JP7783708B2 - Process for producing olefin polymer - Google Patents

Description

The present invention relates to a method for producing an olefin polymer.

Due to its excellent physical properties and formability, linear low-density polyethylene (LLDPE) is widely used, primarily for packaging applications such as laminating films, industrial films, heavy-duty packaging bags, tubes, and food packaging. The properties required of LLDPE vary depending on the molding method and application. For example, during inflation molding, a polymer with a narrow composition distribution is required to prevent stickiness (blocking) in molded products such as films. Ethylene-based polymers obtained using metallocene catalyst systems are known for their advantages, such as a narrow composition distribution and reduced blocking.

For example, Patent Document 1 discloses a method for polymerizing an olefinically unsaturated monomer using a metallocene in which one of the two cyclopentadienyl rings has a substituent with three or more carbon atoms and the other has two or more substituents, thereby obtaining a polymer product with a narrow composition distribution.

Furthermore, Patent Document 2 discloses an ethylene polymer with a narrow composition distribution obtained using a metallocene in which one of the two cyclopentadienyl rings is unsubstituted or has a substituent with at least three or more carbon atoms, and the other has at least one substituent selected from a methyl group, an ethyl group, and an aryl group.

On the other hand, when olefin polymers such as polyethylene, polypropylene, ethylene-α-olefin copolymer, and propylene-α-olefin copolymer are produced by (co)polymerizing olefins in the presence of a solid metallocene catalyst, gas-phase polymerization of olefins in the presence of a solid metallocene catalyst using a fluidized bed reactor can result in the generation of polymer lumps, sheets, etc. in the fluidized bed, or the fluidity of the polymer particles can decrease, resulting in an uneven mixing state in the fluidized bed and making it impossible to operate stably and continuously over the long term.

Furthermore, when slurry polymerization is carried out in the presence of such solid metallocene catalysts, polymer lumps and sheets may be generated inside the polymerization vessel, and polymer may adhere to the stirring blades, making it impossible to operate the vessel stably over the long term.

Patent Documents 3 and 4 describe how these problems can be solved by using a prepolymerized catalyst carrying an antistatic agent as a metallocene solid catalyst.

Special Publication No. 2000-514494 Japanese Patent Application Publication No. 10-251334 Japanese Patent Application Laid-Open No. 2000-297114 Japanese Patent Application Laid-Open No. 2001-48912

The ethylene polymers proposed in the above Patent Documents 1 and 2 have room for further improvement in terms of polymerization activity and suppression of fouling during polymerization.
An object of the present invention is to provide a method for producing an olefin polymer with high polymerization activity while suppressing fouling during polymerization, using a solid metallocene catalyst capable of producing an olefin polymer having a narrow composition distribution as disclosed in Patent Documents 1 and 2.

The present invention relates to, for example, the following [1] and [2].
[1]
(A) a transition metal compound represented by the following general formula (1),

[In general formula (1),
M is a transition metal atom of Group 4 of the periodic table;
n is an integer of 1 to 4 selected so that the transition metal compound (A) is electrically neutral;
X represents a hydrogen atom, a halogen atom, a hydrocarbon group, an anionic ligand, or a neutral ligand capable of coordinating with a lone electron pair, and 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, a boron-containing group, an aluminum-containing group, or a conjugated diene derivative group, and when n is 2 or more, the multiple groups represented by X may be the same or different and may be bonded to each other to form a ring;
R ¹ 's are each independently a hydrogen atom or a hydrocarbon group having 1 to 2 carbon atoms, at least two R ¹ 's are hydrocarbon groups having 1 to 2 carbon atoms, and adjacent R ¹ 's may be bonded to each other to form a ring which may have a substituent;
R2 ^'s are each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 40 carbon atoms, a halogen-containing group, a silicon-containing group, an oxygen-containing group, a nitrogen-containing group, or a sulfur-containing group, at least one ^R2 is a saturated hydrocarbon group having 3 to 10 carbon atoms in the linear portion or a terminally unsaturated hydrocarbon group having 3 to 10 carbon atoms in the linear portion, at least two ^R2 's are hydrogen atoms, and adjacent ^R2 's may be bonded to each other to form a ring which may have a substituent.]
(B) (B-1) organometallic compound,
(B-2) at least one compound selected from the group consisting of an organoaluminum oxy compound, and (B-3) a compound that reacts with the transition metal compound (A) to form an ion pair;
(C) Step (I) of contacting the catalyst with a particulate support to form a solid catalyst component;
(II) prepolymerizing an olefin in the presence of the solid catalyst component to form a prepolymerized solid catalyst component;
the prepolymerized solid catalyst component and an amine compound (D) represented by the following general formula (2):

[In general formula (2), ^R3 is a hydrocarbon group having 1 to 30 carbon atoms, and ^R4 is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. When there are multiple ^R4s , the multiple ^R4s are each independently defined as above. m and n are each independently an integer of 0 or greater, and m + n is 1 or greater.]
(III) forming a prepolymerized solid catalyst for olefin polymerization by contacting the solid catalyst with the olefin polymerization catalyst; and (IV) polymerizing an olefin in the presence of the prepolymerized solid catalyst for olefin polymerization.
A method for producing an olefin polymer comprising the steps of:

[2]
The method for producing an olefin polymer according to [1] above, wherein the step of polymerizing an olefin is a step of homopolymerizing ethylene or a step of copolymerizing ethylene with an α-olefin having from 3 to 20 carbon atoms.

According to the present invention, in a method for producing olefin polymers using a specific solid metallocene catalyst capable of producing olefin polymers with a narrow composition distribution, it is possible to produce olefin polymers with high polymerization activity while suppressing fouling during polymerization.

The process for producing an olefin polymer of the present invention will be explained in more detail below.
The method for producing an olefin polymer of the present invention comprises the steps of:
Step (I) of contacting a transition metal compound (A), a compound (B), and a particulate support (C) to form a solid catalyst component;
(II) prepolymerizing an olefin in the presence of the solid catalyst component to form a prepolymerized solid catalyst component;
a step (III) of contacting the prepolymerized solid catalyst component with an amine compound (D) to form a prepolymerized solid catalyst for olefin polymerization; and a step (IV) of polymerizing an olefin in the presence of the prepolymerized solid catalyst for olefin polymerization.
Contains:

<Step (I)>
In step (I), a transition metal compound (A), a compound (B), and a particulate support (C) are contacted to form a solid catalyst component.

(Transition metal compound (A))
The transition metal compound (A) is represented by the following general formula (1).

<M, n, X>
In formula (1), M is a Group 4 transition metal atom, preferably a zirconium atom or a hafnium atom, and more preferably a zirconium atom.

n is an integer of 1 to 4, preferably 1 or 2, that satisfies the valence of the transition metal atom M.
X is a hydrogen atom, a halogen atom, a hydrocarbon group, an anionic ligand, or a neutral ligand capable of coordinating with a lone electron pair, and 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, a boron-containing group, an aluminum-containing group, or a conjugated diene derivative group.

X is preferably a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group or an oxygen-containing group.
When n is 2 or more, the multiple Xs may be the same or different and may be bonded to each other to form a ring. When multiple rings are present, the rings may be the same or different.

The halogen atom includes fluorine, chlorine, bromine, iodine, etc., and is preferably chlorine or bromine.
Examples of the hydrocarbon group include:
linear or branched alkyl groups such as methyl, ethyl, 1-propyl, 1-butyl, 1-pentyl, 1-hexyl, 1-heptyl, 1-octyl, isopropyl, sec-butyl (butan-2-yl), tert-butyl (2-methylpropan-2-yl), isobutyl (2-methylpropyl), pentan-2-yl, 2-methylbutyl, isopentyl (3-methylbutyl), neopentyl (2,2-dimethylpropyl), cyamyl (1,2-dimethylpropyl), isohexyl (4-methylpentyl), 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, thexyl (2,3-dimethylbut-2-yl), and 4,4-dimethylpentyl;
linear or branched alkenyl groups or unsaturated double bond-containing groups such as a vinyl group, an allyl group, a propenyl group (prop-1-en-1-yl group), an iso-propenyl group (prop-1-en-2-yl group), an allenyl group (prop-1,2-dien-1-yl group), a but-3-en-1-yl group, a crotyl group (but-2-en-1-yl group), a but-3-en-2-yl group, a methallyl group (2-methylallyl group), a buta-1,3-dienyl group, a pent-4-en-1-yl group, a pent-3-en-1-yl group, a pent-2-en-1-yl group, an iso-pentenyl group (3-methylbut-3-en-1-yl group), a 2-methylbut-3-en-1-yl group, a pent-4-en-2-yl group, or a prenyl group (3-methylbut-2-en-1-yl group);
a straight-chain or branched alkynyl group or an unsaturated triple bond-containing group such as an ethynyl group, a prop-2-yn-1-yl group, or a propargyl group (prop-1-yn-1-yl group);
Aromatic-containing linear or branched alkyl groups and unsaturated double bond-containing groups such as benzyl group, 2-methylbenzyl group, 4-methylbenzyl group, 2,4,6-trimethylbenzyl group, 3,5-dimethylbenzyl group, cuminyl group (4-isopropylbenzyl group), 2,4,6-tri-isopropylbenzyl group, 4-tert-butylbenzyl group, 3,5-di-tert-butylbenzyl group, 1-phenylethyl group, and benzhydryl group (diphenylmethyl group);
cyclic saturated hydrocarbon groups such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cycloheptatrienyl group, a norbornyl group, a norbornenyl group, a 1-adamantyl group, and a 2-adamantyl group;
Examples of aromatic substituents include a phenyl group, a tolyl group (methylphenyl group), a xylyl group (dimethylphenyl group), a mesityl group (2,4,6-trimethylphenyl group), a cumenyl group (isopropylphenyl group), a duryl group (2,3,5,6-tetramethylphenyl group), a 2,6-di-isopropylphenyl group, a 2,4,6-tri-isopropylphenyl group, a 4-tert-butylphenyl group, a 3,5-di-tert-butylphenyl group, a naphthyl group, a biphenyl group, a terphenyl group, a binaphthyl group, an acenaphthalenyl group, a phenanthryl group, an anthracenyl group, a pyrenyl group, and a ferrocenyl group.

Among the above hydrocarbon groups, methyl, isobutyl, neopentyl, cyamyl, benzyl, phenyl, tolyl, xylyl, mesityl, and cumenyl groups are preferred.

Examples of the 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, a difluorophenyl group, a trifluorophenyl group, a tetrafluorophenyl group, a pentafluorophenyl group, a trifluoromethylphenyl group, a bistrifluoromethylphenyl group, and a hexachloroantimonate anion.

Among the halogen-containing groups, a pentafluorophenyl group is preferred.
Examples of the silicon-containing group include a trimethylsilyl group, a triethylsilyl group, a tri-isopropylsilyl group, a diphenylmethylsilyl group, a tert-butyldimethylsilyl group, a tert-butyldiphenylsilyl group, a triphenylsilyl group, a tris(trimethylsilyl)silyl group, and a trimethylsilylmethyl group.

