerization according to the present invention preferably further contains a solid carrier (S) from the viewpoint of being able to produce an olefin-based polymer having higher polymerization activity and more excellent molding processability. The solid carrier (S) is not particularly limited, and for example, an inorganic compound or an organic compound, and a solid in the form of granules or fine particles can be used.

Examples of the inorganic compound include porous oxides, inorganic halides, clays, clay minerals, ion-exchangeable layered compounds and the like.

Examples of the porous oxide include a porous oxide having a composition such as _{SiO 2} , Al ₂ O ₃ , MgO, ZrO ₂ , TiO ₂ , B ₂ O ₃ , CaO, ZnO, BaO and ThO _{2, or these.} Examples thereof include a composite oxide containing the composition of the above, or a mixture of these porous oxides. Specifically, 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 and SiO _2- TiO ₂ Examples thereof include porous oxides having a composition such as −MgO. Of these, a porous oxide containing _{SiO 2 is preferable.}

In addition, these porous oxides include a small amount of Na ₂ CO ₃ , K ₂ CO ₃ , CaCO ₃ , MgCO ₃ , Na ₂ SO ₄ , Al ₂ (SO ₄ ) ₃ , BaSO ₄ , KNO ₃ , Mg ( It _{may contain carbonates such as NO 3} ) ₂ , Al (NO ₃ ) ₃ , Na ₂ O, K ₂ O, Li ₂ O, sulfates, nitrates, and oxides.

The properties of such a porous oxide differ depending on the type and manufacturing method, but the average particle size is preferably 0.2 to 300 μm, more preferably 1 to 200 μm. The specific surface area is preferably from 50~1200m ² / g, more preferably 100~1000m ² / g. The pore volume is preferably 0.3 to ³⁰ cm 3 / g. Such a porous oxide is preferably used by firing at 100 to 1000 ° C., more preferably 150 to 700 ° C., if necessary.

Examples of the inorganic halide include MgCl ₂ , MgBr ₂ , MnCl ₂ , and MnBr ₂ . 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 precipitating agent.

Clay contains clay minerals as the main component. Further, the ion-exchangeable layered compound is a compound having a crystal structure in which planes composed of 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-exchangeable layered compounds, not only naturally produced ones but also artificial synthetic compounds can be used.

Examples of clays and clay minerals include kaolin, bentonite, wood knot clay, gairome clay, allophane, hisingel stone, pyrophyllite, ummo group, montmorillonite group, vermiculite, ryokudei stone group, parigolskite, kaolinite, nacrite, and dikite. Halloysite and the like can be mentioned.

Examples of the ion-exchangeable layered compound include ionic crystalline compounds having a layered crystal structure such as hexagonal fine packing type, antimony type, CdCl ₂ type, and CdI _{2 type. Specifically, 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 (NH ₄ PO) ₄₎ crystalline acidic salts of polyvalent metals such as 2 _· H 2 _O and the like.

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 more preferable. Here, the pore volume is measured in the range of a pore radius of 20 to 3 × 10 ^{4 Å by a mercury intrusion method using a mercury porosimeter.}

It is preferable to chemically treat clay and clay minerals. Examples of the chemical treatment include a surface treatment for removing impurities adhering to the surface, a treatment for affecting the crystal structure of clay, and the like. Specific examples thereof include acid treatment, alkali treatment, salt treatment, and organic substance treatment. The acid treatment can increase the surface area by removing impurities on the surface and elution of cations such as Al, Fe, and Mg in the crystal structure. Alkaline treatment destroys the crystal structure of the clay and can bring about 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 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. Introducing another substance between the layers of the layered compound in this way is called intercalation. Examples of the intercalating guest compounds 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. Can be mentioned. These compounds may be used alone or in combination of two or more. Further, when these compounds are intercalated, they are _{obtained by hydrolyzing metal alkoxides such as Si (OR) 4} , Al (OR) ₃ , and Ge (OR) ₄ (R is a hydrocarbon group or the like). A polymer, a colloidal inorganic compound such as _{SiO 2, etc. can coexist.} In addition, examples of the pillars include oxides produced by intercalating the metal hydroxide ions between layers and then heating and dehydrating them.

Clays, clay minerals, and ion-exchangeable layered compounds may be used as they are, or may be used after being treated by a ball mill, sieving, or the like. Further, it may be used after newly adding and adsorbing water or heat dehydration treatment. Further, these may be used alone or in combination of two or more.

Examples of the organic compound include granular or fine particle solids having an average particle size of 10 to 300 μm. Specific examples of the organic compound include a (co) polymer obtained by mainly polymerizing an olefin having 2 to 14 carbon atoms such as ethylene, propylene, 1-butene and 4-methyl-1-pentene, and vinylcyclohexane. Examples thereof include (co) polymers and reactants obtained by mainly polymerizing styrene and divinylbenzene, and granular or fine particle solids composed of variants thereof.

Further, the component (C) is insolubilized by the method described in JP-A-11-140113, JP-A-2000-38410, JP-A-2000-95810, International Publication No. 2010/0505652 and the like. The obtained solid component can also be used as the solid carrier (S).

As the solid carrier (S), a porous oxide or a solid component obtained by insolubilizing the component (C) is preferable, and a porous oxide is more preferable, from the viewpoint of preventing the generation of foreign substances during molding. In particular, it is preferable that the component (C) is the organoaluminum oxy compound (c-2) and the solid carrier (S) is a porous oxide.

(Content ratio of each component)
The molar ratio of the component (A) to the component (B) (component (A) / component (B)) contained in the olefin polymerization catalyst according to the present invention depends on the molecular weight and molecular weight distribution of the olefin polymer to be produced. It can be appropriately determined depending on the situation, but it is preferably 0.01 to 0.5, more preferably 0.02 to 0.3, still more preferably 0.03 to 0.2.

The molar ratio of the component (A) to the component (C) (component (C) / component (A)) contained in the olefin polymerization catalyst is preferably 0.00005 to 0.01, preferably 0.0001 to 0. 005 is more preferable, and 0.0001 to 0.001 is even more preferable.

The molar ratio of the component (B) to the component (C) (component (C) / component (B)) contained in the olefin polymerization catalyst is preferably 0.0001 to 0.05, preferably 0.0005 to 0. 05 is more preferable, and 0.001 to 0.01 is even more preferable.

When the component (C) is the (c-2) organoaluminum oxy compound, the number of moles of the component (C) indicates the number of moles of aluminum.

(Method for preparing catalyst for olefin polymerization)
The catalyst for olefin polymerization according to the present invention can be prepared, for example, by adding the component (A), the component (B) and the component (C) in an activated carbon or in a polymerization system using an inert carbon. .. The order of addition of each component is arbitrary, and examples thereof include the methods shown in (1) to (10) below.
(1) A method of adding the component (C), the component (A), and the component (B) in this order to the polymerization system.
(2) A method of adding the component (C), the component (B), and the component (A) in this order to the polymerization system.
(3) A method in which a contact material in which the component (A) and the component (C) are mixed and contacted is added to the polymerization system, and then the component (B) is added to the polymerization system.
(4) A method in which a contact material in which the component (B) and the component (C) are mixed and contacted is added to the polymerization system, and then the component (A) is added to the polymerization system.
(5) A method in which the component (C) is added to the polymerization system, and then a contact material in which the component (A) and the component (B) are mixed and contacted is added to the polymerization system.
(6) A method in which the component (C), the component (A), and the component (B) are added to the polymerization system in this order, and the component (C) is added to the polymerization system again.
(7) A method in which the component (C), the component (B), and the component (A) are added to the polymerization system in this order, and the component (C) is added to the polymerization system again.
(8) A contact material obtained by mixing and contacting the component (A) and the component (C) is added to the polymerization system, then the component (B) is added to the polymerization system, and then the component (C) is again added to the polymerization system. How to add in.
(9) A contact material obtained by mixing and contacting the component (B) and the component (C) is added to the polymerization system, then the component (A) is added to the polymerization system, and then the component (C) is again added to the polymerization system. How to add in.
(10) The component (C) is added to the polymerization system, then a contact material obtained by mixing and contacting the component (A) and the component (B) is added to the polymerization system, and then the component (C) is again added to the polymerization system. How to add in.

