JP2022037932A - Manufacturing method of olefin polymer - Google Patents

Abstract

To provide a method of manufacturing an olefin polymer with high polymerization activity while suppressing fowling during polymerization by using a metallocene system solid catalyst.SOLUTION: A manufacturing method of an olefin polymer comprising: a step of forming a solid catalyst component containing a transition metal compound (A) represented by the following formula. (M is a periodic table group 4 transition metal atom, n is an integer of 1 to 4, X is a halogen atom or the like, at least two R1 are a hydrocarbon group of 1 to 2 carbons, other R1 is hydrogen atom, R2 is hydrogen atom, hydrocarbon group or the like); a step of preliminary polymerizing olefin under the presence of the solid catalyst component to form a preliminary polymerizing solid catalyst component; a step of contacting the preliminary polymerization solid catalyst component with a predetermined amine compound to form a solid catalyst; and a step of polymerizing olefine under the presence of the solid catalyst.SELECTED DRAWING: None

Description

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

Linear low-density polyethylene (LLDPE) is widely used mainly for packaging applications such as bonding films, industrial films, heavy-duty packaging bags, tubes, and food packaging materials due to its excellent physical properties and moldability. LLDPE has different required characteristics depending on the molding method and application. For example, at the time of inflation molding, a polymer having a narrow composition distribution is required in order to prevent stickiness (blocking) of a molded product such as a film. Ethylene polymers obtained using a metallocene catalyst system are known to have advantages such as a narrow composition distribution and less blocking.

For example, Patent Document 1 describes an olefinically unsaturated monomer using a metallocene in which one of two cyclopentadienyl rings has a substituent having 3 or more carbon atoms and the other has two or more substituents. A method of polymerizing to obtain a polymer product having a narrow composition distribution is disclosed.

Further, in Patent Document 2, one of the two cyclopentadienyl rings is unsubstituted or has a substituent having at least 3 or more carbon atoms, and the other is at least one selected from a methyl group, an ethyl group and an aryl group. There is disclosed an ethylene-based polymer having a narrow composition distribution, which is obtained by using a metallocene having a substituent of.

On the other hand, when producing an olefin polymer such as polyethylene, polypropylene, an ethylene / α-olefin copolymer, or a propylene / α-olefin copolymer by (co) polymerizing an olefin in the presence of a metallocene-based solid catalyst. In addition, when olefins are vapor-phase polymerized in the presence of a metallocene-based solid catalyst using a fluidized bed reactor, polymer lumps, sheet-like substances, etc. are generated in the fluidized bed, and the fluidity of the polymer particles is reduced. In some cases, the mixing state in the fluidized bed became non-uniform, and stable continuous operation could not be performed for a long period of time.

Further, when slurry polymerization is carried out in the presence of the metallocene-based solid catalyst as described above, polymer lumps, sheet-like substances, etc. are generated in the polymerizer, or the polymer adheres to the stirring blades and is stable and continuous for a long period of time. Sometimes I couldn't drive.

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

Special Table 2000-514494A Gazette Japanese Unexamined Patent Publication No. 10-251334 Japanese Unexamined Patent Publication No. 2000-297114 Japanese Unexamined Patent Publication No. 2001-48912

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

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

[In the general formula (1)
M is a Group 4 transition metal atom in the periodic table.
n is an integer of 1 to 4 selected so that the transition metal compound (A) is electrically neutral.
X is a neutral ligand capable of coordinating with a hydrogen atom, a halogen atom, a hydrocarbon group, an anionic ligand or an isolated electron pair, and the anion ligand is a halogen-containing group, a silicon-containing group, or oxygen. It is a containing group, a sulfur-containing group, a nitrogen-containing group, a phosphorus-containing group, a boron-containing group, an aluminum-containing group or a conjugated diene-based derivative group. But they may be different, they may combine with each other to form a ring,
R ¹ is independently a hydrogen atom or a hydrocarbon group having 1 to 2 carbon atoms, and at least two R ^1s are hydrocarbon groups having 1 to 2 carbon atoms, and adjacent R ^1s are adjacent to each other. It may be bonded to form a ring which may have a substituent.
R ² is 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, and at least one R2 is used. Reference numeral ² is a saturated hydrocarbon group having 3 to 10 carbon atoms in the linear portion or a terminal unsaturated hydrocarbon group having 3 to 10 carbon atoms in the linear moiety, and at least two R ^2s are hydrogen atoms. Yes, adjacent R ^2s may be bonded to each other to form a ring that may have a substituent. ]
(B) (B-1) Organometallic compound,
At least one compound selected from the group consisting of (B-2) an organoaluminum oxy compound and (B-3) a compound which reacts with a transition metal compound (A) to form an ion pair.
(C) Step (I) of forming a solid catalyst component by contacting with a fine particle carrier.
Step (II) of prepolymerizing an olefin in the presence of the solid catalyst component to form a prepolymerized solid catalyst component.
The prepolymerized solid catalyst component and the amine compound (D) represented by the following general formula (2)

[In the general formula (2), R ³ is a hydrocarbon group having 1 or more and 30 or less carbon atoms, and R ⁴ is a hydrogen atom or a hydrocarbon group having 1 or more and 20 or less carbon atoms. When there are a plurality of R ⁴ , the plurality of R ^4s are independently defined in the same manner as described above. m and n are each independently an integer of 0 or more, and m + n is 1 or more. ]
A step of forming a prepolymerized solid catalyst for olefin polymerization (III) and a step of polymerizing an olefin in the presence of the prepolymerized solid catalyst for olefin polymerization (IV).
A method for producing an olefin polymer containing.

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

According to the present invention, in a method for producing an olefin-based polymer using a predetermined metallocene-based solid catalyst capable of producing an olefin-based polymer having a narrow composition distribution, olefins have high polymerization activity while suppressing fouling during polymerization. A system polymer can be produced.

Hereinafter, the method for producing the olefin polymer of the present invention will be described in more detail.
The method for producing an olefin polymer of the present invention is
Step (I), in which the transition metal compound (A), the compound (B), and the (C) fine particle carrier are brought into contact with each other to form a solid catalyst component.
Step (II) of 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 the amine compound (D) to form a prepolymerized solid catalyst for olefin polymerization, and a step of polymerizing an olefin in the presence of the prepolymerized solid catalyst for olefin polymerization. (IV)
Includes.

<Step (I)>
In the step (I), the transition metal compound (A), the compound (B), and the (C) fine particle carrier are brought into contact with each other 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 satisfying the valence of the transition metal atom M, and is preferably 1 or 2.
X is a neutral ligand capable of coordinating with a hydrogen atom, a halogen atom, a hydrocarbon group, an anionic ligand or an isolated electron pair, and the anion ligand is a halogen-containing group, a silicon-containing group, or oxygen. It is a containing group, a sulfur-containing group, a nitrogen-containing group, a phosphorus-containing group, a boron-containing group, an aluminum-containing group, or a conjugated diene-based 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, a plurality of Xs may be the same or different from each other, or may be combined with each other to form a ring. Further, when a plurality of the rings are present, the rings may be the same or different from each other.