Among the silicon-containing groups, a trimethylsilylmethyl group is preferred.
Examples of the oxygen-containing group include a hydroxyl group, a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an allyloxy group, an n-butoxy group, a sec-butoxy group, an iso-butoxy group, a tert-butoxy group, a benzyloxy group, a methoxymethoxy group, a phenoxy group, a 2,6-dimethylphenoxy group, a 2,6-di-iso-propylphenoxy group, a 2,6-di-tert-butylphenoxy group, a 2,4,6-trimethylphenoxy group, a 2,4,6-tri-iso-propylphenoxy group, an acetoxy group, a pivaloyloxy group, a benzoyloxy group, a trifluoroacetoxy group, a perchlorate anion, and a periodate anion.

Among the oxygen-containing groups, a methoxy group, an ethoxy group, an isopropoxy group, and a tert-butoxy group are preferred.
Examples of the sulfur-containing group include a mesyl group (methanesulfonyl group), a phenylsulfonyl group, a tosyl group (p-toluenesulfonyl group), a triflyl group (trifluoromethanesulfonyl group), a nonaflyl group (nonafluorobutanesulfonyl group), a mesylate group (methanesulfonate group), a tosylate group (p-toluenesulfonate group), a triflate group (trifluoromethanesulfonate group), and a nonaflate group (nonafluorobutanesulfonate group).

Among the sulfur-containing groups, triflate (trifluoromethanesulfonate) is preferred.
Examples of the 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, a dibenzylamino group, a pyrrolidinyl group, a piperidinyl group, a morpholyl group, a pyrrolyl group, and a bistriflylimide group.

Among the nitrogen-containing groups, a dimethylamino group, a diethylamino group, a pyrrolidinyl group, a pyrrolyl group, and a bistriflylimide group are preferred.
The phosphorus-containing group may, for example, be a hexafluorophosphate anion.

Examples of the boron-containing group include tetrafluoroborate anion, tetrakis(pentafluorophenyl)borate anion, (methyl)(tris(pentafluorophenyl))borate anion, (benzyl)(tris(pentafluorophenyl))borate anion, tetrakis((3,5-bistrifluoromethyl)phenyl)borate anion, and groups represented by BR ₄ (each R independently represents hydrogen, an alkyl group, an aryl group which may have a substituent, a halogen atom, or the like).

Examples of the aluminum-containing group include:

(M represents M in the general formula (1) above.)
Examples of suitable groups include groups represented by AlR ₄ (R represents hydrogen, an alkyl group, an aryl group which may have a substituent, a halogen atom, or the like) which can form the following formula:

Examples of the conjugated diene derivative group include a 1,3-butadienyl group, an isoprenyl group (2-methyl-1,3-butadienyl group), a piperylenyl group (1,3-pentadienyl group), a 2,4-hexadienyl group, a 1,4-diphenyl-1,3-pentadienyl group, a cyclopentadienyl group, and a metallocyclopentene group.

Examples of neutral ligands that can coordinate with lone electron pairs include ethers such as diethyl ether, tetrahydrofuran, dioxane, and 1,2-dimethoxyethane; amines such as triethylamine and diethylamine; heterocyclic compounds such as pyridine, picoline, lutidine, oxazoline, oxazole, thiazole, imidazole, and thiophene; and organophosphorus compounds such as triphenylphosphine, tricyclohexylphosphine, and tri-tert-butylphosphine.

<R ¹ >
In the general formula (1), each R ¹ is independently a hydrogen atom or a hydrocarbon group having 1 to 2 carbon atoms, and at least two, preferably four or more R ^1s are hydrocarbon groups having 1 to 2 carbon atoms.

Specific examples of the hydrocarbon group having 1 to 2 carbon atoms include a methyl group, an ethyl group, a vinyl group, and an ethynyl group. Of these, a methyl group and an ethyl group are preferred, and a methyl group is more preferred.

Adjacent R ¹ groups may be bonded to each other to form a ring which may have a substituent, or may not be bonded to each other, and preferably are not bonded to each other.
The ring is preferably a 5- or 6-membered ring, and examples of the structure formed by combining the ring with the cyclopentadienyl ring moiety of the mother nucleus include a tetrahydropentalenyl ring, a tetrahydroindenyl ring, a pentalenyl ring, and an indenyl ring.

<R ² >
R2 ^'s are each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 40 carbon atoms, a halogen-containing group, a silicon-containing group, an oxygen-containing group, a nitrogen-containing group, or a sulfur-containing group, at least one ^R2 is a saturated hydrocarbon group having 3 to 10 carbon atoms in the linear portion or a terminally unsaturated hydrocarbon group having 3 to 10 carbon atoms in the linear portion, and at least two ^R2 's are hydrogen atoms.

Adjacent R ² groups may be bonded to each other to form a ring which may have a substituent, or may not be bonded to each other, and preferably are not bonded to each other.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

Examples of the hydrocarbon group having 1 to 40 carbon atoms include hydrocarbon groups having 1 to 20 carbon atoms, and more specific examples include the hydrocarbon groups listed above as examples of X.

The hydrocarbon group having 1 to 40 carbon atoms is preferably a hydrocarbon group having 1 to 20 carbon atoms (excluding aromatic hydrocarbon groups) or an aromatic hydrocarbon group having 6 to 40 carbon atoms. The hydrocarbon group having 1 to 20 carbon atoms is preferably an aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms. The hydrocarbon group having 1 to 20 carbon atoms also includes substituents having an aromatic structure, such as an arylalkyl group.

Examples of the hydrocarbon group having 1 to 40 carbon atoms include:
Methyl group, ethyl group, 1-propyl group, 1-butyl group, 1-pentyl group, 1-hexyl group, 1-heptyl group, 1-octyl group, 1-nonyl group, 1-decanyl group, 1-undecanyl group, 1-dodecanyl group, 1-eicosanyl group, isopropyl group, sec-butyl group, tert-butyl group, isobutyl group, pentan-2-yl group, 2-methylbutyl group, isopentyl group, neopentyl group, tert-pentyl group (1,1-dimethylpropyl group), cyamyl group, pentan-3-yl group, 2-methylpentyl group, 3-methylpentyl group, isohexyl group, 1,1-dimethylbutyl group (2-methylpentan-2-yl group), 3-methylpentane linear or branched alkyl groups having 1 to 40 carbon atoms, such as 2-2-yl group, 4-methylpentan-2-yl group, 2,2-dimethylbutyl group, 2,3-dimethylbutyl group, 3,3-dimethylbutyl group, thexyl group, 3-methylpentan-3-yl group, 3,3-dimethylbut-2-yl group, hexane-3-yl group, 2-methylpentan-3-yl group, heptan-4-yl group, 2,4-dimethylpentan-2-yl group, 3-ethylpentan-3-yl group, 4,4-dimethylpentyl group, 4-methylheptan-4-yl group, 4-propylheptan-4-yl group, 2,3,3-trimethylbutan-2-yl group, and 2,4,4-trimethylpentan-2-yl group;
Vinyl group, allyl group, propenyl group, isopropenyl group, allenyl group, but-3-en-1-yl group, crotyl group, but-3-en-2-yl group, methallyl group, but-1,3-dienyl group, pent-4-en-1-yl group, pent-3-en-1-yl group, pent-2-en-1-yl group, isopentenyl group, 2-methylbut-3-en-1-yl group, pent-4-en-2-yl group, prenyl group, 2-methyl-but-2-en-1- yl group, pent-3-en-2-yl group, 2-methyl-but-3-en-2-yl group, pent-1-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-but-1,3-dien-1-yl group), penta-2,4-dien-2-yl group, hex-5-en-1-yl group, hex-4-en-1-yl group, hex-3-en- 1-yl group, hex-2-en-1-yl group, 4-methyl-pent-4-en-1-yl group, 3-methyl-pent-4-en-1-yl group, 2-methyl-pent-4-en-1-yl group, hex-5-en-2-yl group, 4-methyl-pent-3-en-1-yl group, 3-methyl-pent-3-en-1-yl group, 2,3-dimethyl-but-2-en-1-yl group, 2-methylpent-4-en-2-yl group, 3-ethylpent-1-en-3 linear or branched alkenyl groups or unsaturated double bond-containing groups having 2 to 40 carbon atoms, such as a 2-(cyclopentadienyl)-yl group, a hexa-3,5-dien-1-yl group, a hexa-2,4-dien-1-yl group, a 4-methylpenta-1,3-dien-1-yl group, a 2,3-dimethyl-buta-1,3-dien-1-yl group, a hexa-1,3,5-trien-1-yl group, a 2-(cyclopentadienyl)propan-2-yl group, or a 2-(cyclopentadienyl)ethyl group;

Ethynyl group, prop-2-yn-1-yl group, propargyl group, but-1-yn-1-yl group, but-2-yn-1-yl group, but-3-yn-1-yl group, pent-1-yn-1-yl group, pent-2-yn-1-yl group, pent-3-yn-1-yl group, pent-4-yn-1-yl group, 3-methyl-but-1-yn-1-yl group, pent-3-yn-2-yl group, 2-methyl-but-3-yn-1-yl group linear or branched alkynyl groups or unsaturated triple bond-containing groups having 2 to 40 carbon atoms, such as butan-1-yl group, pent-4-yn-2-yl group, hex-1-yn-1-yl group, 3,3-dimethyl-but-1-yn-1-yl group, 2-methyl-pent-3-yn-2-yl group, 2,2-dimethyl-but-3-yn-1-yl group, hex-4-yn-1-yl group, and hex-5-yn-1-yl group;
Benzyl group, 2-methylbenzyl group, 4-methylbenzyl group, 2,4,6-trimethylbenzyl group, 3,5-dimethylbenzyl group, cuminyl group, 2,4,6-tri-iso-propylbenzyl group, 4-tert-butylbenzyl group, 3,5-di-tert-butylbenzyl group, 1-phenylethyl group, benzhydryl group, cumyl 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-phenylphenyl phenylmethyl group, 4-phenylhepta-1,6-dien-4-yl group, 1,2,3-triphenylpropan-2-yl group, 1,1-diphenylethyl group, 1,1-diphenylpropyl group, 1,1-diphenyl-but-3-en-1-yl group, 1,1,2-triphenylethyl group, trityl group (triphenylmethyl group), tri-(4-methylphenyl)methyl 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-i so-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, cinnamyl group (3-phenylallyl group), neophyl group (2-methyl-2-phenylpropyl group), 3-methyl-3-phenylbutyl group, 2-methyl-4-phenylbutan-2-yl group, cyclopentadienyldiphenylmethyl group, 2-(1-indenyl)propan-2-yl group, (1-indenyl)diphenylmethyl group, 2-(1-indenyl)ethyl group, 2-(tetrahydro-1-indacenyl)propane- aromatic-containing linear or branched alkyl groups and unsaturated double bond-containing groups having 7 to 40 carbon atoms, such as a 2-yl group, a (tetrahydro-1-indacenyl)diphenylmethyl group, a 2-(tetrahydro-1-indacenyl)ethyl group, a 2-(1-benzoindenyl)propan-2-yl group, a (1-benzoindenyl)diphenylmethyl group, a 2-(1-benzoindenyl)ethyl group, a 2-(9-fluorenyl)propan-2-yl group, a (9-fluorenyl)diphenylmethyl group, a 2-(9-fluorenyl)ethyl group, a 2-(1-azulenyl)propan-2-yl group, a (1-azulenyl)diphenylmethyl group, and a 2-(1-azulenyl)ethyl group;

Cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclopentenyl group, cyclopentadienyl group, dimethylcyclopentadienyl group, 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-methylcyclohex Sil 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]heptan-2-yl group, 7-methylbicyclo[2.2.1]heptan-7-yl group, bicyclo[2.2.2]octan-1-yl group, bicyclo[2.2.2]octan-2-yl group, 1-adamantyl group, 2-adamantyl group, 1-(2-methyladamantyl), 1-(3-methyladamantyl), 1-(4-methyladamantyl), 1 cyclic saturated and unsaturated hydrocarbon groups having 3 to 40 carbon atoms, such as -(2-phenyladamantyl), 1-(3-phenyladamantyl), 1-(4-phenyladamantyl), 1-(3,5-dimethyladamantyl), 1-(3,5,7-trimethyladamantyl), 1-(3,5,7-triphenyladamantyl), pentalenyl group, indenyl group, fluorenyl group, indacenyl group, tetrahydroindacenyl group, benzoindenyl group, and azulenyl group;
Examples of aromatic substituents having 6 to 40 carbon atoms include a phenyl group, a tolyl group, a xylyl group, a mesityl group, a cumenyl group, a duryl group, a 2,6-di-iso-propylphenyl group, a 2,4,6-tri-iso-propylphenyl group, a 4-tert-butylphenyl group, a 3,5-di-tert-butylphenyl group, an allylphenyl group, a (but-3-en-1-yl)phenyl group, a (but-2-en-1-yl)phenyl group, a methallylphenyl group, a prenylphenyl group, a 4-adamantylphenyl group, a 3,5-di-adamantylphenyl group, a naphthyl group, a biphenyl group, a terphenyl group, a binaphthyl group, an acenaphthalenyl group, a phenanthryl group, an anthracenyl group, a pyrenyl group, and a ferrocenyl group.

Among the linear or branched alkyl groups having 1 to 40 carbon atoms, methyl, ethyl, 1-propyl, 1-butyl, 1-pentyl, 1-hexyl, 1-heptyl, 1-octyl, isopropyl, sec-butyl, tert-butyl, isobutyl, isopentyl, neopentyl, tert-pentyl, pentan-3-yl, isohexyl, 1,1-dimethylbutyl, 3,3-dimethylbutyl, thexyl, 3-methylpentan-3-yl, heptane-4 Preferred are methyl, ethyl, 1-propyl, 1-butyl, 1-pentyl, 1-hexyl, isopropyl, tert-butyl, neopentyl, 2,4-dimethylpentan-2-yl, and 2,4,4-trimethylpentan-2-yl groups, and more preferred are methyl, ethyl, 1-propyl, 1-butyl, 1-pentyl, 1-hexyl, isopropyl, tert-butyl, neopentyl, 2,4-dimethylpentan-2-yl, and 2,4,4-trimethylpentan-2-yl groups.

Among the linear or branched alkenyl groups or unsaturated double bond-containing groups having 2 to 40 carbon atoms, vinyl groups, allyl groups, but-3-en-1-yl groups, crotyl groups, methallyl groups, pent-4-en-1-yl groups, prenyl groups, penta-1,4-dien-3-yl groups, hex-5-en-1-yl groups, 2-methylpent-4-en-2-yl groups, 2-(cyclopentadienyl)propan-2-yl groups, and 2-(cyclopentadienyl)ethyl groups are preferred, with vinyl groups, allyl groups, but-3-en-1-yl groups, pent-4-en-1-yl groups, prenyl groups, and hex-5-en-1-yl groups being more preferred.

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

Among the aromatic-containing linear or branched alkyl groups and unsaturated double bond-containing groups having 7 to 40 carbon atoms, benzyl group, 2-methylbenzyl group, 4-methylbenzyl group, 2,4,6-trimethylbenzyl group, 3,5-dimethylbenzyl group, cuminyl group, 2,4,6-tri-iso-propylbenzyl group, 4-tert-butylbenzyl group, 3,5-di-tert-butylbenzyl group, benzhydryl group, cumyl group, 1,1-diphenylethyl group, trityl 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-t Preferred are 2-(3,5-di-tert-butylphenyl)ethyl, styryl, 2-methyl-1-phenylpropan-2-yl, 3-phenylpropyl, cinnamyl, neophyl, cyclopentadienyldiphenylmethyl, 2-(1-indenyl)propan-2-yl, (1-indenyl)diphenylmethyl, 2-(1-indenyl)ethyl, 2-(9-fluorenyl)propan-2-yl, (9-fluorenyl)diphenylmethyl, and 2-(9-fluorenyl)ethyl groups, with benzyl, benzhydryl, cumyl, 1,1-diphenylethyl, trityl, 2-phenylethyl, 3-phenylpropyl, and cinnamyl groups being more preferred.

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

Among the aromatic substituents having 6 to 40 carbon atoms, phenyl, tolyl, xylyl, mesityl, cumenyl, 2,6-di-isopropylphenyl, 2,4,6-tri-isopropylphenyl, 4-tert-butylphenyl, 3,5-di-tert-butylphenyl, allylphenyl, prenylphenyl, 4-adamantylphenyl, naphthyl, biphenyl, terphenyl, binaphthyl, phenanthyl, Tolyl, anthracenyl, and ferrocenyl groups are preferred, with phenyl, tolyl, xylyl, mesityl, cumenyl, 2,6-di-iso-propylphenyl, 2,4,6-tri-iso-propylphenyl, 4-tert-butylphenyl, 3,5-di-tert-butylphenyl, allylphenyl, 4-adamantylphenyl, naphthyl, biphenyl, phenanthryl, and anthracenyl groups being more preferred.

Examples of the halogen-containing group include a fluoromethyl group, a trifluoromethyl group, a trichloromethyl group, a pentafluoroethyl group, a 2,2,2-trifluoroethyl group, a heptafluoropropyl group, a 3,3,3-trifluoropropyl group, a nonafluorobutyl group, a 4,4,4-trifluorobutyl group, a dodecafluorohexyl group, a 6,6,6-trifluorohexyl group, a chlorophenyl group, a fluorophenyl group, a difluorophenyl group, a trifluorophenyl group, a tetrafluorophenyl group, a pentafluorophenyl group, a di-tert-butyl-fluorophenyl group, a trifluoromethylphenyl group, a bistrifluoromethylphenyl group, a trifluoromethoxyphenyl group, a bistrifluoromethoxyphenyl group, a trifluoromethylthiophenyl group, a bistrifluoromethylthiophenyl group, a fluorobiphenyl group, a difluorobiphenyl group, Examples include a trifluorobiphenyl group, a tetrafluorobiphenyl group, a pentafluorobiphenyl group, a di-tert-butyl-fluorobiphenyl group, a trifluoromethylbiphenyl group, a bistrifluoromethylbiphenyl group, a trifluoromethoxybiphenyl group, a bistrifluoromethoxybiphenyl group, a trifluoromethyldimethylsilyl group, a trifluoromethoxy group, a pentafluoroethoxy group, a fluorophenoxy group, a difluorophenoxy group, a trifluorophenoxy group, a pentafluorophenoxy group, a di-tert-butyl-fluorophenoxy group, a trifluoromethylphenoxy group, a bistrifluoromethylphenoxy group, a trifluoromethoxyphenoxy group, a bistrifluoromethoxyphenoxy group, a difluoromethylenedioxyphenyl group, a bistrifluoromethylphenyliminomethyl group, and a trifluoromethylthio group.

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

Examples of the silicon-containing group include a trimethylsilyl group, a triethylsilyl group, a tri-isopropylsilyl group, a diphenylmethylsilyl group, a tert-butyldimethylsilyl group, a tert-butyldiphenylsilyl group, a triphenylsilyl group, a tris(trimethylsilyl)silyl group, a cyclopentadienyldimethylsilyl group, a di-n-butyl(cyclopentadienyl)silyl group, a cyclopentadienyldiphenylsilyl group, an indenyldimethylsilyl group, and a di-n-butyl(indenyl )silyl group, indenyldiphenylsilyl group, fluorenyldimethylsilyl group, di-n-butyl(fluorenyl)silyl group, fluorenyldiphenylsilyl group, 4-trimethylsilylphenyl group, 4-triethylsilylphenyl group, 4-tri-iso-propylsilylphenyl group, 4-tert-butyldiphenylsilylphenyl group, 4-triphenylsilylphenyl group, 4-tris(trimethylsilyl)silylphenyl group, 3,5-bis(trimethylsilyl)phenyl group, etc.

Among the above silicon-containing groups, trimethylsilyl, triethylsilyl, tri-isopropylsilyl, tert-butyldimethylsilyl, triphenylsilyl, cyclopentadienyldimethylsilyl, cyclopentadienyldiphenylsilyl, indenyldimethylsilyl, indenyldiphenylsilyl, fluorenyldimethylsilyl, fluorenyldiphenylsilyl, 4-trimethylsilylphenyl, 4-triethylsilylphenyl, 4-tri-isopropylsilylphenyl, 4-triphenylsilylphenyl, and 3,5-bis(trimethylsilyl)phenyl groups are preferred, with trimethylsilyl, triethylsilyl, tert-butyldimethylsilyl, 4-trimethylsilylphenyl, 4-triethylsilylphenyl, 4-tri-isopropylsilylphenyl, and 3,5-bis(trimethylsilyl)phenyl groups being more preferred.

The oxygen-containing group is preferably a hydroxyl group or an oxygen-containing group having 1 to 20 carbon atoms. Examples of the latter include a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an allyloxy group, an n-butoxy group, a sec-butoxy group, an iso-butoxy group, a tert-butoxy group, a methallyloxy group, a prenyloxy group, a benzyloxy group, a methoxymethoxy group, a methoxyethoxy group, a phenoxy group, a naphthoxy group, a toluyloxy group, an iso-propylphenoxy group, an allylphenoxy group, a tert-butylphenoxy group, a methoxyphenoxy group, an iso-propoxyphenoxy group, an allyloxyphenoxy group, a biphenyloxy group, a binaphthyloxy group, a methoxymethyl group, an allyloxymethyl group, a benzyloxymethyl group, a phenoxymethyl group, a methoxyethyl group, an allyloxyethyl group, a benzyloxyethyl group, and a phenoxy. Examples of such groups include ethyl, methoxypropyl, allyloxypropyl, benzyloxypropyl, phenoxypropyl, methoxyvinyl, allyloxyvinyl, benzyloxyvinyl, phenoxyvinyl, methoxyallyl, allyloxyallyl, benzyloxyallyl, phenoxyallyl, dimethoxymethyl, di-iso-propoxymethyl, dioxolanyl, tetramethyldioxolanyl, dioxanyl, methoxyphenyl, iso-propoxyphenyl, allyloxyphenyl, phenoxyphenyl, methylenedioxyphenyl, 3,5-dimethyl-4-methoxyphenyl, 3,5-di-tert-butyl-4-methoxyphenyl, furyl, methylfuryl, tetrahydrofuryl, pyranyl, tetrahydropyranyl, furofuryl, benzofuryl, and dibenzofuryl groups.