Among these, the method (1), (2) or (5) is preferable.

When the catalyst for olefin polymerization according to the present invention contains a solid carrier (S), the catalyst for olefin polymerization is, for example, a solid in which the component (C) and the component (A) are supported on the solid carrier (S). A solid catalyst component (hereinafter referred to as a solid catalyst component (XA)) and a solid catalyst component (hereinafter, a solid catalyst) in which the components (C) and the component (B) are supported on a solid carrier (S). A catalyst containing the component (X-B)), and a solid catalyst component (hereinafter, referred to as a solid catalyst component) in which the component (A), the component (B) and the component (C) are supported on a solid carrier (S). Examples thereof include a catalyst containing a solid catalyst component (XC). Among these, a catalyst containing a solid catalyst component (X-C) is preferable from the viewpoint of being able to produce an olefin polymer having better particle properties. The component (C) and the solid carrier (S) contained in the solid catalyst component (XA), and the component (C) and the solid carrier (S) contained in the solid catalyst component (XB). May be the same or different from each other.

In the method for preparing a catalyst containing the solid catalyst component (XA) and the solid catalyst component (XB), the contact order of each component is arbitrary, and for example, the following (i) to (i) to Examples thereof include the method shown in (iv).
(I) The component (C) and the solid carrier (S) are brought into contact with each other, and then the component (A) is brought into contact with each other to prepare a solid catalyst component (XA), and the component (C) and the solid state are prepared. A method for preparing a solid catalyst component (X-B) by contacting a carrier (S) and then a component (B).
(Ii) The component (A) and the component (C) are mixed and contacted, and then the mixture is brought into contact with the solid carrier (S) to prepare the solid catalyst component (XA), and the component (B) is prepared. A method of preparing a solid catalyst component (XB) by mixing and contacting the component (C) with the component (C) and then contacting the mixture with the solid carrier (S).
(Iii) The solid catalyst component (XA) is prepared by contacting the component (C) with the solid carrier (S) and then contacting the contact material between the component (A) and the component (C). A method for preparing a solid catalyst component (X-B) by contacting the component (C) with the solid carrier (S) and then contacting the contact material between the component (B) and the component (C).
(Iv) The component (C) and the solid carrier (S) are brought into contact with each other, then the component (A) is brought into contact with the component (A), and then the component (C) is brought into contact with the component (C) again to prepare the solid catalyst component (XA). Then, the component (C) and the solid carrier (S) are brought into contact with each other, then the component (B) is brought into contact with the component (B), and then the component (C) is brought into contact with the component (C) again to prepare the solid catalyst component (X-B). Method.

Among these, the method (i) or (iii) is preferable.

In the method for preparing a catalyst containing the solid catalyst component (X-C), the contact order of each component is arbitrary, and examples thereof include the methods shown in (v) to (XiX) below.
(V) The component (C) is mixed and contacted with the solid carrier (S), then the component (A) is contacted, and then the component (B) is contacted to prepare the solid catalyst component (X-C). Method.
(Vi) The component (C) is mixed and contacted with the solid carrier (S), then the component (B) is contacted, and then the component (A) is contacted to prepare the solid catalyst component (X-C). Method.
(Vii) A method for preparing a solid catalyst component (X-C) by mixing and contacting the component (C) with the solid carrier (S) and then contacting the contact mixture of the component (A) and the component (B). ..
(Viii) The component (A) and the component (B) are mixed and contacted, then the mixture is contacted with the component (C), and then the solid carrier (S) is contacted to obtain the solid catalyst component (X-C). How to prepare.
(IX) The component (C) is brought into contact with the solid carrier (S), the component (C) is further contacted, and then the component (A) and the component (B) are contacted in this order to form a solid catalyst component (iX). A method for preparing X-C).
(X) The component (C) is brought into contact with the solid carrier (S), the component (C) is further contacted, and then the component (B) and the component (A) are contacted in this order to form a solid catalyst component (X). A method for preparing X-C).
(Xi) After contacting the component (C) with the solid carrier (S), the component (C) is further contacted, and then the contact mixture of the component (A) and the component (B) is brought into contact with the solid catalyst. A method for preparing the component (X-C).
(Xii) The component (C) is mixed and contacted with the solid carrier (S), and then the contact mixture of the component (A), the component (B) and the component (C) is brought into contact with the solid catalyst component (X-C). ) How to prepare.
(Xiii) The component (C) is mixed and contacted with the solid carrier (S), then the contact mixture of the component (A) and the component (C) is brought into contact, and then the component (B) is brought into contact with the solid catalyst component. A method for preparing (X-C).
(Xiv) The component (C) is mixed and contacted with the solid carrier (S), then the contact mixture of the component (B) and the component (C) is brought into contact, and then the component (A) is brought into contact with the solid catalyst component. A method for preparing (X-C).
(Xv) After contacting the component (C) with the solid carrier (S) and further contacting the component (C), a contact mixture of the component (A) and the component (C), the component (B) and the component ( A method for preparing a solid catalyst component (X-C) by contacting the contact mixture with C) in this order.
(Xvi) After contacting the component (C) with the solid carrier (S) and further contacting the component (C), a contact mixture of the component (B) and the component (C), the component (A) and the component ( A method for preparing a solid catalyst component (X-C) by contacting the contact mixture with C) in this order.
(Xvii) The component (C) is brought into contact with the solid carrier (S), and after the component (C) is further brought into contact, the contact mixture of the component (A), the component (B) and the component (C) is brought into contact with the solid carrier (S). A method for preparing a solid catalyst component (X-C).
(Xviii) A mixture of the component (A) and the component (C) and a mixture of the component (B) and the component (C) are mixed in advance, and this is mixed with the solid carrier (S) and the component (C). A method for preparing a solid catalyst component (X-C) by contacting it with a contact material.
(XiX) A mixture of the component (A) and the component (C) and a mixture of the component (B) and the component (C) are mixed in advance, and this is mixed with the solid carrier (S), the component (C), and further. A method for preparing a solid catalyst component (X-C) by contacting a contact with the component (C).

Among these, the method of (v), (vi), (vii), (Xii), (Xiii) or (Xiv) is preferable. When a plurality of components (C) are used, the components (C) may be the same or different from each other.

Examples of the solvent used for preparing the solid catalyst component (X) include an inert hydrocarbon solvent. Specifically, aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane and kerosene, alicyclic hydrocarbons such as cyclopentane, cyclohexane and methylcyclopentane, benzene, toluene and xylene. Examples thereof include aromatic hydrocarbons such as, ethylene chloride, chlorobenzene, halogenated hydrocarbons such as dichloromethane, and mixtures thereof.

In the above method, a step including contact between the solid carrier (S) and the component (C), a step including contact between the solid carrier (S) and the component (A), the solid carrier (S) and the component (B). In the step including contact with the solid carrier (S) and the contact between the component (A) and the component (B), the component (G) is allowed to coexist to cause fouling during the polymerization reaction. It can be suppressed.

As the component (G), a surfactant can be used. The surfactant is not particularly limited, but a nonionic (nonionic) surfactant is preferable, and a polyalkylene oxide block, a higher aliphatic amide, a polyalkylene oxide, a polyalkylene oxide alkyl ether, an alkyl diethanolamine, and a polyoxyalkylene alkyl are preferable. Amines, glycerin fatty acid esters and N-acylamino acids are more preferred. These may be used alone or in combination of two or more.