Examples of the halogen atom include fluorine, chlorine, bromine, iodine and the like, preferably chlorine or bromine.
Examples of the hydrocarbon group include, for example.
Methyl group, ethyl group, 1-propyl group, 1-butyl group, 1-pentyl group, 1-hexyl group, 1-heptyl group, 1-octyl group, iso-propyl group, sec-butyl group (butan-2-) Il group), tert-butyl group (2-methylpropane-2-yl group), iso-butyl group (2-methylpropyl group), pentan-2-yl group, 2-methylbutyl group, iso-pentyl group (3) -Methylbutyl group), neopentyl group (2,2-dimethylpropyl group), sheamil group (1,2-dimethylpropyl group), iso-hexyl group (4-methylpentyl group), 2,2-dimethylbutyl group, 2 , 3-dimethylbutyl group, 3,3-dimethylbutyl group, texyl group (2,3-dimethylbut-2-yl group), 4,4-dimethylpentyl group and other linear or branched alkyl groups;
Vinyl group, allyl group, propenyl group (propa-1-en-1-yl group), iso-propenyl group (propa-1-en-2-yl group), allenyl group (propa-1,2-diene-1) -Il group), buta-3-en-1-yl group, crotyl group (but-2-en-1-yl group), buta-3-en-2-yl group, metallicl group (2-methylallyl group) , Buta-1,3-dienyl group, penta-4-en-1-yl group, penta-3-en-1-yl group, penta-2-en-1-yl group, iso-pentenyl group (3- Methylbuta-3-en-1-yl group), 2-methylbut-3-en-1-yl group, penta-4-en-2-yl group, prenyl group (3-methylbut-2-en-1-yl group) A linear or branched alkenyl group such as a group) or an unsaturated double bond-containing group;
A linear or branched alkynyl group or unsaturated triple bond-containing group such as an ethynyl group, a propa-2-in-1-yl group, a propargyl group (propa-1-in-1-yl group);
Benzyl group, 2-methylbenzyl group, 4-methylbenzyl group, 2,4,6-trimethylbenzyl group, 3,5-dimethylbenzyl group, Kuminyl group (4-iso-propylbenzyl group), 2,4,6 -Aroma-containing linear chain such as tri-iso-propylbenzyl group, 4-tert-butylbenzyl group, 3,5-di-tert-butylbenzyl group, 1-phenylethyl group, benzhydryl group (diphenylmethyl group) Or branched alkyl groups and unsaturated double bond-containing groups;
Cyclic saturated hydrocarbon groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cycloheptatrienyl group, norbornyl group, norbornenyl group, 1-adamantyl group, 2-adamantyl group;
Phenyl group, trill group (methylphenyl group), xylyl group (dimethylphenyl group), mesityl group (2,4,6-trimethylphenyl group), cumenyl group (iso-propylphenyl group), juryl group (2,3) 5,6-Tetramethylphenyl group), 2,6-di-iso-propylphenyl group, 2,4,6-tri-iso-propylphenyl group, 4-tert-butylphenyl group, 3,5-di- Examples thereof include aromatic substituents such as tert-butylphenyl group, naphthyl group, biphenyl group, terphenyl group, binaphthyl group, acenaphthalenyl group, phenanthryl group, anthracenyl group, pyrenyl group and ferrosenyl group.

Among the hydrocarbon groups, a methyl group, an iso-butyl group, a neopentyl group, a siamil group, a benzyl group, a phenyl group, a tolyl group, a xsilyl group, a mesityl group and a cumenyl group are preferable.

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 and a trifluorophenyl group. , Tetrafluorophenyl group, pentafluorophenyl group, trifluoromethylphenyl group, bistrifluoromethylphenyl group, hexachloroantimonate anion.

Among the halogen-containing groups, a pentafluorophenyl group is preferable.
Examples of the silicon-containing group include a trimethylsilyl group, a triethylsilyl group, a tri-iso-propylsilyl group, a diphenylmethylsilyl group, a tert-butyldimethylsilyl group, a tert-butyldiphenylsilyl group, a triphenylsilyl group, and a tris (tris). Trimethylsilyl) Cyril group, trimethylsilylmethyl group and the like can be mentioned.

Among the silicon-containing groups, a trimethylsilylmethyl group is preferable.
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 and a tert-butoxy group. Benzyloxy group, methoxymethoxy group, phenoxy group, 2,6-dimethylphenoxy group, 2,6-di-iso-propylphenoxy group, 2,6-di-tert-butylphenoxy group, 2,4,6-trimethyl Examples thereof include a phenoxy 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 iso-propoxy group and a tert-butoxy group are preferable.
Examples of the sulfur-containing group include a mesyl group (methanesulphonyl group), a phenylsulfonyl group, a tosyl group (p-toluenesulfonyl group), a trifuryl group (trifluoromethanesulfonyl group), a nonafryl group (nonafluorobutanesulfonyl group), and the like. Examples thereof include a mesylate group (methanesulfonate group), a tosylate group (p-toluenesulfonate group), a trifurate group (trifluoromethanesulfonate group), and a nonafrate group (nonafluorobutanesulfonate group).

Among the sulfur-containing groups, triflate (trifluoromethanesulfonate) is preferable.
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 and a piperidinyl. Examples thereof include a group, a morpholyl group, a pyrrolyl group, and a bistrifurylimide group.

Among the nitrogen-containing groups, a dimethylamino group, a diethylamino group, a pyrrolidinyl group, a pyrrolyl group, and a bistrifurylimide group are preferable.
Examples of the phosphorus-containing group include hexafluorophosphate anion.

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

Examples of the aluminum-containing group include, for example.

(M represents M in the general formula (1))
Examples thereof include a group represented by AlR ₄ (R represents a hydrogen, an alkyl group, an aryl group which may have a substituent, a halogen atom, etc.) capable of forming the above.

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), and a 2,4-hexadienyl group. , 1,4-Diphenyl-1,3-pentadienyl group, cyclopentadienyl group and the like, and examples thereof include a metallocyclopentene group.

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

<R ¹ >
In the general formula (1), 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 ¹ , have 1 to 2 carbon atoms. It is a hydrocarbon group.

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. Among these, a methyl group and an ethyl group are preferable, and a methyl group is more preferable.

Adjacent R ^1s may be bonded to each other to form a ring which may have a substituent, may not be bonded to each other, and is preferably not bonded to each other.
The ring is preferably a 5- or 6-membered ring, and examples of the combined structure of the ring and the cyclopentadienyl ring portion of the mother nucleus include a tetrahydropentalenyl ring, a tetrahydroindenyl ring, and a pentarenyl ring. Indenyl ring is mentioned.

<R ² >
R ² is 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, and at least one R2 is used. Reference numeral ² is a saturated hydrocarbon group having 3 to 10 carbon atoms in the linear portion or a terminal unsaturated hydrocarbon group having 3 to 10 carbon atoms in the linear moiety, and at least two R ^2s are hydrogen atoms. be.

Adjacent R ^2s may be bonded to each other to form a ring which may have a substituent, may not be bonded to each other, and is preferably 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 thereof include specific examples of the hydrocarbon groups mentioned as the above-mentioned example of X. Can be mentioned.

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 above-mentioned hydrocarbon group having 1 to 20 carbon atoms is preferably an aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms. Hydrocarbon groups having 1 to 20 carbon atoms also include substituents having an aromatic structure such as arylalkyl groups.