Among the oxygen-containing groups, methoxy, ethoxy, iso-propoxy, allyloxy, n-butoxy, tert-butoxy, prenyloxy, benzyloxy, phenoxy, naphthoxy, toluyloxy, iso-propylphenoxy, allylphenoxy, tert-butylphenoxy, methoxyphenoxy, biphenyloxy, binaphthyloxy, allyloxymethyl, benzyloxymethyl, phenoxymethyl, methoxyethyl, methoxyallyl, benzyloxyallyl, phenoxyallyl, dimethoxymethyl, dioxolanyl, tetramethyldioxolanyl, dioxanyl, dimethyldioxanyl, methoxyphenyl, iso-propoxyphenyl, allyloxy, Preferred are diphenyl, phenoxyphenyl, methylenedioxyphenyl, 3,5-dimethyl-4-methoxyphenyl, 3,5-di-tert-butyl-4-methoxyphenyl, furyl, methylfuryl, tetrahydropyranyl, furofuryl, benzofuryl, and dibenzofuryl groups, with methoxy, iso-propoxy, tert-butoxy, allyloxy, phenoxy, dimethoxymethyl, dioxolanyl, methoxyphenyl, iso-propoxyphenyl, allyloxyphenyl, phenoxyphenyl, 3,5-dimethyl-4-methoxyphenyl, 3,5-di-tert-butyl-4-methoxyphenyl, furyl, methylfuryl, benzofuryl, and dibenzofuryl groups being more preferred.

The nitrogen-containing group is preferably an amino group or a nitrogen-containing group having 1 to 20 carbon atoms. Examples of the latter include a dimethylamino group, a diethylamino group, an allylamino group, a diallylamino group, a didecylamino group, a benzylamino group, a dibenzylamino group, a pyrrolidinyl group, a piperidinyl group, a morpholyl group, an azepinyl group, a dimethylaminomethyl group, a dibenzylaminomethyl group, a pyrrolidinylmethyl group, a dimethylaminoethyl group, a benzylaminomethyl group, a benzylaminoethyl group, a pyrrolidinylethyl group, a dimethylaminovinyl group, a benzylaminovinyl group, a pyrrolidinylvinyl group, a dimethylaminopropyl group, a benzylaminopropyl group, a pyrrolidinylpropyl group, a dimethylaminoallyl group, a benzylaminoallyl group, a pyrrolidinylallyl group, an aminophenyl group, a dimethylaminophenyl group, and 3,5-dimethyl-4 -dimethylaminophenyl group, 3,5-di-iso-propyl-4-dimethylaminophenyl group, julolidinyl group, tetramethyljulolidinyl group, pyrrolidinylphenyl group, pyrrolylphenyl group, pyridylphenyl group, quinolylphenyl group, isoquinolylphenyl group, indolinylphenyl group, indolylphenyl group, carbazolylphenyl group, di-tert-butylcarbazolylphenyl group, pyrrolyl group, methylpyrrolyl group, phenylpyrrolyl group, pyridyl group, quinolyl group, tetrahydroquinolyl group, iso-quinolyl group, tetrahydro-iso-quinolyl group, indolyl group, indolinyl group, carbazolyl group, di-tert-butylcarbazolyl group, imidazolyl group, dimethylimidazolidinyl group, benzimidazolyl group, oxazolyl group, oxazolidinyl group, benzoxazolyl group, and the like.

Among the nitrogen-containing groups, amino group, dimethylamino group, diethylamino group, allylamino group, benzylamino group, dibenzylamino group, pyrrolidinyl group, piperidinyl group, morpholyl group, dimethylaminomethyl group, benzylaminomethyl group, pyrrolidinylmethyl group, dimethylaminoethyl group, pyrrolidinylethyl group, dimethylaminopropyl group, pyrrolidinylpropyl group, dimethylaminoallyl group, pyrrolidinylallyl group, aminophenyl group, dimethylaminophenyl group, 3,5-dimethyl-4-dimethylaminophenyl group, 3,5-di-iso-propyl-4-dimethylaminophenyl group, julolidinyl group, tetramethyljulolidinyl group, pyrrolidinylphenyl group, pyrrolylphenyl group, carbazolylphenyl group, and di-tert-butylcarbazolyl Phenyl groups, pyrrolyl groups, pyridyl groups, quinolyl groups, tetrahydroquinolyl groups, isoquinolyl groups, tetrahydro-isoquinolyl groups, indolyl groups, indolinyl groups, carbazolyl groups, di-tert-butylcarbazolyl groups, imidazolyl groups, dimethylimidazolidinyl groups, benzimidazolyl groups, oxazolyl groups, oxazolidinyl groups, and benzoxazolyl groups are preferred, with amino groups, dimethylamino groups, diethylamino groups, pyrrolidinyl groups, dimethylaminophenyl groups, 3,5-dimethyl-4-dimethylaminophenyl groups, 3,5-di-iso-propyl-4-dimethylaminophenyl groups, julolidinyl groups, tetramethyljulolidinyl groups, pyrrolidinylphenyl groups, pyrrolyl groups, pyridyl groups, carbazolyl groups, and imidazolyl groups being more preferred.

Examples of the sulfur-containing group include a methylthio group, an ethylthio group, a benzylthio group, a phenylthio group, a naphthylthio group, a methylthiomethyl group, a benzylthiomethyl group, a phenylthiomethyl group, a naphthylthiomethyl group, a methylthioethyl group, a benzylthioethyl group, a phenylthioethyl group, a naphthylthioethyl group, a methylthiovinyl group, a benzylthiovinyl group, a phenylthiovinyl group, a naphthylthiovinyl group, a methylthiopropyl group, a benzylthiopropyl group, a phenylthiopropyl group, a naphthylthiopropyl group, a methylthioallyl group, a benzylthioallyl group, a phenyl Examples include thioallyl group, naphthylthioallyl group, mercaptophenyl group, methylthiophenyl group, thienylphenyl group, methylthienylphenyl group, benzothienylphenyl group, dibenzothienylphenyl group, benzodithienylphenyl group, thienyl group, tetrahydrothienyl group, methylthienyl group, thienofuryl group, thienothienyl group, benzothienyl group, dibenzothienyl group, thienobenzofuryl group, benzodithienyl group, dithiolanyl group, dithianyl group, oxathiolanyl group, oxathianyl group, thiazolyl group, benzothiazolyl group, and thiazolidinyl group.

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

At least one of ^R2 is a saturated hydrocarbon group having 3 to 10 carbon atoms in the linear portion or a terminally unsaturated hydrocarbon group having 3 to 10 carbon atoms in the linear portion, and is preferably a saturated hydrocarbon group having 3 to 10 carbon atoms in the linear portion.

A saturated hydrocarbon group having a linear portion containing 3 to 10 carbon atoms is a saturated hydrocarbon group having a linear hydrocarbon group containing 3 to 10 carbon atoms. Examples include n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, isobutyl, sec-butyl, tert-pentyl, 2-methylpentan-2-yl, 1-ethylcyclopentyl, 1-(n-propyl)cyclopentyl, 1-ethylcyclohexyl, and 1-(n-propyl)cyclohexyl groups, with n-propyl, n-butyl, n-pentyl, and n-hexyl groups being preferred.

A terminally unsaturated hydrocarbon group having 3 to 10 carbon atoms in the linear portion is a hydrocarbon group having a linear hydrocarbon group having 3 to 10 carbon atoms and an unsaturated bond at the end. Examples include allyl, but-3-en-1-yl, methallyl, pent-4-en-1-yl, hex-5-en-1-yl, hept-6-en-1-yl, oct-7-en-1-yl, and non-8-en-1-yl. Examples include dec-9-en-1-yl, 2-methylbut-3-en-2-yl, 2-methylpent-4-en-2-yl, 1-vinylcyclopentyl, 1-allylcyclopentyl, 1-vinylcyclohexyl, and 1-allylcyclohexyl groups, with allyl, but-3-en-1-yl, pent-4-en-1-yl, and hex-5-en-1-yl being preferred.

Adjacent ^R2s may be bonded to each other to form a saturated ring which may have a substituent. The ring formed is preferably a 5- to 8-membered ring which is fused to the cyclopentadienyl ring moiety and which may have a substituent. When multiple rings are present, these may be the same or different. Although not particularly limited as long as the effects of the present invention are achieved, the ring is more preferably a 5- or 6-membered ring. Examples of structures formed by combining the ring and the cyclopentadienyl ring moiety of the mother nucleus include a tetrahydropentalenyl ring, a tetrahydroindenyl ring, a pentalenyl ring, an indenyl ring, and an azulenyl ring (which may have a substituent).

<Preferred Embodiments of Transition Metal Compound (A)>
A preferred embodiment of the transition metal (A) is a transition metal compound represented by the general formula (1), in which M is a zirconium atom or a hafnium atom, and Xs are each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, or an oxygen-containing group.

A more preferred embodiment from the viewpoint of ^R1 is a transition metal compound represented by the general formula (1) in which ^R1 is each independently a hydrogen atom or a methyl group, at least two ^R1s are methyl groups, and the remaining ^R1 is a hydrogen atom or a methyl group.

A more preferred embodiment from the viewpoint of ^R2 is a transition metal compound represented by the general formula (1) in which ^R2 are each independently a hydrogen atom or a hydrocarbon group having 1 to 40 carbon atoms, at least one ^R2 is a saturated hydrocarbon group or a terminally unsaturated hydrocarbon group having a linear portion having 3 to 10 carbon atoms, and at least two ^R2 are hydrogen atoms.

A more preferred embodiment from the viewpoint of ^R2 is a transition metal compound represented by the general formula (1) in which ^R2 are each independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, at least one ^R2 is a saturated hydrocarbon group or a terminally unsaturated hydrocarbon group having a linear portion having 3 to 10 carbon atoms, at least two ^R2 are hydrogen atoms, and the remaining ^R2 is a hydrogen atom or a methyl group.

<Examples of transition metal compound (A)>
Specific examples of the transition metal compound (A) include:
(n-propylcyclopentadienyl)(tetramethylcyclopentadienyl)zirconium dichloride,
(n-butylcyclopentadienyl)(tetramethylcyclopentadienyl)zirconium dichloride,
(n-propylcyclopentadienyl)(pentamethylcyclopentadienyl)zirconium dichloride,
(n-butylcyclopentadienyl)(pentamethylcyclopentadienyl)zirconium dichloride,
(1,3-dimethylcyclopentadienyl)(1-n-butyl-3-methylcyclopentadienyl)zirconium dichloride,
Substitution of titanium or hafnium for zirconium in these compounds;
Examples include compounds in which the dichloride in these compounds is replaced by dimethyl.

In the method for producing an olefin polymer of the present invention, the transition metal compound (A) may be used alone or in combination of two or more types. Furthermore, one optical isomer having the same chemical structure may be used alone, or a mixture of optical isomers (e.g., a meso mixture or a racemic mixture) may be used.

(Compound (B))
Compound (B) is
(B-1) organometallic compound,
(B-2) At least one compound selected from the group consisting of organoaluminum oxy compounds and (B-3) compounds that react with the transition metal compound (A) to form an ion pair.