Due to the contact between the component (C) and the solid carrier (S), the reaction site in the component (C) and the reaction site in the solid carrier (S) react with each other, and the component (C) and the solid carrier (S) react. ) Is chemically bonded to form a contact material between the component (C) and the solid carrier (S). The contact time between the component (C) and the solid carrier (S) is preferably 20 hours or less, more preferably 10 hours or less. The contact temperature is preferably −50 to 200 ° C., more preferably −20 to 120 ° C. When the initial contact between the component (C) and the solid carrier (S) is abruptly performed, the solid carrier (S) is disintegrated due to the reaction heat generation and reaction energy, and the morphology of the obtained solid catalyst component (X) is obtained. descend. When this is used for polymerization, continuous operation may be difficult due to poor polymer morphology. Therefore, in the initial contact between the component (C) and the solid carrier (S), for the purpose of suppressing the reaction heat generation, the reaction is brought into contact at a low temperature of -20 to 30 ° C., or the reaction heat generation is controlled to control the initial contact temperature. It is preferable to react at a sustainable rate. The same applies to the case where the component (C) is brought into contact with the solid carrier (S) and further brought into contact with the component (C). The molar ratio of contact between the component (C) and the solid carrier (S) (component (C) / solid carrier (S)) can be arbitrarily selected, but the higher the molar ratio, the more the component (A) and the component. The contact amount of (B) can be increased, and the activity of the solid catalyst component (X) can be improved. The molar ratio is preferably 0.2 to 2.0, more preferably 0.4 to 2.0.

Regarding the contact between the contact material between the component (C) and the solid carrier (S) and the component (A) and the component (B), the contact time is preferably 5 hours or less, more preferably 2 hours or less. The contact temperature is preferably −50 to 200 ° C., more preferably −50 to 100 ° C. The amount of contact of the component (A) and the component (B) with respect to the component (C) largely depends on the type of the component (C). When the component (c-1) is used as the component (C), the molar ratio of the component (c-1) to the total transition metal atom (M) in the component (A) and the component (B) [(c-1). / M] is preferably 0.01 to 100,000, more preferably 0.05 to 50,000. When the component (c-2) is used as the component (C), the molar ratio of the aluminum atom in the component (c-2) to the total transition metal atom (M) in the component (A) and the component (B) [(). c-2) / M] is preferably 10 to 500,000, more preferably 20 to 100,000. When the component (c-3) is used as the component (C), the molar ratio of the component (c-3) to the total transition metal atom (M) in the component (A) and the component (B) [(c-3). ) / M] is preferably 1 to 10, more preferably 1 to 5. The molar ratio of the component (C) to all the transition metal atoms (M) in the component (A) and the component (B) can be determined by inductively coupled plasma emission spectrometry (ICP analysis method).

(Prepolymerization)
For the (co) polymerization of the olefin, the solid catalyst component (X) can be used as it is as a catalyst, but the solid catalyst component (X) is prepolymerized with the olefin to obtain the prepolymerization catalyst component (XP). It can also be used after being formed.

The prepolymerization catalyst component (XP) can be prepared, for example, by introducing an olefin in an inert hydrocarbon solvent in the presence of the solid catalyst component (X). As the reaction method, any of a batch method, a semi-continuous method and a continuous method can be used. The reaction can be carried out under reduced pressure, normal pressure or pressure. By prepolymerization, a polymer of preferably 0.01 to 1000 g, more preferably 0.1 to 800 g, still more preferably 0.2 to 500 g can be produced per 1 g of the solid catalyst component (X). The prepolymerization catalyst component (XP) prepared in the inert hydrocarbon solvent was separated from the suspension, then suspended in the inert hydrocarbon again, and the olefin was introduced into the obtained suspension. Alternatively, the olefin may be introduced after drying.

The prepolymerization temperature is preferably -20 to 80 ° C, more preferably 0 to 60 ° C. The prepolymerization time is preferably 0.5 to 100 hours, more preferably 1 to 50 hours.

As the solid catalyst component (X) used for the prepolymerization, the above-mentioned ones can be used without limitation. Further, in the prepolymerization, the component (C) can be used if necessary, and in particular, the organoaluminum compound represented by the formula (V) in the organometallic compound (c-1) is preferably used. When the organoaluminum compound represented by the formula (V) is used, the molar ratio of the aluminum atom (Al—C) in the compound to the transition metal compound in the component (A) and the component (B) (component (component (V)). C) / transition metal compound) is preferably 0.1 to 10000, more preferably 0.5 to 5000.

The concentration of the solid catalyst component (X) in the prepolymerization system is preferably 1 to 1000 g / liter, more preferably 10 to 500 g / liter, in a ratio of the solid catalyst component (X) / polymerization volume of 1 liter.

At the time of prepolymerization, the component (G) can coexist for the purpose of suppressing fouling or improving the particle properties. Further, for the purpose of improving the fluidity of the prepolymerization catalyst component (XP), heat spot seating during polymerization, and suppressing the generation of polymer lumps, the component (G) is relative to the prepolymerization catalyst component (XP) generated by the prepolymerization. May be contacted.

The temperature at which the component (G) is mixed and contacted is preferably −50 to 50 ° C., more preferably −20 to 50 ° C. The contact time is preferably 1 to 1000 minutes, more preferably 5 to 600 minutes. When the solid catalyst component (X) and the component (G) are mixed and contacted, the amount of the component (G) is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the solid catalyst component (X). 0.3 to 10 parts by mass is more preferable, and 0.4 to 5 parts by mass is further preferable. The mixed contact between the solid catalyst component (X) and the component (G) can be performed in an inert hydrocarbon solvent. Examples of the inert hydrocarbon solvent include the same solvents as those used for preparing the solid catalyst component (X).

The obtained prepolymerization catalyst component (XP) can also be dried and used as a dry prepolymerization catalyst. Since the dry prepolymerization catalyst has excellent fluidity, it can be stably supplied to the polymerization reactor. Further, since it is not necessary to accompany the solvent used for suspension in the gas phase polymerization system, stable polymerization can be performed.

The prepolymerization catalyst component (XP) can be dried after removing the dispersion medium from the obtained suspension of the prepolymerization catalyst component (XP) by filtration or the like. The prepolymerization catalyst component (XP) is dried by keeping the prepolymerization catalyst component (XP) at a temperature in the range of preferably 70 ° C. or lower, more preferably 20 to 50 ° C. under the flow of an inert gas. Can be done. The drying time is preferably 3 to 8 hours, although it depends on the drying temperature. The amount of the volatile component of the obtained dry prepolymerization catalyst is preferably 2.0% by mass or less, more preferably 1.0% by mass or less. When the amount of the volatile component is 2.0% by mass or less, the fluidity of the dry prepolymerization catalyst is further improved, and the dry prepolymerization catalyst can be more stably supplied to the polymerization reactor. The smaller the amount of the volatile component, the better, and the lower limit thereof is not particularly limited, but it is practically 0.001% by mass or more.

Here, the amount of the volatile component of the dry prepolymerization catalyst can be measured by a weight loss method, a method using gas chromatography, or the like. In the weight loss method, the weight loss when the dry prepolymerization catalyst is heated at 110 ° C. for 1 hour in an inert gas atmosphere is obtained and expressed as a percentage of the dry prepolymerization catalyst before heating. In the method using gas chromatography, volatile components such as hydrocarbons are extracted from the dry prepolymerization catalyst, a calibration curve is prepared according to the internal standard method, and the amount is calculated as% by mass from the GC area. When the amount of the volatile component of the dry prepolymerization catalyst is about 1% by mass or more, the weight loss method is adopted. On the other hand, when the amount of the volatile component of the dry prepolymerization catalyst is less than about 1% by mass, a method using gas chromatography is adopted.

Examples of the inert gas used for drying the prepolymerization catalyst component (XP) include nitrogen gas, argon gas, neon gas and the like. The oxygen concentration (volume basis) of the inert gas is preferably 20 ppm or less, more preferably 10 ppm or less, still more preferably 5 ppm or less. The water content (based on mass) of the inert gas is preferably 20 ppm or less, more preferably 10 ppm or less, still more preferably 5 ppm or less. When the oxygen concentration and the water content of the inert gas are within the above ranges, the olefin polymerization activity of the dry prepolymerization catalyst is improved.

[Method for producing ethylene polymer]
In the method for producing an ethylene-based polymer according to the present invention, ethylene alone or ethylene and an olefin having 3 to 20 carbon atoms are polymerized in the presence of the olefin polymerization catalyst according to the present invention. In this method, by using the catalyst for olefin polymerization according to the present invention, an ethylene-based polymer having high polymerization activity, excellent molding processability and mechanical strength, and excellent molding processability having many long-chain branches is efficiently produced. Can be manufactured as a target. The "ethylene-based polymer" refers to a polymer having an ethylene content of 10 mol% or more in the polymer, and may be an ethylene homopolymer or an ethylene copolymer.