Examples of the hydrocarbon group having 1 to 40 carbon atoms include, for example.
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, iso-propyl group, sec-butyl group, tert-butyl group, iso-butyl group, pentan-2-yl group, 2-methylbutyl group, iso-pentyl group, neopentyl group , Tart-pentyl group (1,1-dimethylpropyl group), sheamil group, pentan-3-yl group, 2-methylpentyl group, 3-methylpentyl group, iso-hexyl group, 1,1-dimethylbutyl group (1,1-dimethylbutyl group) 2-Methylpentan-2-yl group), 3-methylpentane-2-yl group, 4-methylpentane-2-yl group, 2,2-dimethylbutyl group, 2,3-dimethylbutyl group, 3,3 -Dimethylbutyl group, texyl group, 3-methylpentane-3-yl group, 3,3-dimethylbut-2-yl group, hexane-3-yl group, 2-methylpentane-3-yl group, heptan-4 -Il group, 2,4-dimethylpentane-2-yl group, 3-ethylpentane-3-yl group, 4,4-dimethylpentyl group, 4-methylheptan-4-yl group, 4-propylheptan-4 -A linear or branched alkyl group having 1 to 40 carbon atoms, such as an yl group, a 2,3,3-trimethylbutan-2-yl group, and a 2,4,4-trimethylpentan-2-yl group. ;
Vinyl group, allyl group, propenyl group, iso-propenyl group, allenyl group, buta-3-en-1-yl group, crotyl group, buta-3-en-2-yl group, metalryl group, pig-1,3 -Dienyl group, penta-4-en-1-yl group, penta-3-en-1-yl group, penta-2-en-1-yl group, iso-pentenyl group, 2-methylbut-3-en- 1-yl group, penta-4-en-2-yl group, prenyl group, 2-methyl-but-2-en-1-yl group, penta-3-en-2-yl group, 2-methyl-buta -3-en-2-yl group, penta-1-en-3-yl group, penta-2,4-dien-1-yl group, penta-1,3-dien-1-yl group, penta-1 , 4-diene-3-yl group, iso-prenyl group (2-methyl-buta-1,3-dien-1-yl group), penta-2,4-dien-2-yl group, hexa-5- En-1-yl group, hexa-4-en-1-yl group, hexa-3-en-1-yl group, hexa-2-en-1-yl group, 4-methyl-penta-4-en- 1-yl group, 3-methyl-pent-4-en-1-yl group, 2-methyl-penta-4-en-1-yl group, hexa-5-en-2-yl group, 4-methyl- Penta-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-ene -2-Il group, 3-ethylpenta-1-ene-3-yl group, hexa-3,5-diene-1-yl group, hexa-2,4-dien-1-yl group, 4-methylpenta-1 , 3-Dien-1-yl group, 2,3-dimethyl-buta-1,3-dien-1-yl group, hexa-1,3,5-triene-1-yl group, 2- (cyclopentadi) A linear or branched alkenyl group or unsaturated double bond-containing group having 2 to 40 carbon atoms such as an enyl) propan-2-yl group and a 2- (cyclopentadienyl) ethyl group;

Ethynyl group, propa-2-in-1-yl group, propargyl group, buta-1-in-1-yl group, bututa-2-in-1-yl group, bututa-3-in-1-yl group, Penta-1-in-1-yl group, penta-2-in-1-yl group, penta-3-in-1-yl group, penta-4-in-1-yl group, 3-methyl-buta- 1-in-1-yl group, penta-3-in-2-yl group, 2-methyl-but-3-in-1-yl group, penta-4-in-2-yl group, hexa-1- In-1-yl group, 3,3-dimethyl-buta-1-in-1-yl group, 2-methyl-penta-3-in-2-yl group, 2,2-dimethyl-but-3-in A linear or branched alkynyl group or unsaturated triple having 2 to 40 carbon atoms such as a -1-yl group, a hexa-4-in-1-yl group, and a hexa-5-in-1-yl group. Bond-containing group;
Benzyl group, 2-methylbenzyl group, 4-methylbenzyl group, 2,4,6-trimethylbenzyl group, 3,5-dimethylbenzyl group, Kuminyl 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-phenylpropane-2-yl group), 2- (4-methylphenyl) ) Propan-2-yl group, 2- (3,5-dimethylphenyl) propan-2-yl group, 2- (4-tert-butylphenyl) propan-2-yl group, 2- (3,5-di) -Tert-Butylphenyl) Propan-2-yl group, 3-phenylpentane-3-yl group, 4-phenylhepta-1,6-dien-4-yl group, 1,2,3-triphenylpropane-2 -Il 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-iso-propylphenyl) Ethyl group, 2- (4-tert-butylphenyl) ethyl group, 2- (3,5-di-tert-butylphenyl) ethyl group, 2-methyl-1-phenylpropane-2-yl group, 3-phenylpropi Lu group, cinnamyl group (3-phenylallyl group), neophil group (2-methyl-2-phenylpropyl group), 3-methyl-3-phenylbutyl group, 2-methyl-4-phenylbutane-2-yl group , Cyclopentadienyldiphenylmethyl group, 2- (1-indenyl) propan-2-yl group, (1-indenyl) diphenylmethyl group, 2- (1-indenyl) ethyl group, 2- (tetrahydro-1-indacenyl) ) Propan-2-yl group, (tetrahydro-1-indacenyl) diphenylmethyl group, 2- (tetrahydro-1-indacenyl) ethyl group, 2- (1-benzoindenyl) propan-2-yl group, (1- Benzoindenyl) diphenylmethyl group, 2- (1-benzoindenyl) ethyl group, 2- (9-fluorenyl) propane -2-yl group, (9-fluorenyl) diphenylmethyl group, 2- (9-fluorenyl) ethyl group, 2- (1-azurenyl) propan-2-yl group, (1-azulenyl) diphenylmethyl group, 2- An aromatic-containing linear or branched alkyl group having 7 to 40 carbon atoms such as (1-azulenyl) ethyl group and an unsaturated double bond-containing group;

Cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclopentenyl group, cyclopentadienyl group, dimethylcyclopentadienyl group, n-butylcyclopentadienyl group, n-butyl-methylcyclopentadienyl group, tetramethylcyclo Pentazienyl group, 1-methylcyclopentyl group, 1-allylcyclopentyl group, 1-benzylcyclopentyl group, cyclohexyl group, cyclohexenyl group, cyclohexadienyl group, 1-methylcyclohexyl group, 1-allylcyclohexyl group, 1-benzyl Cyclohexyl group, cycloheptyl group, cycloheptenyl group, cycloheptatrienyl group, 1-methylcycloheptyl group, 1-allylcycloheptyl group, 1-benzylcycloheptyl group, cyclooctyl group, cyclooctenyl group, cyclooctadienyl group, Cyclooctatrienyl group, 1-methylcyclooctyl group, 1-allylcyclooctyl group, 1-benzylcyclooctyl group, 4-cyclohexyl-tert-butyl group, norbornyl group, norbornenyl group, norbornadienyl group, 2- Methylbicyclo [2.2.1] heptane-2-yl group, 7-methylbicyclo [2.2.1] heptane-7-yl group, bicyclo [2.2.2] octane-1-yl group, bicyclo [2.2.2] Octane-2-yl group, 1-adamantyl group, 2-adamantyl group, 1- (2-methyladamantyl), 1- (3-methyladamantyl), 1- (4-methyladamantyl) , 1- (2-phenyladamantyl), 1- (3-phenyladamantyl), 1- (4-phenyladamantyl), 1- (3,5-dimethyladamantyl), 1- (3,5,7-trimethyladamantyl) ), 1- (3,5,7-triphenyladamantyl), pentarenyl group, indenyl group, fluorenyl group, indasenyl group, tetrahydroindasenyl group, benzoindenyl group, azulenyl group, etc. have 3 to 40 carbon atoms. Cyclic saturated and unsaturated hydrocarbon groups;
Phenyl group, trill group, xylyl group, mesityl group, cumenyl group, juryl group, 2,6-di-iso-propylphenyl group, 2,4,6-tri-iso-propylphenyl group, 4-tert-butylphenyl Group, 3,5-di-tert-butylphenyl group, allylphenyl group, (but-3-en-1-yl) phenyl group, (but-2-en-1-yl) phenyl group, metallicylphenyl group , Plenylphenyl group, 4-adamantylphenyl group, 3,5-di-adamantylphenyl group, naphthyl group, biphenyl group, terphenyl group, binaphthyl group, acenaphthalenyl group, phenanthryl group, anthracenyl group, pyrenyl group, ferrosenyl group, etc. Examples thereof include aromatic substituents having 6 to 40 carbon atoms.