The organometallic compound (B-1) may be an organometallic compound represented by the following general formula (B-1a), (B-1b) or (B-1c).
R ^a _m Al (OR ^b ) _n H _p X _q … (B-1a)
[In general formula (B-1a), R ^a and R ^b represent a hydrocarbon group having 1 to 15 carbon atoms and may be the same or different from each other, X represents a halogen atom, m is a number that satisfies 0<m≦3, n is a number that satisfies 0≦n<3, p is a number that satisfies 0≦p<3, q is a number that satisfies 0≦q<3, and m+n+p+q=3.]
M ^a AlR ^a ₄ … (B-1b)
[In general formula (B-1b), M ^a represents Li, Na, or K, and R ^a represents a hydrocarbon group having 1 to 15 carbon atoms.]
R ^a _r M ^b R ^b _s X _t … (B-1c)
[In general formula (B-1c), R ^a and R ^b represent a hydrocarbon group having 1 to 15 carbon atoms and may be the same or different; M ^b is selected from Mg, Zn, and Cd; X represents a halogen atom; r represents 0<r≦2; s represents 0≦s≦1; t represents 0≦t≦1; and r+s+t=2.]
As the organometallic compound (B-1), compounds disclosed in JP-A No. 11-315109 and EP 0874005A can be used without any restrictions.

The organometallic compound (B-1) is preferably one represented by general formula (B-1a), and specific examples thereof include trialkylaluminums such as trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, and tri-2-ethylhexylaluminum; dialkylaluminum halides such as dimethylaluminum chloride, diethylaluminum chloride, diisopropylaluminum chloride, diisobutylaluminum chloride, and dimethylaluminum bromide; alkylaluminum sesquihalides such as methylaluminum sesquichloride, ethylaluminum sesquichloride, isopropylaluminum sesquichloride, butylaluminum sesquichloride, and ethylaluminum sesquibromide; methylaluminum dichloride; ethylaluminum dichloride; Examples of suitable aluminum hydrides include alkyl aluminum dihalides such as dimethyl aluminum hydride, diethyl aluminum hydride, dihydrophenyl aluminum hydride, diisopropyl aluminum hydride, di-n-butyl aluminum hydride, diisobutyl aluminum hydride, diisohexyl aluminum hydride, diphenyl aluminum hydride, dicyclohexyl aluminum hydride, di-sec-heptyl aluminum hydride, and di-sec-nonyl aluminum hydride; and dialkyl aluminum alkoxides such as dimethyl aluminum ethoxide, diethyl aluminum ethoxide, diisopropyl aluminum methoxide, and diisobutyl aluminum ethoxide.

These may be used alone or in combination of two or more.
As the organoaluminum oxy compound (B-2), aluminoxanes prepared from trialkylaluminum or tricycloalkylaluminum are preferred, and organoaluminum oxy compounds prepared from trimethylaluminum or triisobutylaluminum are particularly preferred. These organoaluminum oxy compounds may be used alone or in combination of two or more.

As compound (B-3), Lewis acids, ionic compounds, borane compounds, and carborane compounds, as well as heteropoly compounds and isopoly compounds, described in, for example, JP-T-1-501950, JP-T-1-502036, JP-A-3-179005, JP-A-3-179006, JP-A-3-207703, JP-A-3-207704, and U.S. Pat. No. 5,321,106, can be used without limitation.

When used in combination with an organoaluminum oxy compound (B-2) such as methylaluminoxane as a cocatalyst component, the ethylene polymerization catalyst of the present invention not only exhibits extremely high catalytic activity toward ethylene, but also reacts with active hydrogen in the solid support to easily prepare a solid support component containing the cocatalyst component. Therefore, it is preferable to use an organoaluminum oxy compound (B-2) as the (B) compound.

(Fine particle carrier (C))
The fine particle carrier (C) is an inorganic or organic compound, and is a granular or fine particle solid.

Inorganic compounds used as the particulate support (C) include porous oxides, solid aluminoxane compounds, inorganic chlorides, clays, clay minerals, and ion-exchange layered compounds.

_{The porous oxides that can be used include SiO2, Al2O3, MgO, ZrO, TiO2, B2O3 , CaO , ZnO ,} BaO, and _ThO2 , as well as composites or mixtures containing these, specifically natural or synthetic zeolites, _SiO2 -MgO, _SiO2 - _Al2O3 , SiO2- _TiO2 , _{SiO2 - V2O5} , _{SiO2 - Cr2O3 ,} and _SiO2 - _TiO2 -MgO. Of these, _{those containing SiO2 as} the main component are preferred.

The porous oxide may contain small amounts of carbonates, _sulfates , _nitrates , _and oxides such as _Na2CO3 , _K2CO3 , _CaCO3 , _MgCO3 , _{Na2SO4 , Al2} ( _SO4 ) ₃ , BaSO4, _KNO3 , Mg( _NO3 ) ₂ , Al( _NO3 ) ₃ , _Na2O , _K2O , and _Li2O .

Although the properties of such porous oxides vary depending on the type and production method, the particulate support (C) used in the present invention preferably has a particle size of usually 0.2 to 300 μm, preferably 1 to 200 μm, a specific surface area of usually 50 to 1200 ^m /g, preferably 100 to 1000 ^m /g, and a pore volume of usually 0.3 to 30 ^cm /g. Such supports are calcined, if necessary, at, for example, 100 to 1000° C., preferably 150 to 700° C. before use.

The solid aluminoxane compound can be any known solid aluminoxane without limitation. For example, the solid polyaluminoxane composition described in WO 2014/123212 and the solid aluminoxane compounds described in paragraphs [0119] to [0129] of JP 2019-69920 A can be used. Known production methods include those described in JP-B-7-42301, JP-A-6-220126, JP-A-6-220128, JP-A-11-140113, JP-A-11-310607, JP-A-2000-38410, JP-A-2000-95810, and WO 2010/55652.

Examples of the inorganic halide include _MgCl2 , _MgBr2 , _MnCl2 , and _MnBr2 . The inorganic halide may be used as is, or may be used after being pulverized using a ball mill or a vibration mill. Alternatively, the inorganic halide may be dissolved in a solvent such as alcohol and then precipitated into fine particles using a precipitating agent.

Clay is usually composed primarily of clay minerals. Ion-exchangeable layered compounds are compounds with a crystalline structure in which planes formed by ionic bonds or other factors are stacked parallel to one another with weak bonding forces, and the ions they contain are exchangeable. Most clay minerals are ion-exchangeable layered compounds. These clays, clay minerals, and ion-exchangeable layered compounds are not limited to naturally occurring substances; synthetic compounds can also be used.

Examples of clays, clay minerals, or ion-exchangeable layered compounds include clays, clay minerals, and ionic crystalline compounds having layered crystal structures such as hexagonal close packing type, antimony type, CdCl ₂ type, and CdI ₂ type.

Examples of such clays and clay minerals include kaolin, bentonite, kibushi clay, gairome clay, allophane, hisingerite, pyrophyllite, ummo group, montmorillonite group, vermiculite, ryokudeite group, palygorskite, kaolinite, nacrite, dickite, halloysite, and the like. Examples of ion-exchange layered compounds include α-Zr(HAsO ₄ ) ₂ ·H ₂ O, α-Zr(HPO ₄ ) ₂ , α-Zr(KPO ₄ ) ₂ ·3H ₂ O, α-Ti(HPO ₄ ) ₂ , α-Ti(HAsO ₄ ) ₂ ·H ₂ O, α-Sn(HPO ₄ ) ₂ ·H ₂ O, γ-Zr(HPO ₄ ) ₂ , γ-Ti(HPO ₄ ) ₂ and crystalline acid salts of polyvalent metals such as γ-Ti(NH ₄ PO ₄ ) ₂ ·H ₂ O.

Such clays, clay minerals, or ion-exchange layered compounds preferably have a pore volume of 0.1 cc/g or more, particularly 0.3 to 5 cc/g, having a radius of 20 Å or more as measured by mercury intrusion porosimetry. Here, the pore volume is measured by mercury intrusion porosimetry using a mercury porosimeter over a pore radius range of 20 to 3×10 ⁴ Å. When a carrier having a pore volume of less than 0.1 cc/g having a radius of 20 Å or more is used, it tends to be difficult to obtain high polymerization activity.

It is also preferable to chemically treat clay and clay minerals. Chemical treatments include surface treatments that remove impurities from the surface and treatments that affect the crystalline structure of the clay. Specific examples of chemical treatments include acid treatment, alkali treatment, salt treatment, and organic treatment. Acid treatment not only removes surface impurities, but also increases the surface area by eluting cations such as Al, Fe, and Mg from the crystalline structure. Alkali treatment destroys the crystalline structure of the clay, resulting in structural changes. Salt treatment and organic treatment also form ionic complexes, molecular complexes, organic derivatives, and the like, which can change the surface area and interlayer distance.

The ion-exchangeable layered compound may be a layered compound in which the interlayer spacing is expanded by utilizing the ion exchange property and exchanging the exchangeable ions between the layers with other large, bulky ions. Such bulky ions act as supports supporting the layered structure and are commonly called pillars. The introduction of another substance between the layers of a layered compound is called intercalation. Examples of guest compounds to be intercalated include cationic inorganic compounds such as _TiCl4 and ZrCl4, metal alkoxides such as Ti(OR) ₄ , Zr(OR) ₄ , PO(OR) ₃ , _and B(OR) ₃ (where R is a hydrocarbon group, etc.), _and metal hydroxide ions such as [ _Al13O4 (OH) ₂₄ ] ⁷⁺ , [ _Zr4 (OH) ₁₄ ] ²⁺ , and [ _Fe3O ( _OCOCH3 ) ₆ ] ⁺ . These compounds may be used alone or in combination of two or more. Furthermore, when these compounds are intercalated, polymers obtained by hydrolysis of metal alkoxides (R is a hydrocarbon group or the like) such as Si(OR) ₄ , Al(OR) ₃ , and Ge(OR) ₄ , and colloidal inorganic compounds such as SiO ₂ can also be present. Examples of pillars include oxides produced by intercalating the above metal hydroxide ions between layers and then dehydrating them with heat.

The clays, clay minerals, and ion-exchange layered compounds may be used as is, or after treatment such as ball milling or sieving. They may also be used after adding and adsorbing new water or after heat dehydration. Furthermore, they may be used alone or in combination of two or more types.

Examples of organic compounds used as the particulate carrier (C) include granular or particulate solids having a particle size in the range of 10 to 300 μm. Specific examples of the organic compound include polymers produced mainly from olefins having 2 to 14 carbon atoms, such as ethylene, propylene, 1-butene, and 4-methyl-1-pentene, polymers and reactants produced mainly from vinylcyclohexane, styrene, and divinylbenzene, and granular or particulate solids made of modified products thereof.
As the particulate carrier (C), a porous oxide is preferred from the viewpoint of preventing foreign matter during molding.

<Usage and addition order of each ingredient>
In step (I), the transition metal compound (A) (hereinafter also referred to as component (A)), the compound (B) (hereinafter also referred to as component (B)), and the particulate support (C) (hereinafter also referred to as component (C)) are contacted, for example, by mixing and contacting them in an inert hydrocarbon, to form a solid catalyst component.