In the method according to the present invention, the polymerization can be carried out by a liquid phase polymerization method such as a dissolution polymerization method or a suspension polymerization method or a vapor phase polymerization method, but a suspension polymerization method or a vapor phase polymerization method is preferable.

Specific examples of the inert hydrocarbon medium used in the liquid phase polymerization method include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; cyclopentane, cyclohexane, and methylcyclopentane. Aliphatic hydrocarbons such as; aromatic hydrocarbons such as benzene, toluene and xylene; halogenated hydrocarbons such as ethylene chloride, chlorobenzene and dichloromethane, and mixtures thereof. Further, in the liquid phase polymerization method, the olefin itself can be used as a solvent.

When polymerizing an olefin using the catalyst for olefin polymerization according to the present invention, the amounts of the component (A) and the component (B) are preferably ^10-12 to ^1-1 mol, more preferably 10-12 to -1 mol, per 1 liter of the reaction volume. A catalyst for olefin polymerization is used in an amount of ^10-8 to ^{10-2 mol.}

The polymerization temperature of the olefin is preferably −50 to 200 ° C., more preferably 0 to 170 ° C., and even more preferably 60 to 170 ° C. The polymerization pressure is preferably from normal pressure to 100 kg / cm ^2, more preferably atmospheric pressure to 50 kg / cm ^2. The polymerization reaction can be carried out by any of a batch type, a semi-continuous type and a continuous type. 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 polymer can be adjusted by the presence of hydrogen in the polymerization system or by changing the polymerization temperature. At the time of polymerization, the component (G) can coexist for the purpose of suppressing fouling or improving the particle properties.

The olefin other than ethylene supplied to the polymerization reaction is not particularly limited, but is preferably an olefin having 3 to 20 carbon atoms. Specific examples of olefins having 3 to 20 carbon atoms include propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-. Α-olefins such as tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene; cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene, 2-methyl-1,4,5,8- Cyclic olefins such as dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene and the like can be mentioned. Further, styrene, vinylcyclohexane, diene, acrylic acid, methacrylic acid, fumaric acid, maleic anhydride and the like; and polar monomers such as methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate and methacrylic acid can also be mentioned. .. These may be used alone or in combination of two or more.

(Ethylene polymer)
The ethylene-based polymer obtained by the above method usually satisfies the following requirement (1), preferably the following requirement (1), and the following requirement (2) or the following (3), and more preferably the following requirement ( All of 1) to (3) are satisfied. The measuring method of these requirements is as described in the examples.

Requirement (1): density of 875kg / ^{m 3} or more 945 kg / ^{m 3} or less. The lower limit of the density range is preferably 885 kg / m ³ , more preferably 900 kg / m ³ . The upper limit of the density range is preferably 935 kg / m ³ , more preferably 930 kg / m ³ . When the density is 875 kg / m ³ or more, the surface stickiness of the film obtained by molding the ethylene-based polymer is small, and the blocking resistance is excellent. When the density is 945 kg / m ³ or less, the impact strength of the film obtained by molding the ethylene polymer is good, and the mechanical strength such as heat seal strength and bag breaking strength is good.

In general, the density depends on the content of α-olefin in the ethylene-based polymer, and the lower the content of α-olefin, the higher the density, and the higher the content of α-olefin, the lower the density. Further, it is known that the content of α-olefin in an ethylene-based polymer is determined by the composition ratio of α-olefin and ethylene in the polymerization system (for example, Walter). Kaminsky, Makromol. Chem. 193, p. 606 (1992)). Therefore, by increasing or decreasing the α-olefin / ethylene, an ethylene-based polymer having a density in the above range can be produced.

Requirement (2): According to the standard method of ASTM D1238-89, the melt flow rate [MFR (g / 10 minutes)] at 190 ° C. under a 2.16 kg load is 0.01 to 100 g / 10 minutes. The lower limit of the range of the MFR is preferably 0.1 g / 10 minutes, more preferably 0.5 g / 10 minutes. The upper limit of the range of the MFR is preferably 50 g / 10 minutes, more preferably 30 g / 10 minutes. When the MFR is 0.01 g / 10 minutes or more, the shear viscosity of the ethylene polymer is not too high and the moldability is excellent, and the appearance of the film is good, for example. When the MFR is 100 g / 10 minutes or less, the tensile strength and heat seal strength of the ethylene polymer are good.

Requirement (3): Extreme viscosity measured in 135 ° C. decalin ([η] (dl / g)) and weight measured by gel permeation chromatography (GPC) -viscosity detector method (GPC-VISCO). The average molecular weight (Mw) satisfies the following formula (Eq-1).

0.90 × 10 ^-4 × Mw ^0.776 ≦ [η] ≦ 1.65 × 10 ^-4 × Mw ^0.776 (Eq-1)
The lower limit of the range of [η] is preferably 0.95 × 10 ^-4 × Mw ^0.776 , and more preferably 1.00 × 10 ^-4 × Mw ^0.776 . The upper limit of the range of [η] is preferably 1.58 × 10 ^-4 × Mw ^0.776 , and more preferably 1.50 × 10 ^-4 × Mw ^0.776 .

It is known that when a long-chain branch is introduced into an ethylene-based polymer, the ultimate viscosity [η] (dl / g) becomes smaller for the molecular weight than a linear ethylene-based polymer without a long-chain branch. (Eg Walther Burcard, ADVANCES IN POLYMER SCIENCE, 143, Branched Polymer II, p. 137 (1999)). Therefore, even in the ethylene-based polymer according to the present invention, when the ultimate viscosity [η] (dl / g) is within the above range, the ethylene-based polymer has a large number of long-chain branches and is therefore molded. Excellent in property and fluidity.

In order to suppress variations in physical property values, the ethylene-based polymer particles obtained by the polymerization reaction and other components added as desired can be melted by any method and subjected to kneading, granulation, or the like. ..

The ethylene-based polymer obtained by the method according to the present invention may be pelletized by, for example, the following method.
(I) A method in which an ethylene polymer and other components added as desired are mechanically blended using an extruder, a kneader, or the like and cut into a predetermined size.
(Ii) The ethylene-based polymer and other components added as desired are dissolved in a suitable good solvent (for example, a hydrocarbon solvent such as hexane, heptane, decane, cyclohexane, benzene, toluene and xylene), and the solvent is dissolved. After removal, a method of mechanically blending using an extruder, kneader, etc. and cutting to a predetermined size.

The ethylene-based polymer obtained by the method according to the present invention is a weather resistant stabilizer, a heat-resistant stabilizer, an antistatic agent, an antislip agent, an antiblocking agent, an antifogging agent, and a lubricant, as long as the object of the present invention is not impaired. , Pigments, dyes, nucleating agents, plasticizers, antistatic agents, hydrochloric acid absorbers, antioxidants and the like may be blended as necessary.

The ethylene-based polymer obtained by the method according to the present invention and, if necessary, a resin composition containing a thermoplastic resin and an additive may be processed by, for example, film molding, blow molding, injection molding, extrusion molding or the like. can. Examples of the film molding include extrusion laminating molding, T-die film molding, and inflation molding (air cooling, water cooling, multi-stage cooling, high-speed processing). The film obtained by using the ethylene-based polymer can be used as a single layer, but can be further imparted with various functions by forming a multilayer. Examples of the method for producing a multi-layered film include the coextrusion method in each of the above-mentioned molding methods. Further, a method of laminating with a paper or a barrier film (aluminum foil, a vapor-deposited film, a coating film, etc.), which is difficult to co-extrude, by a laminating laminating molding method such as an extrusion laminating molding or a dry laminating method can be mentioned. The production of a high-performance product composed of multiple layers by the coextrusion method in blow molding, injection molding, extrusion molding and the like can be carried out in the same manner as in film molding.