Among the linear or branched alkyl groups having 1 to 40 carbon atoms, methyl group, ethyl group, 1-propyl group, 1-butyl group, 1-pentyl group, 1-hexyl group and 1-heptyl group. Group, 1-octyl group, iso-propyl group, sec-butyl group, tert-butyl group, iso-butyl group, iso-pentyl group, neopentyl group, tert-pentyl group, pentan-3-yl group, iso-hexyl Group, 1,1-dimethylbutyl group, 3,3-dimethylbutyl group, texyl group, 3-methylpentane-3-yl group, heptane-4-yl group, 2,4-dimethylpentane-2-yl group, 3-Ethylpentane-3-yl group, 4,4-dimethylpentyl group, 4-methylheptane-4-yl group, 4-propylheptane-4-yl group, 2,4,4-trimethylpentane-2-yl Groups are preferred, such as methyl group, ethyl group, 1-propyl group, 1-butyl group, 1-pentyl group, 1-hexyl group, iso-propyl group, tert-butyl group, neopentyl group, 2,4-dimethylpentane. -2-Il group and 2,4,4-trimethylpentane-2-yl group are more preferable.

Among the linear or branched alkenyl groups or unsaturated double bond-containing groups having 2 to 40 carbon atoms, vinyl group, allyl group, buta-3-en-1-yl group, crotyl group and methallyl Group, penta-4-en-1-yl group, prenyl group, penta-1,4-dien-3-yl group, hexa-5-en-1-yl group, 2-methylpenta-4-en-2- Il group, 2- (cyclopentadienyl) propan-2-yl group, 2- (cyclopentadienyl) ethyl group and the like are preferable, and vinyl group, allyl group, buta-3-en-1-yl group and penta. A -4-en-1-yl group, a prenyl group, and a hexa-5-en-1-yl group are more preferable.

Among the linear or branched alkynyl groups or unsaturated triple bond-containing groups having 2 to 40 carbon atoms, the ethynyl group, propa-2-in-1-yl group, propargyl group, and pig-2-in -1-yl group, buta-3-in-1-yl group, penta-3-in-1-yl group, penta-4-in-1-yl group, 3-methyl-but-1-in-1 -Il group, 3,3-dimethyl-buta-1-in-1-yl group, hexa-4-in-1-yl group, hexa-5-in-1-yl group and the like are preferable, and propa-2- More preferably, an in-1-yl group, a propargyl group, a pig-2-in-1-yl group, and a pig-3-in-1-yl group.

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, Kuminyl group, 2,4,6-tri-iso-propylbenzyl group, 4-tert-butylbenzyl group, 3,5-di-tert-butylbenzyl Group, Benzyl Group, Kumil 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-tert-butylphenyl) ethyl group, 2- (3) , 5-Di-tert-butylphenyl) ethyl group, styryl group, 2-methyl-1-phenylpropane-2-yl group, 3-phenylpropyl group, cinnamyl group, neophil group, cyclopentadienyldiphenylmethyl group, 2- (1-Indenyl) propane-2-yl group, (1-indenyl) diphenylmethyl group, 2- (1-indenyl) ethyl group, 2- (9-fluorenyl) propan-2-yl group, (9- Fluorenyl) diphenylmethyl group, 2- (9-fluorenyl) ethyl group and the like are preferable, and benzyl group, benzhydryl group, cumyl group, 1,1-diphenylethyl group, trityl group, 2-phenylethyl group and 3-phenylpropyl group are preferable. , Synamyl groups are more preferred.

Among the cyclic saturated and unsaturated hydrocarbon groups having 3 to 40 carbon atoms, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclopentenyl group, cyclopentadienyl group, 1-methylcyclopentyl group and 1-allylcyclopentyl Group, 1-benzylcyclopentyl group, cyclohexyl group, cyclohexenyl group, 1-methylcyclohexyl group, 1-allylcyclohexyl group, 1-benzylcyclohexyl group, cycloheptyl group, cycloheptenyl group, cycloheptatrienyl group, 1-methylcyclo Heptyl group, 1-allylcycloheptyl group, 1-benzylcycloheptyl group, cyclooctyl group, cyclooctenyl group, cyclooctadienyl group, 4-cyclohexyl-tert-butyl group, norbornyl group, 2-methylbicyclo [2.2 .1] Heptane-2-yl group, bicyclo [2.2.2] octane-1-yl group, 1-adamantyl group, 2-adamantyl group, pentarenyl group, indenyl group, fluorenyl group and the like are preferable, and cyclopentyl group, cyclopentyl group, etc. Cyclopentenyl group, 1-methylcyclopentyl group, cyclohexyl group, cyclohexenyl group, 1-methylcyclohexyl group and 1-adamantyl group are more preferable.

Among the aromatic substituents having 6 to 40 carbon atoms, phenyl group, trill group, xsilyl group, mesityl group, cumenyl group, 2,6-di-iso-propylphenyl group, 2,4,6-tri -Iso-propylphenyl group, 4-tert-butylphenyl group, 3,5-di-tert-butylphenyl group, allylphenyl group, prenylphenyl group, 4-adamantylphenyl group, naphthyl group, biphenyl group, terphenyl group , Binaphthyl group, phenanthryl group, anthracenyl group, ferrosenyl group and the like, preferably phenyl group, trill group, xylyl group, mesityl group, cumenyl group, 2,6-di-iso-propylphenyl group, 2,4,6-tri -Iso-propylphenyl group, 4-tert-butylphenyl group, 3,5-di-tert-butylphenyl group, allylphenyl group, 4-adamantylphenyl group, naphthyl group, biphenyl group, phenanthryl group, anthracenyl group preferable.

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, and a 3,3,3-tri. Fluoropropyl group, nonafluorobutyl group, 4,4,4-trifluorobutyl group, dodecafluorohexyl group, 6,6,6-trifluorohexyl group, chlorophenyl group, fluorophenyl group, difluorophenyl group, trifluorophenyl Group, tetrafluorophenyl group, pentafluorophenyl group, di-tert-butyl-fluorophenyl group, trifluoromethylphenyl group, bistrifluoromethylphenyl group, trifluoromethoxyphenyl group, bistrifluoromethoxyphenyl group, trifluoromethylthiophenyl Group, bistrifluoromethylthiophenyl group, fluorobiphenyl group, difluorobiphenyl group, trifluorobiphenyl group, tetrafluorobiphenyl group, pentafluorobiphenyl group, di-tert-butyl-fluorobiphenyl group, trifluoromethylbiphenyl group, bistrifluoromethyl Biphenyl group, trifluoromethoxybiphenyl group, bistrifluoromethoxybiphenyl group, trifluoromethyldimethylsilyl group, trifluoromethoxy group, pentafluoroethoxy group, fluorophenoxy group, difluorophenoxy group, trifluorophenoxy group, pentafluorophenoxy group, Di-tert-butyl-fluorophenoxy group, trifluoromethylphenoxy group, bistrifluoromethylphenoxy group, trifluoromethoxyphenoxy group, bistrifluoromethoxyphenoxy group, difluoromethylenedioxyphenyl group, bistrifluoromethylphenyliminomethyl group, tri Fluoromethylthio groups, etc. may be mentioned.