As a method for contacting each component, when paying attention to the order of contact, for example,
(i) a method of contacting component (C) with component (B) and then with component (A); (ii) a method of contacting component (A) with component (B) and then with component (C); (iii) a method of contacting component (C) with component (B) and then with a mixture of component (A) and component (B);
(iv) A method in which component (C) is contacted with component (B), then with component (B), and then with a mixture of component (A) and component (B). When multiple types of component (B) are used, the components (B) may be the same or different. Of the above methods, (i) and (ii) are preferred.

In each of the methods showing the contact order form described above, in the step involving contact of component (C) with component (B) and the step involving contact of component (C) with component (A), the coexistence of component (G) suppresses fouling during the polymerization reaction and improves the particle properties of the resulting polymer. Component (G) can be a compound having a polar functional group, preferably a nonionic surfactant, and more preferably a polyalkylene oxide block, higher aliphatic amide, polyalkylene oxide, polyalkylene oxide alkyl ether, alkyldiethanolamine, polyoxyalkylene alkylamine, glycerin fatty acid ester, or N-acylamino acid. These may be used alone or in combination of two or more.

Solvents used in preparing the solid catalyst component include inert hydrocarbon solvents, such as aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; alicyclic hydrocarbons such as cyclopentane, cyclohexane, and methylcyclopentane; aromatic hydrocarbons such as benzene, toluene, and xylene; halogenated hydrocarbons such as ethylene chloride, chlorobenzene, and dichloromethane; and mixtures of these.

When components (B) and (C) contact each other, reactive sites in component (B) react with reactive sites in component (C) to form a chemical bond, forming a contact product of components (B) and (C). The contact time between components (B) and (C) is typically 1 minute to 20 hours, preferably 30 minutes to 10 hours, and the contact temperature is typically -50 to 200°C, preferably -20 to 120°C. If components (B) and (C) are initially contacted too quickly, the heat generated by the reaction and the reaction energy can cause component (C) to collapse, deteriorating the morphology of the resulting solid catalyst component. When used in polymerization, this often results in poor polymer morphology, making continuous operation difficult. Therefore, it is preferable to initially contact components (B) and (C) at a lower temperature to suppress the heat generated by the reaction, or to control the heat generated by the reaction and react at a rate that maintains the initial contact temperature. The same applies when components (B) and (C) are first contacted and then component (B) is subsequently contacted. The contact weight ratio between component (B) and component (C) (weight of component (B)/weight of component (C)) can be selected arbitrarily, but a higher contact weight ratio allows more component (A) to be contacted, improving the catalytic activity per weight of the solid catalyst component.

The contact weight ratio of component (B) to component (C) [= weight of component (B) / weight of component (C)] is
It is preferably 0.05 to 3.0, and particularly preferably 0.1 to 2.0.
When the contact product of component (B) and component (C) is contacted with component (A), the contact time is usually 1 minute to 20 hours, and preferably 1 minute to 10 hours, and the contact temperature is usually within the range of −50 to 200° C., and preferably −50 to 100° C.

Component (B-1) is used in an amount such that the molar ratio of component (B-1) to the total transition metal atoms (M) in component (A) [(B-1)/M] is typically 0.01 to 100,000, preferably 0.05 to 50,000.

Component (B-2) is used in an amount such that the molar ratio of component (B-2) (in terms of aluminum atoms) to the total transition metal atoms (M) in component (A) [(B-2)/M] is generally 10 to 500,000, preferably 20 to 100,000.

Component (B-3) is used in an amount such that the molar ratio of component (B-3) to the total transition metal atoms (M) in component (A) [(B-3)/M] is generally 1 to 10, preferably 1 to 5.
The ratio of component (B) to the total transition metal atoms (M) in component (A) can be determined by inductively coupled plasma emission spectrometry (ICP analysis).

<Step (II)>
In step (II), an olefin is prepolymerized in the presence of the solid catalyst component formed in step (I) to form a prepolymerized solid catalyst component. The prepolymerized solid catalyst component is formed from the solid catalyst component formed in step (I) and an olefin polymer produced by prepolymerization.

The prepolymerized solid catalyst component can be prepared by prepolymerizing an olefin in the presence of the solid catalyst component, typically in an inert hydrocarbon solvent. The prepolymerization can be carried out batchwise, semi-continuously, or continuously, and can be carried out under reduced, normal, or elevated pressure. Furthermore, it is desirable that the prepolymerized solid catalyst component be produced in an amount of 0.01 to 1,000 g, preferably 0.1 to 800 g, and more preferably 0.2 to 500 g, per gram of the solid catalyst component.

Examples of the inert hydrocarbon solvent include the same inert hydrocarbon solvents as those used in step (I).
The prepolymerized solid catalyst component produced in the inert hydrocarbon solvent may be separated from the suspension and then resuspended in the inert hydrocarbon, and the olefin may be introduced into the resulting suspension. Alternatively, the olefin may be introduced into the suspension after drying.

The prepolymerization temperature is −20 to 80° C., preferably 0 to 60° C., and the prepolymerization time is about 0.5 to 100 hours, preferably about 1 to 50 hours.
The form of the solid catalyst component used in the prepolymerization can be any of those already mentioned above, without any limitations. Furthermore, during the prepolymerization, component (B) is used together with the solid catalyst component as needed, and in particular, an organoaluminum compound [B-1a] represented by general formula (B-1a) is preferably used. When component (B) is used, component (B) used together with the solid catalyst component is used in an amount such that the molar ratio (Al/M) of aluminum atoms (Al) in component (B) to transition metal atoms (M) in the transition metal compound (A) is 0.1 to 10,000, preferably 0.5 to 5,000.

The concentration of the solid catalyst component formed in step (I) in the prepolymerization system is typically 1 to 1,000 grams/liter, preferably 10 to 500 grams/liter, in terms of the solid catalyst component/polymerization volume ratio. During prepolymerization, component (G) may be present to suppress fouling or improve particle properties.

The inert hydrocarbon solvent is preferably removed from the resulting suspension of prepolymerized solid catalyst component, and the prepolymerized solid catalyst component is dried by vacuum drying or the like.

<Step (III)>
In step (III), the prepolymerized solid catalyst component is contacted with an amine compound (D) to form a prepolymerized solid catalyst for olefin polymerization. The prepolymerized solid catalyst for olefin polymerization is formed from the prepolymerized solid catalyst component formed in step (II) and an amine compound (D).
The amine compound (D) is represented by the following general formula (2).

[In general formula (2), ^R3 is a hydrocarbon group having 1 to 30 carbon atoms, and ^R4 is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. When there are multiple ^R4s , the multiple ^R4s are each independently defined as above. m and n are each independently an integer of 0 or greater, and m + n is 1 or greater.]

In general formula (I), ^R3 represents a hydrocarbon group having from 1 to 30 carbon atoms, and may be saturated or unsaturated, aliphatic or aromatic, and may be linear, branched, or cyclic. For example, any of aliphatic hydrocarbon groups, such as alkyl or alkenyl groups, and aromatic hydrocarbon groups may be used. Preferred examples include alkyl or alkenyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, lauryl, and oleoyl. Other examples include cycloalkyl groups such as cyclopentyl and cyclohexyl; aryl groups such as phenyl and tolyl; and aralkyl groups such as benzyl and neophyl. Among these, alkyl groups having 6 to 22 carbon atoms are preferred, alkyl groups having 8 to 18 carbon atoms are more preferred, and alkyl groups having 12 to 18 carbon atoms are particularly preferred.

In general formula (I), ^R4 is a hydrogen atom or a hydrocarbon group having from 1 to 20 carbon atoms. When ^R4 is a hydrocarbon group having from 1 to 20 carbon atoms, preferred specific examples include the same as the hydrocarbon groups described above. Of these, a hydrogen atom or an alkyl group having 1 to 2 carbon atoms is preferred, and a hydrogen atom or a methyl group is more preferred.

In general formula (I), m and n are each an integer of 0 or greater. m+n is 1 or greater. m and n are preferably 0 to 10, and m+n is preferably 1 to 20.
Specific examples of the polyoxyalkylene alkylamine compound (B) represented by general formula (I) include polyoxyethylene octylamine, polyoxyethylene decylamine, polyoxyethylene laurylamine, polyoxyethylene octadecylamine, polyoxyethylene coconut oil alkylamine, polyoxyethylene tallow amine, polyoxyethylene hydrogenated tallow amine, polyoxypropylene laurylamine, polyoxypropylene coconut oil alkylamine, and polyoxypropylene tallow amine. Among these, polyoxyethylene octylamine, polyoxyethylene decylamine, polyoxyethylene laurylamine, polyoxyethylene coconut oil alkylamine, and polyoxypropylene coconut oil alkylamine are preferred.

In step (III), the temperature when the prepolymerized solid catalyst component is contacted with the amine compound (D) is typically -50 to 50°C, preferably -20 to 50°C, and the contact time is typically 1 minute to 20 hours, preferably 5 minutes to 10 hours.

In step (III), the amine compound (D) is used in an amount of 0.1 to 20 parts by mass, preferably 0.3 to 10 parts by mass, and more preferably 0.4 to 5 parts by mass, per 100 parts by mass of the prepolymerized solid catalyst component.

The contact between the prepolymerized solid catalyst component and the amine compound (D) can be carried out in an inert hydrocarbon solvent, and examples of the inert hydrocarbon solvent include the same inert hydrocarbon solvents as those used in step (I).

The inert hydrocarbon solvent is preferably removed from the resulting suspension of prepolymerized solid catalyst for olefin polymerization.

<Step (IV)>
In the step (IV), an olefin is polymerized in the presence of the prepolymerized solid catalyst for olefin polymerization.
The step of polymerizing an olefin is preferably a step of homopolymerizing ethylene or copolymerizing ethylene with an olefin having 3 to 20 carbon atoms.
Examples of the polymerization method include liquid phase polymerization methods such as solution polymerization and suspension polymerization, and gas phase polymerization methods, with suspension polymerization methods and gas phase polymerization methods being preferred.

Specific examples of inert hydrocarbon media used in liquid-phase polymerization include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; alicyclic hydrocarbons such as cyclopentane, cyclohexane, and methylcyclopentane; aromatic hydrocarbons such as benzene, toluene, and xylene; halogenated hydrocarbons such as ethylene chloride, chlorobenzene, and dichloromethane, and mixtures thereof.

When olefin polymerization is carried out in the presence of the prepolymerized solid catalyst for olefin polymerization, the prepolymerized solid catalyst for olefin polymerization is used in an amount such that component (A) is generally 1×10 ⁻¹² to 1×10 ⁻¹ mol, preferably 1×10 ⁻⁸ to 1×10 ⁻² mol per liter of reaction volume.

Preferably, the compound (B), more preferably the compound represented by the general formula (B-1a), is added to the polymerization system together with the prepolymerized solid catalyst for olefin polymerization.
When polymerizing olefins, the lower limit of the polymerization temperature is 0°C, preferably 40°C, and particularly preferably 60°C. Higher temperatures are advantageous in industrial-scale production in terms of heat removal, etc. The upper limit is usually 200°C, preferably 170°C, and the polymerization pressure is usually atmospheric pressure to 100 kgf/ ^cm2 , preferably atmospheric pressure to 50 kgf/ ^cm2 .