Examples of the molded product obtained by processing the ethylene-based polymer obtained by the method according to the present invention and, if necessary, a resin composition containing a thermoplastic resin and an additive include a film, a blow infusion bag, and a blow bottle. , Gasoline tank, extruded tube, pipe, tear cap, injection molded product such as daily miscellaneous goods, fiber, large molded product by rotary molding, etc.

Further, the film obtained by processing the ethylene-based polymer obtained by the method according to the present invention and, if necessary, a resin composition containing a thermoplastic resin and an additive can be, for example, a water packaging bag or a liquid soup package. Bags, liquid paper containers, lami raw fabric, specially shaped liquid packaging bags (standing pouches, etc.), standard bags, heavy bags, wrap films, sugar bags, oil packaging bags, various packaging films for food packaging, protect films, etc. It can be suitably used as an infusion bag, an agricultural material, or the like. Further, the film can be used as a multilayer film by laminating it with a base material such as nylon or polyester.

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.

[Identification of compound]
In the synthesis of component (A) and component (B), the compound was identified at ^{270 MHz, 1} H-NMR (trade name: GSH-270, manufactured by JEOL Ltd.), gas chromatograph mass spectrometer (GC-MS). (Product name: GCMS-QP5050A and GCMS-QP2010Ultra, manufactured by Shimadzu Corporation), FD-mass spectrometry (trade name: SX-102A, manufactured by JEOL Ltd.).

[Melt flow rate (MFR)]
The melt flow rate (MFR) of the ethylene polymer was measured according to ASTM D1238-89 under the conditions of 190 ° C. and 2.16 kg load (kgf).

[density]
The density of the ethylene-based polymer was measured according to JIS K7112 by a density gradient tube method after heat-treating the strands obtained at the time of MFR measurement at 100 ° C. for 1 hour and allowing them to stand at room temperature for 1 hour.

[Ultimate viscosity [η]]
For the ultimate viscosity [η] of the ethylene polymer, about 20 mg of the measurement sample was dissolved in 15 ml of decalin, and the specific viscosity ηsp was measured in an oil bath at 135 ° C. After adding 5 ml of a decalin solvent to this decalin solution and diluting it, the specific viscosity ηsp was measured in the same manner. This dilution operation is repeated twice more, and the value of ηsp / C when the concentration (C) is extrapolated to 0 as shown in the following formula (Eq-2) is the limit viscosity [η] (unit: dl / g). ).

[Η] = lim (ηsp / C) (C → 0) (Eq-2)
[Measurement by gel permeation chromatography (GPC)]
The gel permeation chromatography (GPC) measurement was performed using GPC / V2000 (trade name) manufactured by Waters Co., Ltd. as follows. Shodex AT-G (trade name) was used for the guard column, and two AT-806 (trade name) were used for the analysis column. The column temperature was 145 ° C. O-dichlorobenzene and 0.3% by mass of BHT as an antioxidant were used as the mobile phase, and the mixture was transferred at 1.0 ml / min. The sample concentration was 0.1% by mass. A differential refractometer and a 3-capillary viscometer were used as detectors. As the standard polystyrene, standard polystyrene manufactured by Tosoh Corporation was used. Calculate the measured viscosity from the viscometer and refractometer, and calculate the weight average molecular weight (Mw), number average molecular weight (Mn), Z average molecular weight (Mz), and ratio (Mw / Mn and Mz / Mw) from the measured universal calibration. did.

<(1) Synthesis of component (A)>
[Synthesis Example 1]
Dimethylsilylene-1- (3-n-propylcyclopentadienyl) -1- (cyclopentadienyl) zirconium dichloride represented by the following formula (A-1) (hereinafter referred to as component (A-1)). Was synthesized by the method described in Japanese Patent No. 5455354.

<(2) Synthesis of component (B)>
[Synthesis Example 2]
1.89 g (20.1 mmol) of 1,3-dimethylcyclopentadiene and 40 mL of tetrahydrofuran were placed in a 200 mL reactor that had been sufficiently dried and substituted with argon, and 13.0 mL of n-butyllithium solution (hexane solution, 1.63 mol / L, 21.2 mmol) was added under ice-cooling, and the mixture was stirred at room temperature for 2 hours. This suspension was slowly added to 12.0 mL (100 mmol) of dimethylsilyldichloride in 10 mL of n-hexane under cooling at −78 ° C., and stirring was continued for 19 hours while returning to room temperature. After distilling off the solvent of the reaction solution and unreacted dimethylsilyldichloride, 20 mL of tetrahydrofuran and 2.00 mL (21.3 mmol) of 1,3-dimethyl-2-imidazolidinone were added to the residue. 10.4 g (tetrahydrofuran solution, 25% by mass, 21.3 mmol) of n-butylcyclopentadiene solution and 20 mL of tetrahydrofuran were placed in a 200 mL reactor that had been sufficiently dried and substituted with argon, and 13.0 mL of n-butyllithium solution (hexane) was charged. The solution (1.63 mol / L, 21.2 mmol) was added under ice-cooling, and the mixture was stirred at room temperature for 2 hours. This solution was added dropwise to the reaction residue diluted solution cooled to −78 ° C., and stirring was continued for 19 hours while slowly returning to room temperature. A saturated aqueous solution of ammonium chloride was added, the soluble component was extracted with n-hexane, 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. As a result, a compound represented by the following formula (B-1a) (hereinafter referred to as compound (B-1a)) was obtained as an isomer mixture of 1.82 g (yield 33%).

^{1 1} H NMR (270 MHz, CDCl ₃ ) δ 6.76-5.00 (5H, m), 3.50-2.52 (2H, m), 2.50-2.22 (2H, m), 2 .22-1.10 (10H, m), 1.00-0.78 (3H, m), -0.21 (6H, s, Si-CH ₃ ) ppm

[Synthesis Example 3]
1.49 g (5.45 mmol) of the compound (B-1a) obtained in Synthesis Example 2, 20 mL of toluene and 0.9 mL of tetrahydrofuran were charged into a 200 mL reactor that had been sufficiently dried and substituted with argon, and stirred. After adding 6.70 mL (hexane solution, 1.63 mol / L, 10.9 mmol) of n-butyllithium solution to this solution at room temperature, stirring was continued for 3 hours in an oil bath at 40 ° C. After distilling off the solvent, 20 mL of tetrahydrofuran was added to the obtained solid. The solution was cooled to −78 ° C., 0.65 mL (5.44 mmol) of dimethylsilyldichloride was added, and stirring was continued for 17 hours while returning to room temperature. A saturated aqueous solution of ammonium chloride was added, the soluble component was extracted with n-hexane, 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. As a result, a compound represented by the following formula (B-1b) (hereinafter referred to as compound (B-1b)) was obtained as an isomer mixture in an amount of 1.33 g (yield 74%).

^{1 1} H NMR (270 MHz, CDCl ₃ ) δ 6.81 (1H, s, C = CH-C), 6.38 (1H, s, C = CH-C), 6.08 (1H, s, C = CH-C), 3.45 (1H, s, Si-CH), 3.17 (1H, d, J = 1.6Hz, Si-CH), 2.43 (2H, t, J = 1.6Hz) _{, -CH 2 -C 3 H 7)} , 2.22-1.93 (6H, m, C-CH 3), 1.72-1.15 (4H, m, -CH 2 -C 2 H 4 - _{CH 3), 0.93 (3H,} t, J = 7.2Hz, -C 3 H 6 -CH 3), 0.64-0.30 (6H, m, Si-CH 3), - 0.40 (3H, s, Si-CH ₃ ), -0.52 (3H, s, Si-CH ₃ ) ppm

[Synthesis Example 4]
0.33 g (1.01 mmol) of the compound (B-1b) obtained in Synthesis Example 3, 10 mL of toluene and 0.17 mL of tetrahydrofuran were charged in a 100 mL reactor sufficiently dried and substituted with argon, and stirred. To this solution, 1.25 mL of an n-butyllithium solution (hexane solution, 1.63 mol / L, 2.04 mmol) was added at room temperature, and then stirring was continued for 4 hours in an oil bath at 40 ° C. After distilling off the solvent, 10 mL of diethyl ether was added to the obtained solid. The solution was cooled to 0 ° C., 0.23 g (1.00 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 material was removed by a membrane syringe filter. After distilling off the solvent of the obtained solution, a suspension was prepared by adding n-hexane to the obtained solid, the insoluble material was filtered off with a glass filter, and the residue was dried under reduced pressure. As a result, 0.28 g (yield 27%) of a white powdery compound represented by the following formula (B-1) (hereinafter referred to as component (B-1)) was obtained.