Among the halogen-containing groups, fluoromethyl group, trifluoromethyl group, pentafluoroethyl group, 2,2,2-trifluoroethyl group, 3,3,3-trifluoropropyl group, 4,4,4-tri Fluorobutyl group, fluorophenyl group, difluorophenyl group, trifluorophenyl group, tetrafluorophenyl group, pentafluorophenyl group, trifluoromethylphenyl group, bistrifluoromethylphenyl group, trifluoromethoxyphenyl group, pentafluorobiphenyl group, Trifluoromethylbiphenyl group, bistrifluoromethylbiphenyl group, trifluoromethoxy group, pentafluorophenoxy group, bistrifluoromethylphenoxy group, bistrifluoromethylphenoxy group, difluoromethylenedioxyphenyl group, trifluoromethylthio group are preferable. Methyl group, fluorophenyl group, pentafluorophenyl group, trifluoromethylphenyl group, bistrifluoromethylphenyl group, pentafluorobiphenyl group, trifluoromethoxy group and pentafluorophenoxy group are more preferable.

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

Among the silicon-containing groups, trimethylsilyl group, triethylsilyl group, tri-iso-propylsilyl group, tert-butyldimethylsilyl group, triphenylsilyl group, cyclopentadienyldimethylsilyl group, cyclopentadienyldiphenylsilyl group, Indenyldimethylsilyl group, indenyldiphenylsilyl group, fluorenyldimethylsilyl group, fluorenyldiphenylsilyl group, 4-trimethylsilylphenyl group, 4-triethylsilylphenyl group, 4-tri-iso-propylsilylphenyl group, 4-Triphenylsilylphenyl group, 3,5-bis (trimethylsilyl) phenyl group and the like are preferable, and trimethylsilyl group, triethylsilyl group, tert-butyldimethylsilyl group, 4-trimethylsilylphenyl group, 4-triethylsilylphenyl group, 4 -Tri-iso-propylsilylphenyl group and 3,5-bis (trimethylsilyl) phenyl group are more preferable.

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

Among the oxygen-containing groups, methoxy group, ethoxy group, iso-propoxy group, allyloxy group, n-butoxy group, tert-butoxy group, prenyloxy group, benzyloxy group, phenoxy group, naphthoxy group, toluyloxy group, iso -Propylphenoxy group, allylphenoxy group, tert-butylphenoxy group, methoxyphenoxy group, biphenyloxy group, binaphthyloxy group, allyloxymethyl group, benzyloxymethyl group, phenoxymethyl group, methoxyethyl group, methoxyallyl group, benzyl Oxyallyl group, phenoxyallyl group, dimethoxymethyl group, dioxolanyl group, tetramethyldioxolanyl group, dioxanyl group, dimethyldioxanyl group, methoxyphenyl group, iso-propoxyphenyl group, allyloxyphenyl group, phenoxyphenyl group, Methylenedioxyphenyl group, 3,5-dimethyl-4-methoxyphenyl group, 3,5-di-tert-butyl-4-methoxyphenyl group, frill group, methylfuryl group, tetrahydropyranyl group, flofuryl group, benzofuryl Groups, dibenzofuryl groups and the like are preferable, and methoxy group, iso-propoxy group, tert-butoxy group, allyloxy group, phenoxy group, dimethoxymethyl group, dioxolanyl group, methoxyphenyl group, iso-propoxyphenyl group and allyloxyphenyl group are preferable. , Phenoxyphenyl group, 3,5-dimethyl-4-methoxyphenyl group, 3,5-di-tert-butyl-4-methoxyphenyl group, frill group, methylfuryl group, benzofuryl group, dibenzofuryl group are more preferable.

The nitrogen-containing group is preferably an amino group and a nitrogen-containing group having 1 to 20 carbon atoms, and the latter is, for example, a dimethylamino group, a diethylamino group, an allylamino group, a diallylamino group, a didecylamino group, a benzylamino group, or a di. Phenylamino group, pyrrolidinyl group, piperidinyl group, molyphoryl group, azepinyl group, dimethylaminomethyl group, dibenzylaminomethyl group, pyrrolidinylmethyl group, dimethylaminoethyl group, benzylaminomethyl group, benzylaminoethyl group, pyrrolidini Luethyl group, dimethylaminovinyl group, benzylaminovinyl group, pyrrolidinylvinyl group, dimethylaminopropyl group, benzylaminopropyl group, pyrrolidinylpropyl group, dimethylaminoallyl group, benzylaminoallyl group, pyrrolidinylallyl Group, aminophenyl group, dimethylaminophenyl group, 3,5-dimethyl-4-dimethylaminophenyl group, 3,5-di-iso-propyl-4-dimethylaminophenyl group, durolidinyl group, tetramethyldurolidinyl group , Pyrrolidinyl phenyl group, Pyrrolyl phenyl group, Pyridyl phenyl group, Kinolyl phenyl group, Isoquinolyl phenyl group, Indolinyl phenyl group, Indrill phenyl group, Carbazolyl phenyl group, Di-tert-Butyl carbazoli Phenyl 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 -Phenylcarbazolyl group, imidazolyl group, dimethylimidazolidinyl group, benzoimidazolyl group, oxazolyl group, oxazolidinyl group, benzoxazolyl group and the like can be mentioned.

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 and pyrrolidini Lumethyl 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, durolidinyl group, tetramethylduroridinyl group, pyrrolidinylphenyl group, pyrrolylphenyl group, carbazolyl Phenyl group, di-tert-butylcarbazolylphenyl group, pyrrolyl group, pyridyl group, quinolyl group, tetrahydroquinolyl group, iso-quinolyl group, tetrahydro-iso-quinolyl group, indolyl group, indolinyl group, carbazolyl group, di -Tert-Butylcarbazolyl group, imidazolyl group, dimethylimidazolidinyl group, benzoimidazolyl group, oxazolyl group, oxazolidinyl group, benzoxazolyl group and the like are preferable, and amino group, dimethylamino group, diethylamino group and pyrrolidinyl are preferable. Group, dimethylaminophenyl group, 3,5-dimethyl-4-dimethylaminophenyl group, 3,5-di-iso-propyl-4-dimethylaminophenyl group, durolidinyl group, tetramethyldurolidinyl group, pyrrolidinyl A phenyl group, a pyrrolyl group, a pyridyl group, a carbazolyl group, and an imidazolyl group are more preferable.

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 and a benzylthioethyl group. Phenylthioethyl group, naphthylthioethyl group, methylthiovinyl group, benzylthiovinyl group, phenylthiovinyl group, naphthylthiovinyl group, methylthiopropyl group, benzylthiopropyl group, phenylthiopropyl group, naphthylthiopropyl group, Methylthioallyl group, benzylthioallyl group, phenylthioallyl group, naphthylthioallyl group, mercaptophenyl group, methylthiophenyl group, thienylphenyl group, methylthienylphenyl group, benzothienylphenyl group, dibenzothienylphenyl group, benzodithienylphenyl Group, thienyl group, tetrahydrothienyl group, methylthienyl group, thienofryl group, thienothienyl group, benzothienyl group, dibenzothienyl group, thienobenzofuryl group, benzodithienyl group, dithiolanyl group, dithianyl group, oxathiolanyl group, oxathianyl group, thiazolyl Examples include a group, a benzothiazolyl group, a thiazolidinyl group and the like.

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

Of R ² , at least one is a saturated hydrocarbon group having 3 to 10 carbon atoms in the linear portion or a terminal unsaturated hydrocarbon group having 3 to 10 carbon atoms in the linear portion, preferably directly. It is a saturated hydrocarbon group having 3 to 10 carbon atoms in the chain portion.