The polymerization reaction can be carried out in any of batch, semi-continuous and continuous systems. Furthermore, the polymerization can be carried out in two or more stages with different reaction conditions.
The molecular weight of the olefin polymer obtained by the process for producing an olefin polymer according to the present invention can be adjusted by making hydrogen present in the polymerization system or by changing the polymerization temperature. During the polymerization, the above-mentioned component (G) can be present together for the purpose of suppressing fouling or improving particle properties.

In the present invention, the monomer supplied to the polymerization reaction is preferably ethylene alone, or ethylene and an olefin having 3 to 20 carbon atoms. Specific examples of olefins having 3 to 20 carbon atoms include α-olefins such as propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene, as well as cyclic olefins such as cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene, and 2-methyl-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene.

Furthermore, small amounts of styrene, vinylcyclohexane, dienes, acrylic acid, methacrylic acid, fumaric acid, maleic anhydride, etc.; polar monomers such as methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, and methacrylic acid may be added as long as the effects of the present invention are not impaired.

<Olefin polymer>
One embodiment of the olefin polymer produced by the production method of the present invention is an ethylene-based polymer containing ethylene-derived structural units in a range of preferably 60 to 100 mol%, more preferably 80 to 100 mol%. When the ethylene-based polymer is a copolymer, it contains structural units derived from an α-olefin having 3 to 20 carbon atoms in a total amount of preferably 1 to 40 mol%, more preferably 2 to 20 mol%, where the sum of the content of ethylene-derived structural units and the content of structural units derived from an α-olefin having 3 to 20 carbon atoms is taken as 100 mol%.

Among these polymers, ethylene homopolymer, ethylene/propylene copolymer, ethylene/1-butene copolymer, ethylene/propylene/1-butene copolymer, ethylene/1-octene polymer, ethylene/1-hexene polymer, ethylene/4-methyl-1-pentene polymer, ethylene/propylene/1-octene polymer, ethylene/propylene/1-hexene polymer, and ethylene/propylene/4-methyl-1-pentene polymer are preferred. Also suitable are so-called block copolymers (impact copolymers) obtained by mixing or continuously producing two or more polymers selected from these polymers.

<Applications of olefin polymers>
The olefin polymer produced by the production method of the present invention can be processed to give a film by air-cooled inflation molding, air-cooled two-stage cooling inflation molding, high-speed inflation molding, T-die film molding, water-cooled inflation molding, or other molding processes.

Films obtained from the olefin polymers of the present invention are suitable for a variety of packaging applications, such as standard bags, sugar bags, oily food packaging bags, and watery food packaging bags, as well as agricultural materials. They can also be used as multilayer films by laminating them with substrates such as nylon and polyester.

The olefin polymer of the present invention may contain additives such as weather resistance stabilizers, heat resistance stabilizers, antistatic agents, antislip agents, antiblocking agents, antifogging agents, lubricants, pigments, dyes, nucleating agents, plasticizers, antioxidants, hydrochloric acid absorbers, and antioxidants, as needed, provided the additives do not impair the objectives of the present invention.

The present invention will be explained in more detail using the following examples. However, the present invention is not limited to the descriptions in the following examples.

[Transition metal compound]
The transition metal compounds (A) [component (A)] used in the examples and comparative examples are as follows:
"A-1": (n-butylcyclopentadienyl)(tetramethylcyclopentadienyl)zirconium dichloride [synthesized by the same method as described in JP-A-2000-514494]
"A-2": bis(1-n-butyl-3-methylcyclopentadienyl)zirconium dichloride [synthesized by the same method as described in JP-A-2000-514494]
"A-3": (n-propylcyclopentadienyl)(pentamethylcyclopentadienyl)zirconium dichloride [synthesized by the method described in JP-A-2000-514494]
"A-4": (n-butylcyclopentadienyl)(pentamethylcyclopentadienyl)zirconium dichloride [synthesized by the same method as described in JP-A-2000-514494]
"A-5": (n-propylcyclopentadienyl)(tetramethylcyclopentadienyl)zirconium dichloride [synthesized by the same method as described in JP-A-2000-514494]
"A-6": (1,3-dimethylcyclopentadienyl)(1-n-butyl-3-methylcyclopentadienyl)zirconium dichloride [synthesized by the same method as described in JP-A-2000-514494]

[Stabilizer]
The amine compound (D) [component (D)] used as a stabilizer in the examples and comparative examples is as follows:
"D-1": Lauryldiethanolamine [Electrostripper (registered trademark) EA, manufactured by Kao Corporation]
"D-2": stearyldiethanolamine [CAS number 10213-78-2, manufactured by Tokyo Chemical Industry Co., Ltd.]
"D-3": Polyoxyalkylene alkylamine compound [Amit (registered trademark) 102, manufactured by Kao Corporation] (The analysis results of the types and composition ratios of the compounds contained are disclosed in Table 1 of the patent document (JP 2019-157019 A)).
"D-4": Polyoxyalkylene alkylamine compound [Amit (registered trademark) 105, manufactured by Kao Corporation]
"D-5": Alkyldiethanolamine compound [ATOMER (registered trademark) 163, manufactured by Croda Japan Co., Ltd.] (The analysis results of the types and composition ratios of the compounds contained are disclosed in Table 1 of the patent document (JP 2019-157019 A)).
"D-6": alkyl (C16-C18) diethanolamine compound [ARMOSAT (registered trademark) 1800, manufactured by Akzo Nobel Co., Ltd.]

Preparation Example 1 (Preparation of solid catalyst component (X-1))
Using a 270 L reactor equipped with a stirrer, 10 kg of silica gel (Fuji Silysia Chemical Ltd., average particle size 70 μm, specific surface area 340 m ² /g, pore volume 1.3 cm ³ /g, dried at 250°C for 10 hours) was suspended in 77 L of toluene under a nitrogen atmosphere, and then cooled to 0 to 5°C. While maintaining the temperature in the system at 0 to 5°C, 19.4 L of a toluene solution of methylaluminoxane (3.5 mol/L in terms of Al atoms) was added dropwise to this suspension over 30 minutes. After contacting the added components for 30 minutes, the temperature in the system was raised to 95°C over 1.5 hours, and then the mixture was contacted at 93 to 97°C for 4 hours. The temperature was then lowered to room temperature, the supernatant was removed by decantation, and the residue was washed twice with toluene to obtain a total of 115 L of a toluene slurry of a solid support supporting methylaluminoxane. A portion of this slurry was sampled and analyzed, and the solid concentration was found to be 123 g/L.

12.2 L of the resulting slurry (1.50 kg as solids) was charged into a 114 L reactor equipped with a stirrer under a nitrogen atmosphere, and toluene was added to bring the total volume to 28 L. Next, a solution of 22.0 g (54.2 mmol in terms of Zr atoms) of (n-butylcyclopentadienyl)(tetramethylcyclopentadienyl)zirconium dichloride (A-1) as component (A) dissolved in 5.0 L of toluene was pressure-fed into the reactor and contacted for 1 hour at a system temperature of 20-25°C. The supernatant was removed by decantation, and the residue was washed three times with hexane. Further hexane was then added to the washed material to bring the total volume to 30 L, yielding a hexane slurry of solid catalyst component (X-1).

Preparation Example 2 (Preparation of Prepolymerized Solid Catalyst Component (XP-1))
30 L of a hexane slurry of the solid catalyst component (X-1) obtained in Preparation Example 1 was cooled to 10°C, and 2.89 mol of diisobutylaluminum hydride (hereinafter also referred to as "DiBAl-H") was added thereto. While maintaining the temperature in the system at 10 to 15°C, ethylene was continuously fed into the system under normal pressure for several minutes, and then 70 ml of 1-hexene was added. Thereafter, ethylene feed was started at a rate of 1.46 kg/h, and prepolymerization was carried out at a system temperature of 32 to 37°C. 70 ml of 1-hexene was added a total of five times every 30 minutes after the start of prepolymerization, and when the ethylene feed reached 4.37 kg 180 minutes after the start of prepolymerization, the ethylene feed was stopped. Thereafter, the supernatant liquid was removed by decantation, and the residue was washed four times with hexane. Subsequently, hexane was further added to the washed matter to make the total volume 30 L, thereby obtaining a hexane slurry of a prepolymerized solid catalyst component.

The hexane slurry was then placed in a 43 L agitator-equipped evaporator under a nitrogen atmosphere, and the pressure was reduced to -68 kPaG over approximately 60 minutes. Once the pressure reached -68 kPaG, the mixture was vacuum dried for approximately 4.3 hours to remove the hexane and volatiles. The pressure was further reduced to -100 kPaG, and once the pressure reached -100 kPaG, the mixture was vacuum dried for 8 hours to obtain 6.20 kg of a prepolymerized solid catalyst component (XP-1).

Preparation Example 3 (Preparation of Prepolymerized Solid Catalyst Component (XP-2))
A 200 ml reactor equipped with a stirrer was charged with 10.0 g of the prepolymerized solid catalyst component (XP-1) obtained in Preparation Example 2 under a nitrogen atmosphere, and hexane was added to bring the total volume to 50 ml. Next, the temperature within the system was raised to 35°C, and then 100.0 mg of lauryldiethanolamine (D-1) as component (D) diluted with 5 ml of toluene was added. The mixture was then contacted at 32 to 37°C for 2 hours to obtain a hexane slurry of the prepolymerized solid catalyst component. This hexane slurry was transferred to a 100 ml glass Schlenk flask, and the hexane and toluene were distilled off under reduced pressure at 25°C to obtain 10.1 g of a prepolymerized solid catalyst component (the "prepolymerized solid catalyst for olefin polymerization" in this invention) (XP-2).

[Example 1] (Production of ethylene/1-hexene copolymer)
(Polymerization evaluation (i): Evaluation of autoclave wall condition during polymerization)
A 1-L stainless steel autoclave that had been thoroughly purged with nitrogen was charged with 500 ml of n-heptane, and the nitrogen in the system was purged with ethylene. 10 ml of 1-hexene and 250 mg of the prepolymerized solid catalyst component (XP-2) obtained in Preparation Example 3 were then added, and the temperature was raised to 55°C. It took approximately 10 minutes from the addition of the prepolymerized solid catalyst component (XP-2) for the temperature to reach 55°C. Thereafter, 200 mg of the prepolymerized solid catalyst component (XP-2) was added, and the temperature in the system was raised to 73°C. Polymerization was then initiated by introducing ethylene, and polymerization was carried out for 90 minutes while the pressure was maintained at 8.0 kgf/cm ² -G while continuously supplying ethylene. After completion of the polymerization, the pressure was released, the polymer was removed, and the condition of the autoclave was checked. No polymer adhesion to the autoclave vessel wall or stirring blades was observed.