^{1 1} H NMR (270 MHz, CDCl ₃ ) δ 6.54 (2H, s, Cp-H), 6.02 (1H, s, Cp-H), 2.69 (2H, t, J = 7.3 Hz, Cp-CH _2- ), 2.19 (6H, s, Cp-CH ₃ ), 1.70-1.55 (2H, m, -CH _2- ), 1.46-1.28 (2H, m) _{, -CH 2 -), 0.92 (} 3H, t, J = 7.3Hz, -C 3 H 6 -CH 3), 0.85 (6H, s, Si-CH 3), 0.54 (6H , S, Si-CH ₃ ) ppm
FD-Mass Spectrometry (M ⁺ ): 488

[Synthesis Example 5]
2.02 g (83.1 mmol) of magnesium pieces were charged into a 200 mL reactor that had been 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 25 mL of tetrahydrofuran were charged and stirred. A 20 mL diluted solution of 2-bromoinden 3.92 g (20.1 mmol) in tetrahydrofuran was slowly added, and the mixture was heated under reflux in an oil bath at 80 ° C. for 1 hour. This reaction solution was slowly added to 12.0 mL (100 mmol) of dimethylsilyl dichloride in 10 mL of n-hexane under cooling at −78 ° C., and stirring was continued for 18 hours while returning to room temperature. After distilling off the solvent of the reaction solution and unreacted dimethylsilyldichloride, 20 mL of tetrahydrofuran and 1.90 mL (20.2 mmol) of 1,3-dimethyl-2-imidazolidinone were added to the residue. 9.79 g of n-butylcyclopentadiene solution (tetrahydrofuran solution, 25% by mass, 20.0 mmol) and 20 mL of tetrahydrofuran were charged in a 100 mL reactor sufficiently dried and substituted with argon, and 12.5 mL of n-butyllithium solution (hexane) was charged. The solution (1.60 mol / L, 20.0 mmol) was added and stirred at room temperature for 2 hours. This solution was added dropwise to the reaction residue diluted solution cooled to −78 ° C., and stirring was continued for 17 hours while slowly returning to room temperature. A saturated aqueous solution of ammonium chloride was added, the soluble component was extracted with n-hexane, 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. As a result, a compound represented by the following formula (B-2a) (hereinafter referred to as compound (B-2a)) was obtained as an isomer mixture of 4.65 g (yield 79%).

^{1 1} H NMR (270 MHz, CDCl ₃ ) δ 7.52-7.35 (2H, m, Ar-H), 3.32-7.08 (3H, m, Ar-H & C = CH-C), 7. 02-5.70 (3H, m, C = CH-C), 3.60-2.87 (3H, m, Ar-CH 2 -C & Si-CH), 2.39 (2H, t, J = 7 _{.7Hz, -CH 2 -C 3 H 7} ), 1.59-1.41 (2H, m, -CH 2 -), 1.41-1.20 (2H, m, -CH 2 -), 0 _{.87 (3H, t, J =} 7.2Hz, -C 3 H 6 -CH 3), 0.50-0.02 (6H, m, Si-CH 3) ppm

[Synthesis Example 6]
In a 200 mL reactor that had been sufficiently dried and substituted with argon, 3.83 g (13.0 mmol) of the compound (B-2a) obtained in Synthesis Example 5, 50 mL of toluene and 2.2 mL of tetrahydrofuran were charged and stirred. After adding 16.3 mL of n-butyllithium solution (hexane solution, 1.60 mol / L, 26.1 mmol) to this solution under cooling at 0 ° C., stirring was continued for 3 hours in an oil bath at 40 ° C. After distilling off the solvent, 50 mL of tetrahydrofuran was added to the obtained solid. The solution was cooled to −78 ° C., 1.55 mL (13.0 mmol) of dimethylsilyldichloride was added, and stirring was continued for 17 hours while returning to room temperature. A saturated aqueous solution of ammonium chloride was added, the soluble component was extracted with n-hexane, 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. As a result, a compound represented by the following formula (B-2b) (hereinafter referred to as compound (B-2b)) was obtained as an isomer mixture in an amount of 3.55 g (yield 78%).

^{1 1} H NMR (270 MHz, CDCl ₃ ) δ 7.48 (2H, t, J = 7.3 Hz, Ar-H), 7.30-7.13 (3H, m, Ar-H & C = CH-C), 6.90 (1H, s, C = CH-C), 6.43 (1H, s, C = CH-C), 3.91-3.37 (2H, m, Ar-CH 2 -C & Si-CH _{), 2.47 (2H, t,} J = 7.9Hz, -CH 2 -C 3 H 7), 1.67-1.49 (2H, m, -CH 2 -), 1.49-1. _{22 (2H, m, -CH 2} -), 0.95 (3H, t, J = 7.2Hz, -C 3 H 6 -CH 3), 0.63 (3H, s, Si-CH 3), 0.59 (3H, s, Si-CH ₃ ), -0.42 (3H, s, Si-CH ₃ ), -0.75 (3H, s, Si-CH ₃ ) ppm

[Synthesis Example 7]
In a 100 mL reactor sufficiently dried and substituted with argon, 0.35 g (1.01 mmol) of the compound (B-2b) obtained in Synthesis Example 6, 10 mL of toluene and 0.17 mL of tetrahydrofuran were charged and stirred. To this solution, 1.25 mL of an n-butyllithium solution (hexane solution, 1.60 mol / L, 2.00 mmol) was added at room temperature, and then stirring was continued for 4 hours in an oil bath at 40 ° C. After distilling off the solvent, 10 mL of diethyl ether was added to the obtained solid. The solution was cooled to 0 ° C., 0.23 g (1.00 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 material was removed by a membrane syringe filter. The obtained solution was concentrated under reduced pressure, and then a suspension was prepared by adding n-hexane, the insoluble material was filtered off with a glass filter, and the residue was dried under reduced pressure. As a result, 0.17 g (yield 34%) of a pale yellow powdery compound represented by the following formula (B-2) (hereinafter referred to as component (B-2)) was obtained.

^{1 1} H NMR (270 MHz, CDCl ₃ ) δ 7.75 (1H, dt, J = 1.1and8.3 Hz, Ar-H), 7.37-7.19 (3H, m, Ar-H), 7. 13 (1H, d, J = 0.7Hz, Cp-H), 6.23 (1H, d, J = 1.6Hz, Cp-H), 6.41 (1H, d, J = 1.7Hz, Cp-H), 2.55 (2H, t, J = _{7.6Hz, Cp-CH 2-} ), 1.65-1.47 (2H, m, -CH _2- ), 1.40-1. 22 (2H, m, -CH _2- ), 1.02 (3H, s, Si-CH ₃ ), 0.96 (3H, s, Si-CH ₃ ), 0.88 (3H, t, J = _{7.3Hz, -C 3 H 6 -CH 3} ), 0.73 (3H, s, Si-CH 3), 0.60 (3H, s, Si-CH 3) ppm
FD-Mass Spectrometry (M ⁺ ): 510

[Synthesis Example 8]
(1,1'-dimethylsilylene) (2,2'-dimethylsilylene)-(3', 5'-cyclopentadienyl) (3,5-dimethylcyclopenta) represented by the following formula (B-3) Dienyl) Zirconium dichloride (hereinafter referred to as component (B-3)) was synthesized according to the method described in JP-A-2003-105016.