The saturated hydrocarbon group having 3 to 10 carbon atoms in the linear portion is a saturated hydrocarbon group having a linear hydrocarbon group having 3 to 10 carbon atoms, and examples thereof include n-propyl group and the like. n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, isobutyl group, sec-butyl group, tert-pentyl group, 2- Examples thereof include methylpentane-2-yl group, 1-ethylcyclopentyl group, 1- (n-propyl) cyclopentyl group, 1-ethylcyclohexyl group, 1- (n-propyl) cyclohexyl group, and n-propyl group and n. -Butyl group, n-pentyl group, n-hexyl group are preferable.

The terminal 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 having an unsaturated bond at the terminal. As an example, allyl group, buta-3-en-1-yl group, methallyl group, penta-4-en-1-yl group, hexa-5-en-1-yl group, hepta-6-ene. -1-yl group, octa-7-en-1-yl group, nona-8-en-1-yl group, deca-9-en-1-yl group, 2-methylbut-3-en-2-yl group Examples include a group, a 2-methylpenta-4-en-2-yl group, a 1-vinylcyclopentyl group, a 1-allylcyclopentyl group, a 1-vinylcyclohexyl group, a 1-allylcyclohexyl group, and the like, an allyl group and a pig-3-. It is preferably an en-1-yl group, a penta-4-en-1-yl group, or a hexa-5-en-1-yl group.

Adjacent R ^2s may be bonded to each other to form a saturated ring which may have a substituent. As these formed rings, a 5- to 8-membered ring which may have a substituent which is condensed in the cyclopentadienyl ring portion is preferable. When there are a plurality of rings, they may be the same or different from each other. The ring is more preferably a 5- or 6-membered ring, although it is not particularly limited as long as the effect of the present invention is exhibited. As a structure in which the ring and the cyclopentadienyl ring portion of the mother nucleus are combined, for example, a tetrahydropentalenyl ring, a tetrahydroindenyl ring, a pentarenyl ring, an indenyl ring, and an azulenyl ring (these have substituents). It may be.).

<< Preferred Embodiment of Transition Metal Compound (A) >>
As a preferable form of the transition metal (A), in the general formula (1), M is a zirconium atom or a hafnium atom, and X is independently a hydrogen atom, a halogen atom, and 1 to 20 carbon atoms. Examples thereof include transition metal compounds which are hydrocarbon groups, silicon-containing groups or oxygen-containing groups.

As a more preferable form from the viewpoint of R ¹ , in the above general formula (1), R ¹ is independently a hydrogen atom or a methyl group, and at least two R ^1s are methyl groups, and the remaining R 1 is used. ¹ can be a transition metal compound which is a hydrogen atom or a methyl group.

As a more preferable form from the viewpoint of R ² , in the general formula (1), R ² is independently a hydrogen atom or a hydrocarbon group having 1 to 40 carbon atoms, and at least one R ² is. A transition metal compound in which the linear moiety is a saturated hydrocarbon group or a terminal unsaturated hydrocarbon group having 3 to 10 carbon atoms and at least two R ^2s are hydrogen atoms can be mentioned.

As a more preferable form from the viewpoint of R ² , in the general formula (1), R ² is independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and at least one R ² is. The linear moiety is a saturated or end-unsaturated hydrocarbon group with 3 to 10 carbon atoms, at least two R ^2s are hydrogen atoms and the remaining R ² are hydrogen atoms or methyl groups. Transition metal compounds can be mentioned.

<< Example of transition metal compound (A) >>
As a specific example of the transition metal compound (A),
(N-propylcyclopentadienyl) (Tetramethylcyclopentadienyl) Zirconium Dichloride,
(N-Butylcyclopentadienyl) (Tetramethylcyclopentadienyl) Zirconium Dichloride,
(N-propylcyclopentadienyl) (pentamethylcyclopentadienyl) zirconium dichloride,
(N-Butyl Cyclopentadienyl) (Pentamethyl Cyclopentadienyl) Zirconium Dichloride,
(1,3-dimethylcyclopentadienyl) (1-n-butyl-3-methylcyclopentadienyl) zirconium dichloride,
Zirconium replaced with titanium or hafnium in these compounds,
Examples of these compounds include those in which dichloride is replaced with 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. Further, one kind of optical isomers having the same chemical structure may be used alone, or a mixture of optical isomers (for example, a meso-isomer mixture or a racemic mixture) may be used.

(Compound (B))
Compound (B) is
(B-1) Organometallic compound,
It is at least one compound selected from the group consisting of (B-2) an organoaluminum oxy compound and (B-3) a compound which reacts with a transition metal compound (A) to form an ion pair.

Examples of the organometallic compound (B-1) include organometallic compounds represented by the following general formulas (B-1a), (B-1b) or (B-1c).
R ^a _m Al (OR ^b ) _n H _p X _q … (B-1a)
[In the general formula (B-1a), Ra and ^Rb represent hydrocarbon groups having 1 to 15 carbon atoms, which may be the same or different from each other, where X represents ^a halogen atom and m represents 0. <m ≦ 3, n is 0 ≦ n <3, p is 0 ≦ p <3, q is a number of 0 ≦ q <3, and m + n + p + q = 3. ]
M ^a AlR ^a ₄ … (B-1b)
[In the general formula (B-1b), Ma 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 the general formula (B-1c), R ^a and R ^b represent hydrocarbon groups having 1 to 15 carbon atoms, which may be the same or different from each other, and M ^b is derived from Mg, Zn and Cd. Selected, X represents a halogen atom, r is 0 <r ≦ 2, s is 0 ≦ s ≦ 1, t is 0 ≦ t ≦ 1, and r + s + t = 2. ]
As the organometallic compound (B-1), the compounds disclosed in JP-A No. 11-315109 and EP0874005A can be used without limitation.

The organic metal compound (B-1) is preferably represented by the general formula (B-1a), and specifically, trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, trihexylaluminum, and tri. Trialkylaluminum such as octylaluminum, tri2-ethylhexylaluminum, dimethylaluminum chloride, diethylaluminum chloride, diisopropylaluminum chloride, diisobutylaluminum chloride, dialkylaluminum halide such as dimethylaluminum bromide, methylaluminum sesquichloride, ethylaluminum sesquichloride, isopropyl Alkylaluminum sesquihalides such as aluminum sesquichloride, butylaluminum sesquichloride, ethylaluminum sesquibramide, alkylaluminum dichlorides such as methylaluminum dichloride, ethylaluminum dichloride, isopropylaluminum dichloride, ethylaluminum dibromid, dimethylaluminum hydride, diethylaluminum 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, di-sec-nonyl aluminum Examples thereof include alkylaluminum hydrides such as hydrides, dimethylaluminum ethoxides, diethylaluminum ethoxides, diisopropylaluminum methoxides, diisobutylaluminum ethoxides and the like.

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

Examples of the compound (B-3) include JP-A No. 1-501950, JP-A No. 1-502060, JP-A-3-179005, JP-A-3-179006, and JP-A-3-207703. , JP-A-3-207704, US Pat. No. 5,321,106, etc., can be used without limitation, as well as Lewis acids, ionic compounds, borane compounds and carborane compounds, as well as heteropoly compounds and isopoly compounds. ..

In the ethylene polymerization catalyst according to the present invention, when an organoaluminum oxy compound (B-2) such as methylaluminoxane is used in combination as a co-catalytic component, it not only exhibits extremely high catalytic activity for ethylene, but also in a solid carrier. Since the solid carrier component containing the co-catalyst component can be easily prepared by reacting with the active hydrogen of the above, it is preferable to use the organoaluminum oxy compound (B-2) as the compound (B).