(Polymerization Evaluation (ii): Polymerization Activity Evaluation)
A 1-L stainless steel autoclave, thoroughly purged with nitrogen, was charged with 500 ml of n-heptane, and the system was purged with ethylene. 20 ml of 1-hexene and 0.06 ml of a decane solution of triisobutylaluminum (1.0 mol/L) were then added, and the system was maintained at room temperature for 5 minutes. Subsequently, 180 mg of prepolymerized solid catalyst component (XP-2) was added, and the temperature in the system was raised to 73°C. Polymerization was then initiated by introducing ethylene, and polymerization was carried out for 90 minutes while continuously supplying ethylene, maintaining the pressure at 8.0 kgf/cm ² -G. After polymerization was completed, the pressure was released, and the polymer was filtered, washed, and dried under reduced pressure at 80°C for 10 hours, yielding 112.7 g of polymer. The polymer yield per gram of catalyst (polymerization activity) was 626 (g-PE/g-cat), and the powder bulk density was 421 g/L.

Preparation Example 4 (Preparation of solid catalyst component (X-2))
A hexane slurry of the solid catalyst component (X-1) obtained in Preparation Example 1 was charged into a 200 ml reactor equipped with a stirrer under a nitrogen atmosphere so that the solid content was 10.0 g, and hexane was added so that the total amount was 50 ml. Next, the temperature inside the system was raised to 35°C, and then 100.0 mg of lauryldiethanolamine (D-1) as component (D) diluted with 5 ml of toluene was added, and the mixture was allowed to contact for 2 hours at 32 to 37°C to obtain a hexane slurry of the solid catalyst component. This hexane slurry was transferred to a 100 ml glass Schlenk flask, and the hexane and toluene were distilled off under reduced pressure at 25°C to obtain 10.1 g of solid catalyst component (X-2).

Preparation Examples 5 to 9 (Preparation of Prepolymerized Solid Catalyst Components (XP-3) to (XP-7))
Prepolymerized solid catalyst components (XP-3) to (XP-7) were prepared in the same manner as in Preparation Example 3, except that the amine compound (D-1) was replaced with the amine compound (D-2), (D-3), (D-4), (D-5) or (D-6).

Preparation Examples 10 to 14 (Preparation of Solid Catalyst Components (X-3) to (X-7))
Solid catalyst components (X-3) to (X-7) were prepared in the same manner as in Preparation Example 4, except that amine compound (D-1) was replaced with amine compound (D-2), (D-3), (D-4), (D-5), or (D-6).

Preparation Example 15 (Preparation of Prepolymerized Solid Catalyst Component (XP-8))
A prepolymerized solid catalyst component (XP-8) was prepared in the same manner as in Preparation Examples 1 to 3, except that the transition metal compound (A-2) was used instead of the transition metal compound (A-1).

Preparation Example 16 (Preparation of solid catalyst component (X-8))
A solid catalyst component (X-8) was prepared in the same manner as in Preparation Examples 1 and 4, except that the transition metal compound (A-2) was used instead of the transition metal compound (A-1).

[Examples 2 to 6, Comparative Examples 1 to 7, and Reference Examples 1 and 2] (Production of ethylene/1-hexene copolymer)
Ethylene/1-hexene copolymers were produced in the same manner as in Example 1, except that the solid catalyst component used was changed as shown in Table 1, and polymerization evaluations (i) and (ii) were carried out. The results are shown in Table 1.

As is clear from Table 1, in Example 1, in which prepolymerization was performed and component (D-1) was further used, adhesion of the polymer to the autoclave vessel wall and stirring blades was suppressed compared to Comparative Example 1, in which prepolymerization was not performed, and Comparative Example 2, in which component (D-1) was not used. Furthermore, the powder bulk density of the resulting polymer was higher than in Comparative Example 1.

That is, in Example 1, an olefin polymer could be produced more stably than in Comparative Examples 1 and 2.
Furthermore, in Examples 2 to 6, in which components (D-2) to (D-6) were used instead of component (D-1), adhesion of the polymer to the autoclave vessel wall and stirring blades was also suppressed compared to Comparative Examples 3 to 7.

In Reference Examples 1 and 2, in which a symmetric bis-Cp type metallocene compound (transition metal compound (A-2)) was used instead of an asymmetric biscyclopentadienyl type (hereinafter referred to as "bis-Cp type") metallocene compound as the transition metal compound, adhesion of the polymer to the autoclave vessel wall and stirring blades was suppressed regardless of whether prepolymerization was performed or not.

The reason why such differences in effect occur depending on the structure of the transition metal compound is presumed to be as follows.
Polymer adhesion to the autoclave walls and stirring blades occurs when the metallocene compound leaches from the solid catalyst component. The solid catalyst component and the metallocene compound interact as an ion pair, with the metallocene compound acting as a cation and the solid catalyst component acting as an anion. In asymmetric bis-Cp metallocene compounds, steric distortion occurs due to the asymmetry of the upper and lower ligands, which is thought to weaken the ionic bond compared to symmetric bis-Cp metallocene compounds. Therefore, while asymmetric bis-Cp metallocene compounds are thought to be more susceptible to leaching, prepolymerization makes them less susceptible to leaching due to the polymer coating that occurs around them, which is thought to suppress polymer adhesion to the autoclave walls and stirring blades. On the other hand, symmetric bis-Cp metallocene compounds are more difficult to leach than asymmetric bis-Cp metallocene compounds. Therefore, in Reference Example 2, polymer adhesion to the autoclave walls and stirring blades did not occur even without prepolymerization.

From the above, it can be seen that the manufacturing method of the present invention is particularly useful when an asymmetric bis-Cp metallocene compound is used as the transition metal compound.

Preparation Examples 17 to 20 (Preparation of Prepolymerized Solid Catalyst Components (XP-9) to (XP-12))
Prepolymerized solid catalyst components (XP-9) to (XP-12) were prepared in the same manner as in Preparation Examples 1 to 3, except that the transition metal compound (A-1) was replaced with the transition metal compound (A-3), (A-4), (A-5), or (A-6), respectively.

Preparation Examples 21 to 24 (Preparation of Solid Catalyst Components (X-9) to (X-12))
Solid catalyst components (X-9) to (X-12) were prepared in the same manner as in Preparation Examples 1 and 4, except that the transition metal compound (A-1) was replaced with the transition metal compound (A-3), (A-4), (A-5), or (A-6).

[Examples 7 to 10, Comparative Examples 8 to 11] (Production of ethylene/1-hexene copolymer)
Ethylene/1-hexene copolymers were produced and polymerization evaluations (i) and (ii) were carried out in the same manner as in Example 1, except that the solid catalyst component used was changed as shown in Table 2. The results are shown in Table 2.

As is clear from Table 2, in Examples 7 to 10, in which prepolymerization was performed, adhesion of the polymer to the autoclave walls and stirring blades was suppressed compared to Comparative Examples 8 to 11, in which prepolymerization was not performed. Furthermore, the powder bulk density of the obtained polymer was also high.

[Example 11] (Production of ethylene/1-hexene copolymer)
(Polymerization evaluation (iii): Operability evaluation by gas phase polymerization)
Copolymerization of ethylene and 1-hexene was carried out using a gas-phase fluidized-bed polymerization apparatus. The polymerization pressure was 1.7 MPaG, and the polymerization temperature was 80°C. The prepolymerized solid catalyst component (XP-2) prepared in Preparation Example 3 was fed into the polymerization reactor at a rate of 4.2 g/hr. Furthermore, lauryldiethanolamine was fed as a stabilizer into the circulation gas line so that it was present in an amount of 30 ppm by mass relative to the mass of the polymer. Ethylene, hydrogen, 1-hexene, and isopentane were continuously fed into the gas-phase polymerization reactor so that the gas composition was ethylene partial pressure = 1.0 MPa, hydrogen/ethylene = 4.8 × 10 ^-4 (molar ratio), 1-hexene/ethylene = 0.022 (molar ratio). Polymer was produced at a rate of 6.0 kg/hr. The residence time was 4 hours. The polymer density at this time was 916 kg/m ³ , and the melt flow rate was 3.8 g/10 min. The melt flow rate was measured under conditions of 190° C. and a load of 2.16 kg in accordance with ASTM D1238-65T.

Operation was carried out under the above conditions for 48 hours, and no heat spots were observed in any part of the polymerization vessel or piping, allowing for stable polymerization.

[Comparative Example 12]
A polymer was produced at a rate of 6.0 kg/hr in the same manner as in Example 11, except that the solid catalyst component (X-2) was used instead of the prepolymerized solid catalyst component (XP-2). As a result of operation under these conditions, heat spots occurred in the polymerization vessel and the like, and operation could not be continued within 4 hours.

[Comparative Example 13]
A polymer was produced at a rate of 6.0 kg/hr in the same manner as in Example 11, except that the prepolymerized solid catalyst component (XP-1) was used instead of the prepolymerized solid catalyst component (XP-2). As a result of operation under these conditions, heat spots occurred in the polymerization vessel and the like, and operation could not be continued within 4 hours.

Claims (2)

(A) a transition metal compound represented by the following general formula (1),
[In general formula (1),
M is a transition metal atom of Group 4 of the periodic table;
n is an integer of 1 to 4 selected so that the transition metal compound (A) is electrically neutral;
X represents a hydrogen atom, a halogen atom, a hydrocarbon group, an anionic ligand, or a neutral ligand capable of coordinating with a lone electron pair, and 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, a boron-containing group, an aluminum-containing group, or a conjugated diene derivative group, and when n is 2 or more, the multiple groups represented by X may be the same or different and may be bonded to each other to form a ring;
R ¹ 's are each independently a hydrogen atom or a hydrocarbon group having 1 to 2 carbon atoms, at least two R ¹ 's are hydrocarbon groups having 1 to 2 carbon atoms, and adjacent R ¹ 's may be bonded to each other to form a ring which may have a substituent;
R2 ^'s are each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 40 carbon atoms, a halogen-containing group, a silicon-containing group, an oxygen-containing group, a nitrogen-containing group, or a sulfur-containing group, at least one ^R2 is a saturated hydrocarbon group having 3 to 10 carbon atoms in the linear portion or a terminally unsaturated hydrocarbon group having 3 to 10 carbon atoms in the linear portion, at least two ^R2 's are hydrogen atoms, and adjacent ^R2 's may be bonded to each other to form a ring which may have a substituent.]
(B) (B-1) organometallic compound,
(B-2) at least one compound selected from the group consisting of an organoaluminum oxy compound, and (B-3) a compound that reacts with the transition metal compound (A) to form an ion pair;
(C) Step (I) of contacting the catalyst with a particulate support to form a solid catalyst component;
(II) prepolymerizing an olefin in the presence of the solid catalyst component to form a prepolymerized solid catalyst component;
the prepolymerized solid catalyst component and an amine compound (D) represented by the following general formula (2):
[In general formula (2), ^R3 is a hydrocarbon group having 1 to 30 carbon atoms, and ^R4 is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. When there are multiple ^R4s , the multiple ^R4s are each independently defined as above. m and n are each independently an integer of 0 or greater, and m + n is 1 or greater.]
(III) forming a prepolymerized solid catalyst for olefin polymerization by contacting the solid catalyst with the olefin polymerization catalyst; and (IV) polymerizing an olefin in the presence of the prepolymerized solid catalyst for olefin polymerization.
A method for producing an olefin polymer comprising the steps of: The method for producing an olefin polymer according to claim 1, wherein the step of polymerizing an olefin is a step of homopolymerizing ethylene or a step of copolymerizing ethylene with an α-olefin having 3 to 20 carbon atoms.