<Synthesis of reaction product of (3) component (C) and solid carrier (S)>
[Synthesis Example 9]
Using a reactor with a stirrer with an internal volume of 270 L, silica gel (manufactured by Fuji Silysia Chemical Ltd., cumulative 50% volume distribution of laser light diffraction scattering method, particle size: 70 μm, specific surface area: 340 m ² / g, fine Pore volume: 1.3 cm ³ / g, dried at 250 ° C. for 10 hours, 10 kg (hereinafter referred to as solid carrier (S-1)) was suspended in 77 L of toluene, and then cooled to 0 to 5 ° C. To this suspension, 19.4 liters of a toluene solution (3.5 mol / L in terms of Al atom) of methylaluminoxane (hereinafter referred to as component (C-1)) 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 is lowered to room temperature, the supernatant is removed by decantation, and the solid carrier is washed twice with toluene to obtain a toluene slurry of a solid carrier having a total volume of 115 liters (hereinafter, component (C-1) and a solid carrier). (Shown as the slurry of (S-1)) was prepared. When a part of the slurry of the obtained component (C-1) and the solid carrier (S-1) was collected and analyzed, the solid content concentration was 122.6 g / L.

[Example 1]
(Preparation of solid catalyst component (X-1))
In a reactor with a stirrer having an internal volume of 200 mL sufficiently substituted with nitrogen, 30 mL of toluene and 1.63 mL of the slurry of the component (C-1) and the solid carrier (S-1) obtained in Synthesis Example 9 under a nitrogen atmosphere. (Solid content mass 0.2 g) was charged. Next, 0.24 μmol of the toluene solution of the component (A-1) obtained in Synthesis Example 1 was added as Zr, and 4.64 μmol of the toluene solution of the component (B-1) obtained in Synthesis Example 4 was added as Zr. After contacting them at an in-system temperature of 20 to 25 ° C. for 1 hour, the supernatant was removed by decantation, and the mixture was further washed twice with hexane. As a result, a slurry of the solid catalyst component (X-1) having a total volume of 40 mL was prepared.

(Manufacturing of ethylene polymer)
After adding 500 ml of heptane to a SUS autoclave having an internal volume of 1 liter sufficiently substituted with nitrogen under a nitrogen atmosphere, ethylene was circulated and the liquid phase and the gas phase were saturated with ethylene. Next, 10 mL of 1-hexene, 0.375 mmol of triisobutylaluminum, and 80 mg of the solid catalyst component (X-1) as a solid component were charged, and then the temperature was raised to 0.8 MPaG at 80 ° C. and the pressure was increased. , The polymerization reaction was carried out for 90 minutes. The obtained polymer was filtered and then vacuum dried at 80 ° C. for 10 hours to obtain 133.2 g of an ethylene polymer. The polymerization activity per transition metal was 4.6 × 10 ⁴ (g / mmol-Zr / hr).

To the obtained ethylene polymer, 0.1% by mass of IrganonoX 1076 (trade name, manufactured by Ciba Specialty Chemicals Co., Ltd.) and 0.1% by mass of Irgafos 168 (trade name, manufactured by Ciba Specialty Chemicals Co., Ltd.) were added as heat-resistant stabilizers. , Labplast mill (manufactured by Toyo Seiki Seisakusho Co., Ltd.), melt-kneaded at a resin temperature of 180 ° C. and a rotation speed of 50 rpm for 5 minutes. Further, this molten polymer was cooled using a press molding machine (manufactured by Shinto Metal Industry Co., Ltd.) under the conditions of a cooling temperature of 20 ° C., a cooling time of 5 minutes, and a cooling pressure of 100 kg / cm ² . Physical properties were measured using the obtained sample as a measurement sample. The results are shown in Table 6.

[Example 2]
(Preparation of solid catalyst component (X-2))
In a reactor with a stirrer having an internal volume of 200 mL sufficiently substituted with nitrogen, 30 mL of toluene and 2.45 mL of the slurry of the component (C-1) and the solid carrier (S-1) obtained in Synthesis Example 9 were placed in a nitrogen atmosphere. (Solid content mass 0.3 g) was charged. Next, 0.30 μmol of the toluene solution of the component (A-1) obtained in Synthesis Example 1 was added as Zr, and 7.14 μmol of the toluene solution of the component (B-2) obtained in Synthesis Example 7 was added as Zr. After contacting them at an in-system temperature of 20 to 25 ° C. for 1 hour, the supernatant was removed by decantation, and the mixture was further washed twice with hexane. As a result, a slurry of the solid catalyst component (X-2) having a total volume of 40 mL was prepared.

(Manufacturing of ethylene polymer)
81.2 g of an ethylene polymer was obtained by the same method as in Example 1 except that the solid catalyst component (X-2) was used. The polymerization activity per transition metal was 2.8 × 10 ⁴ (g / mmol-Zr / hr). The obtained ethylene-based polymer was melt-kneaded and cooled by the same method as in Example 1, and the physical properties were measured using the obtained sample as a measurement sample. The results are shown in Table 6.

[Example 3]
(Preparation of solid catalyst component (X-3))
In a reactor with a stirrer having an internal volume of 200 mL sufficiently substituted with nitrogen, 30 mL of toluene and 1.63 mL of the slurry of the component (C-1) and the solid carrier (S-1) obtained in Synthesis Example 9 under a nitrogen atmosphere. (Solid content mass 0.2 g) was charged. Next, 0.25 mmol of the toluene solution of the component (A-1) obtained in Synthesis Example 1 was added as Zr, and 4.84 mmol of the toluene solution of the component (B-3) obtained in Synthesis Example 8 was added as Zr. After contacting them at an in-system temperature of 20 to 25 ° C. for 1 hour, the supernatant was removed by decantation, and the mixture was further washed twice with hexane. As a result, a slurry of the solid catalyst component (X-3) having a total volume of 40 mL was prepared.

(Manufacturing of ethylene polymer)
62.80 g of an ethylene polymer was obtained by the same method as in Example 1 except that 40 mg of the solid catalyst component (X-3) was used as a solid component. The polymerization activity per transition metal was 4.2 × 10 ⁴ (g / mmol-Zr / hr). The obtained ethylene-based polymer was melt-kneaded and cooled by the same method as in Example 1, and the physical properties were measured using the obtained sample as a measurement sample. The results are shown in Table 6.

[Example 4]
(Preparation of solid catalyst component (X-4))
In a reactor with a stirrer having an internal volume of 2 L sufficiently substituted with nitrogen, 150 mL of toluene and 398 mL of a slurry of the component (C-1) and the solid carrier (S-1) obtained in Synthesis Example 9 (solid content mass 48. 8g) was charged. Next, 0.12 mmol of the toluene solution of the component (A-1) obtained in Synthesis Example 1 was added as Zr, and 1.09 mmol of the toluene solution of the component (B-1) obtained in Synthesis Example 4 was added as Zr. After contacting them at an in-system temperature of 20 to 25 ° C. for 1 hour, the supernatant was removed by decantation, and the mixture was further washed twice with hexane. As a result, a slurry of solid catalyst components having a total volume of 1100 mL was prepared.

After cooling the obtained slurry of the solid catalyst component to 10 ° C., 92.1 mmol of diisobutylaluminum hydride (DiBAl-H) was added. Further, ethylene was continuously supplied into the system for several minutes under normal pressure. During this period, the temperature in the system was maintained at 10 to 15 ° C. Then 13.3 mL of 1-hexene was added. After the addition of 1-hexene, the temperature inside the system was raised to 35 ° C., and 3 equal amounts of ethylene were polymerized with respect to the solid catalyst component in terms of mass. Then, the supernatant was removed by decantation, washed 4 times with hexane, and then hexane was added to make the total volume 600 mL. Next, after raising the temperature in the system to 35 ° C., 1.9 g of a hexane solution of Chemistat 2500 (trade name, manufactured by Sanyo Chemical Industries, Ltd.), which is a higher fatty acid amide, was added as a component (G), and 2 Contacted for hours. Then, the supernatant was removed by decantation and washed 4 times with hexane. Next, the obtained hexane slurry was transferred to a glass filter, and hexane was distilled off by filtration and drying under reduced pressure to obtain 190.5 g of a prepolymerized solid catalyst component (X-4).