(Particular carrier (C))
The fine particle carrier (C) is an inorganic compound or an organic compound, and is a solid in the form of granules or fine particles.

Examples of the inorganic compound used as the fine particle carrier (C) include porous oxides, solid aluminoxane compounds, inorganic chlorides, clays, clay minerals and ion-exchange layered compounds.

Examples of the porous oxide include SiO ₂ , Al ₂ O ₃ , MgO, ZrO, TiO ₂ , B ₂ O ₃ , CaO, ZnO, BaO, ThO ₂ , and the like, or a composite or mixture containing these, specifically. Is natural or synthetic zeolite, SiO ₂ -MgO, SiO ₂ -Al ₂ O ₃ , SiO ₂ -TiO ₂ , SiO ₂ -V ₂ O ₅ , SiO ₂ -Cr ₂ O ₃ and SiO ₂ -TiO ₂ -MgO, etc. Is used. Of these, those containing SiO ₂ as the main component are preferable.

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

Although the properties of such a porous oxide differ depending on the type and manufacturing method, the particle size of the fine particle carrier (C) used in the present invention is usually 0.2 to 300 μm, preferably 1 to 200 μm. The specific surface area is usually in the range of 50 to 1200 m ² / g, preferably 100 to 1000 m ² / g, and the pore volume is usually in the range of 0.3 to 30 cm ³ / g. Such a carrier is used by firing at, for example, 100 to 1000 ° C., preferably 150 to 700 ° C., if necessary.

As the solid aluminoxane compound, known solid aluminoxane can be used without limitation. For example, the solid polyaluminoxane composition described in International Publication No. 2014/123212, JP-A-2019-69920 [0119]. ] To [0129], the solid aluminoxane compound described in [0129] can also be used. Known manufacturing methods include, for example, Japanese Patent Application Laid-Open No. 7-42301, Japanese Patent Application Laid-Open No. 6-220126, Japanese Patent Application Laid-Open No. 6-220128, Japanese Patent Application Laid-Open No. 11-140113, Japanese Patent Application Laid-Open No. 11-310607, and Japanese Patent Application Laid-Open No. Examples thereof include the production methods described in Kai 2000-38410, JP-A-2000-95810, International Publication No. 2010/55652, and the like.

Examples of the inorganic halide include MgCl ₂ , MgBr ₂ , MnCl ₂ , and MnBr ₂ . The inorganic halide may be used as it is, or may be used after being pulverized by a ball mill or a vibration mill. Further, it is also possible to use a product obtained by dissolving an inorganic halide in a solvent such as alcohol and then precipitating it in the form of fine particles with a precipitating agent.

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

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

Examples of such clays and clay minerals include kaolin, bentonite, wood-knot clay, gamma clay, alophen, hisingel stone, pyrophyllite, ummo group, montmorillonite group, vermiculite, ryokudei stone group, parigolskite, kaolinite, nacrite, and dikite. , Halloysite, etc., and examples of the ion-exchangeable layered compound include α-Zr (HAsO ₄ ) ₂ · H ₂ O, α-Zr (HPO ₄ ) ₂ , α-Zr (KPO ₄ ) _2.3 H ₂ O, α-Ti (HPO ₄ ) ₂ , α-Ti (HAsO ₄ ) ₂ · H ₂ O, α-Sn (HPO ₄ ) ₂ · H ₂ O, γ-Zr (HPO ₄ ) ₂ , γ-Ti (HPO ₄ ) ) ₂ , γ-Ti (NH ₄ PO ₄ ) ₂ , H ₂ O and other polyvalent metals such as crystalline acidic salts.

The clay, clay mineral or ion-exchange layered compound preferably has a pore volume of 0.1 cc / g or more with a radius of 20 Å or more measured by a mercury intrusion method, preferably 0.3 to 5 cc / g. Especially preferable. Here, the pore volume is measured in the range of a pore radius of 20 to 3 × 10 ⁴ Å by a mercury intrusion method using a mercury porosimeter. When a carrier having a pore volume of 20 Å or more and a pore volume smaller than 0.1 cc / g is used as a carrier, it tends to be difficult to obtain high polymerization activity.

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

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

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

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

<Usage and order of addition of each component>
In the step (I), the transition metal compound (A) (hereinafter, also referred to as a component (A)), the compound (B) (hereinafter, also referred to as a component (B)), and the fine particle carrier (C). ) (Hereinafter also referred to as component (C)), for example, these are mixed and contacted in an inert hydrocarbon to form a solid catalyst component.

As a method of contacting each component, paying attention to the order of contact, for example,
(I) A method of contacting the component (B) with the component (C) and then contacting the component (A) (ii) A method of contacting the component (B) with the component (A) and then contacting the component (C). (Iii) A method of contacting the component (B) with the component (C) and then contacting the mixture of the component (A) and the component (B).
(Iv) Examples thereof include a method of contacting the component (B) with the component (C), further contacting the component (B), and then contacting the mixture of the component (A) and the component (B). When a plurality of types of the component (B) are used, the components (B) may be the same or different from each other. Of the above methods, (i) and (ii) are preferable.

In each of the methods showing the contact sequence form, in the step including the contact between the component (C) and the component (B) and the step including the contact between the component (C) and the component (A), the component (G) is used. By coexisting with the above, fouling during the polymerization reaction is suppressed and the particle properties of the produced polymer are improved. As the component (G), a compound having a polar functional group can be used, a nonionic (nonionic) surfactant is preferable, and a polyalkylene oxide block, a higher aliphatic amide, a polyalkylene oxide, and a polyalkylene oxide alkyl ether are preferable. , Alkyldiethanolamine, polyoxyalkylenealkylamine, glycerin fatty acid ester, N-acylamino acid are more preferable. These may be used alone or in combination of two or more.

Examples of the solvent used for preparing the solid catalyst component include inert hydrocarbon solvents, specifically, aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene, and cyclo. Examples thereof include alicyclic hydrocarbons such as pentane, cyclohexane and methylcyclopentane, aromatic hydrocarbons such as benzene, toluene and xylene, halogenated hydrocarbons such as ethylene chloride, chlorbenzene and dichloromethane, or mixtures thereof. ..

In the contact between the component (B) and the component (C), the reaction site in the component (B) and the reaction site in the component (C) are chemically bonded to each other, and the component (B) and the component (C) are chemically bonded. ) Is formed. The contact time between the component (B) and the component (C) is usually 1 minute to 20 hours, preferably 30 minutes to 10 hours, and the contact temperature is usually −50 to 200 ° C., preferably −20 to 120 ° C. It is done in. When the initial contact between the component (B) and the component (C) is abruptly performed, the reaction heat generation and the reaction energy cause the component (C) to collapse, and the morphology of the obtained solid catalyst component deteriorates, which is used for polymerization. If so, continuous operation is often difficult due to poor polymer morphology. Therefore, in the initial contact between the component (B) and the component (C), the reaction is brought into contact at a lower temperature for the purpose of suppressing the reaction heat generation, or the reaction heat generation is controlled and the reaction is carried out at a rate at which the initial contact temperature can be maintained. Is preferable. The same applies to the case where the component (B) and the component (C) are brought into contact with each other and the component (B) is further brought into contact with each other. The contact weight ratio between the component (B) and the component (C) (weight of the component (B) / weight of the component (C)) can be arbitrarily selected, but the higher the contact weight ratio, the more components (A). ) Can be brought into contact with each other, and the catalytic activity per weight of the solid catalyst component can be improved.