(Manufacturing of ethylene polymer)
Using a fluidized layer type gas phase polymerization reactor with an internal volume of 1.0 m ³ , the polymerization pressure is 1.7 MPa · A, the ethylene partial pressure is 1.0 MPa, the gas linear velocity is 0.7 m / s, and the catalyst supply amount is 4.0 g / hr. , Polymerization temperature 80 ° C., gas phase hydrogen / ethylene ratio 30 molppm / mol%, gas phase 1-hexene / ethylene ratio 0.0066, chemistat supply amount 0.40 g / hr. The solid catalyst component (X-4), ethylene, 1-hexene, hydrogen and Chemistat 2500 were continuously supplied. The polymerization reaction product was continuously withdrawn from the reactor and dried in a drying apparatus to obtain an ethylene polymer. The polymerization activity per transition metal was 4.1 × 10 ⁴ (g / mmol-Zr / hr).

In the obtained ethylene polymer, as a heat-resistant stabilizer, 6-tert-butyl-4- [3-[(2,4,8,10-tetra-tert-butyldibenzo [d, f] [1,3]) , 2] Dioxaphosfepine-6-yl) oxy) propyl] -2-methylphenol (trade name: Sumilyzer GP, manufactured by Sumitomo Chemical Co., Ltd.) 680 ppm, calcium stearate (manufactured by Nitto Kasei Kogyo Co., Ltd.) 170 ppm rice field. This is melt-kneaded using a 2-axis same-direction 46 mmφ extruder (manufactured by Ikegai Co., Ltd.) under the conditions of a set temperature of 200 ° C., a screw rotation speed of 300 rpm, and a feeder rotation speed of 30 rpm. Combined pellets were obtained. Physical properties were measured using the obtained pellets as a measurement sample. The results are shown in Table 6.

[Comparative Example 1]
(Preparation of solid catalyst component (X-5))
In a reactor with a stirrer having an internal volume of 200 mL sufficiently substituted with nitrogen, 30 mL of toluene and 2.45 mL of the slurry of the component (C-1) and the solid carrier (S-1) obtained in Synthesis Example 9 were placed in a nitrogen atmosphere. (Solid content mass 0.3 g) was charged. Then, without adding the component (A), 7.64 μmol of the toluene solution of the component (B-3) obtained in Synthesis Example 8 was added as Zr. After contacting them at an in-system temperature of 20 to 25 ° C. for 1 hour, the supernatant was removed by decantation, and the mixture was further washed twice with hexane. As a result, a slurry of the solid catalyst component (X-5) having a total volume of 40 mL was prepared.

(Manufacturing of ethylene polymer)
After adding 500 ml of heptane to a SUS autoclave with an internal volume of 1 liter sufficiently substituted with nitrogen under a nitrogen atmosphere, an ethylene / hydrogen mixed gas (hydrogen gas concentration 0.45 mol%) was circulated to flow the liquid phase and gas. The phase was saturated with an ethylene / hydrogen mixed gas. Next, 10 mL of 1-hexene, 0.375 mmol of triisobutylaluminum, and 200 mg of the solid catalyst component (X-5) as a solid component were charged, and then the temperature was raised to 80 ° C. and 0.8 MPaG, and the pressure was increased. , The polymerization reaction was carried out for 90 minutes. The obtained polymer was filtered and then vacuum dried at 80 ° C. for 10 hours to obtain 21.5 g of an ethylene polymer. The polymerization activity per transition metal was 2.8 × 10 ³ (g / mmol-Zr / hr). The obtained ethylene-based polymer was melt-kneaded and cooled by the same method as in Example 1, and the physical properties were measured using the obtained sample as a measurement sample. The results are shown in Table 6.

In Examples 1 to 4, the polymerization activity was higher than that in Comparative Example 1. Further, in Examples 1 to 4, the value of [η] is between * 1 and * 2, whereas in Comparative Example 1, the value of [η] is not between * 1 and * 2. rice field. From this, it was found that in Examples 1 to 4, an ethylene-based polymer having more long-chain branches than in Comparative Example 1, that is, having excellent molding processability could be efficiently produced.

Claims (7)

A catalyst for olefin polymerization containing the following component (A), the following component (B), and the following component (C).
Component (A); Cross-linked metallocene compound represented by the following formula (I)

(In formula (I), R ^{1 to} R ⁸ are monovalent groups, each independently a hydrogen atom or a hydrocarbon group , which may be the same or different from each other, but at least R ^{1 to} R ⁸ one is a hydrocarbon group having 3 to 8 carbon atoms, .Q ¹ remainder is a hydrocarbon group or a hydrogen atom is a divalent group, a hydrocarbon group, a halogen-containing group having 1 to 20 carbon atoms, a silicon It is a containing group, a germanium-containing group or a tin-containing group. X is a monovalent group and independently contains a hydrogen atom, a halogen atom, a hydrocarbon group, a halogen-containing group, a silicon-containing group, an oxygen-containing group and a sulfur-containing group. A group, a nitrogen-containing group or a phosphorus-containing group, which may be the same or different from each other. M is a titanium atom, a zirconium atom or a hafnium atom.)
Component (B); Double crosslinked metallocene compound represented by the following formula (II)

In formula (II), R ⁹ to R ¹² and R ¹⁴ are monovalent groups, each independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R ¹³ is a monovalent group. There, a hydrogen atom or an alkyl group having 4 to 8 carbon atoms, it may also be the same or different ^bur, all R 9 ^{to R 11} are not simultaneously hydrogen ^atoms, all R 12 ^{to R 14} simultaneously Adjacent groups of R ^{9 to} R ¹¹ may be bonded to each other to form a ring instead of a hydrogen atom. ^{Q 2} and Q ³ are divalent groups and are independently silicon-containing groups . , They may be the same or different from each other, or they may be bonded to each other to form a ring. X is a monovalent group, and each of them independently has a hydrogen atom, a halogen atom, a hydrocarbon group, and an anion ligand. , Or a neutral ligand that can be coordinated with an isolated electron pair. The anionic ligand is a halogen-containing group, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a phosphorus-containing group, or boron. It is a containing group, an aluminum-containing group or a conjugated diene-based divalent derivative group. X may be the same as or different from each other. M is a titanium atom, a zirconium atom or a hafnium atom.)
Component (C); (c-1) an organometallic compound represented by the following formula (III), (IV) or (V), (c-2) organoaluminum oxy compound, and (c-3) the component (c-3). a) or the component (B) at least one compound reacted with a compound to form an ion pair is selected from the group consisting of _{^{R a m Al (oR b)}} n H p X q (III)
(In formula (III), ^Ra and R ^b represent hydrocarbon groups having 1 to 15 carbon atoms, which may be the same or different from each other. X represents a halogen atom. M is 0 <m ≦ 3, n satisfies 0 ≦ n <3, p satisfies 0 ≦ p <3, q satisfies 0 ≦ q <3, and m + n + p + q = 3).
M ^a AlR ^a ₄ (IV)
(In the formula (IV), ^{M a} is Li, .R ^a indicating the Na or K represents a hydrogen atom or a hydrocarbon group having 1 to 15 carbon atoms.)
R ^a _r M ^b R ^b _s X _t (V)
(In the formula (V), ^Ra and R ^b represent hydrocarbon groups having 1 to 15 carbon atoms, which may be the same or different from each other. M ^b is Mg, Zn or Cd. X is a halogen. Indicates an atom. R is 0 <r ≦ 2, s is 0 ≦ s ≦ 1, t is 0 ≦ t ≦ 1, and r + s + t = 2). The catalyst for olefin polymerization according to claim 1, further comprising a solid carrier (S). The catalyst for olefin polymerization according to claim 2, wherein the component (A), the component (B) and the component (C) contain a solid catalyst component supported on the solid carrier (S). The component (C) and the component (A) are supported on the solid carrier (S), and the component (C) and the component (B) are supported on the solid carrier (S). The catalyst for olefin polymerization according to claim 2, which comprises the solid catalyst component obtained. The catalyst for olefin polymerization according to any one of claims 2 to 4, wherein the solid carrier (S) is a porous oxide. The catalyst for olefin polymerization according to any one of claims 1 to 5, wherein the component (C) is the organoaluminum oxy compound (c-2). A method for producing an ethylene-based polymer in which ethylene alone or ethylene and an olefin having 3 to 20 carbon atoms are polymerized in the presence of the catalyst for olefin polymerization according to any one of claims 1 to 6.