The contact weight ratio of the component (B) to the component (C) [= weight of the component (B) / weight of the component (C)] is
It is preferably 0.05 to 3.0, and particularly preferably 0.1 to 2.0.
When the contact material between the component (B) and the component (C) and the component (A) are brought into contact with each other, the contact time is usually 1 minute to 20 hours, preferably 1 minute to 10 hours, and the contact temperature. Is usually in the range of −50 to 200 ° C., preferably −50 to 100 ° C.

The molar ratio [(B-1) / M] of the component (B-1) to the total transition metal atom (M) in the component (B-1) is usually 0.01 to 100. It is used in an amount of 000, preferably 0.05 to 50,000.

The molar ratio [(B-2) / M] of the component (B-2) to the total transition metal atom (M) in the component (B-2) (aluminum atom equivalent) is usually 10. It is used in an amount of up to 500,000, preferably 200 to 100,000.

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

<Step (II)>
In step (II), the 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 the step (I) and the olefin polymer produced by the prepolymerization.

The prepolymerized solid catalyst component can be prepared by prepolymerizing an olefin in the presence of the solid catalyst component, usually in an inert hydrocarbon solvent, and can be prepared by any of batch type, semi-continuous type and continuous type. It can also be carried out under reduced pressure, normal pressure or pressurized. Further, it is desirable that the prepolymerized solid catalyst component is produced in an amount of 0.01 to 1000 g, preferably 0.1 to 800 g, more preferably 0.2 to 500 g per 1 g of the solid catalyst component.

Examples of the inert hydrocarbon solvent include the same as the inert hydrocarbon solvent used in the step (I).
The prepolymerized solid catalyst component produced in the inert hydrocarbon solvent may be separated from the suspension, then suspended in the inert hydrocarbon again, and the olefin may be introduced into the obtained suspension. Further, the olefin may be introduced after drying.

The prepolymerization temperature is −20 to 80 ° C., preferably 0 to 60 ° C., and the prepolymerization time is 0.5 to 100 hours, preferably about 1 to 50 hours.
As the form of the solid catalyst component used for the prepolymerization, those already described can be used without limitation. Further, in the prepolymerization, the component (B) is used together with the solid catalyst component as needed, and the organoaluminum compound [B-1a] represented by the general formula (B-1a) is particularly preferably used. When the component (B) is used, the component (B) used together with the solid catalyst component is composed of an aluminum atom (Al) in the component (B) and a transition metal atom (M) in the transition metal compound (A). It is used in an amount such that the molar ratio (Al / M) is 0.1 to 10000, preferably 0.5 to 5000.

The concentration of the solid catalyst component formed in the step (I) in the prepolymerization system is usually 1 to 1000 g / liter, and further 10 to 500 g / liter in terms of the solid catalyst component / polymerization volume ratio. desirable. At the time of prepolymerization, the above-mentioned component (G) may coexist for the purpose of suppressing fouling or improving the particle properties.

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

<Step (III)>
In the step (III), the prepolymerized solid catalyst component is brought into contact with the 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 the amine compound (D).
The amine compound (D) is represented by the following general formula (2).

[In the general formula (2), R ³ is a hydrocarbon group having 1 or more and 30 or less carbon atoms, and R ⁴ is a hydrogen atom or a hydrocarbon group having 1 or more and 20 or less carbon atoms. When there are a plurality of R ⁴ , the plurality of R ^4s are independently defined in the same manner as described above. m and n are each independently an integer of 0 or more, and m + n is 1 or more. ]

R ³ in the general formula (I) is a hydrocarbon group having 1 or more and 30 or less carbon atoms, and may be saturated or unsaturated, may be aliphatic or aromatic, and may be linear, branched or cyclic. For example, any of an aliphatic hydrocarbon group such as an alkyl group and an alkenyl group, and an aromatic hydrocarbon group can be used. Preferred specific examples are an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a lauryl group and an oleoyl group, or an alkenyl group. The group is mentioned. In addition, cycloalkyl groups such as cyclopentyl group and cyclohexyl group; aryl groups such as phenyl group and tolyl group; aralkyl groups such as benzyl group and neofil group may also be mentioned. Of these, an alkyl group having 6 to 22 carbon atoms is preferable, an alkyl group having 8 to 18 carbon atoms is more preferable, and an alkyl group having 12 to 18 carbon atoms is particularly preferable.

R ⁴ in the general formula (I) is a hydrogen atom or a hydrocarbon group having 1 or more and 20 or less carbon atoms. When R ⁴ is a hydrocarbon group having 1 or more carbon atoms and 20 or less carbon atoms, preferred specific examples thereof include the same hydrocarbon groups as described above. Among them, a hydrogen atom and an alkyl group having 1 to 2 carbon atoms are preferable, and a hydrogen atom and a methyl group are more preferable.

M and n in the general formula (I) are integers of 0 or more, respectively. m + n is 1 or more. 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 the general formula (I) include polyoxyethylene octylamine, polyoxyethylene decylamine, polyoxyethylene laurylamine, polyoxyethylene octadecylamine, and polyoxy. Examples thereof include ethylene palm oil alkylamine, polyoxyethylene beef fat amine, polyoxyethylene hydrogenated beef fat amine, polyoxypropylene laurylamine, polyoxypropylene palm oil alkylamine, and polyoxypropylene beef fat amine. Of these, polyoxyethylene octylamine, polyoxyethylene decylamine, polyoxyethylene laurylamine, polyoxyethylene coconut oil alkylamine, and polyoxypropylene coconut oil alkylamine are preferable.

In the step (III), the temperature at which the prepolymerized solid catalyst component and the amine compound (D) are brought into contact with each other is usually −50 to 50 ° C., preferably −20 to 50 ° C., and the contact time is usually 1. Minutes to 20 hours, preferably 5 minutes to 10 hours.

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

The contact between the prepolymerized solid catalyst component and the amine compound (D) can be performed in an inert hydrocarbon solvent, and the inert hydrocarbon solvent used in step (I) is the inert hydrocarbon solvent. The same can be mentioned.

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

<Process (IV)>
In step (IV), the olefin is polymerized in the presence of the prepolymerization solid catalyst for olefin polymerization.
The step of polymerizing the 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 vapor phase polymerization methods, and suspension polymerization methods and vapor phase polymerization methods are preferable.

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

When polymerizing an olefin in the presence of the prepolymerized solid catalyst for olefin polymerization, the component (A) of the prepolymerized solid catalyst for olefin polymerization is usually 1 × 10 ^-12 to 1 × 10 per 1 liter of reaction volume. It is used in an amount of ^-1 mol, preferably 1 × 10 ^-8 to 1 × 10 ⁻² mol.

The compound (B) is preferably added to the polymerization system, and more preferably the compound represented by the general formula (B-1a) is added together with the prepolymerized solid catalyst for olefin polymerization.
When polymerizing an olefin, the lower limit of the polymerization temperature is 0 ° C., preferably 40 ° C., particularly preferably 60 ° C. The higher the temperature, the more advantageous in terms of heat removal etc. in production on an industrial scale. The upper limit is usually 200 ° C., preferably 170 ° C., and the polymerization pressure is usually normal pressure to 100 kgf / cm ² , preferably normal pressure to 50 kgf / cm ² .

The polymerization reaction can be carried out by any of a batch type, a semi-continuous type and a continuous type. Further, it is also possible to carry out the polymerization in two or more stages having different reaction conditions.
The molecular weight of the olefin polymer obtained by the method for producing an olefin polymer according to the present invention can be adjusted by allowing hydrogen to be present in the polymerization system or by changing the polymerization temperature. At the time of polymerization, the above-mentioned component (G) can coexist for the purpose of suppressing fouling or improving the particle properties.

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

Further, a small amount of styrene, vinylcyclohexane, diene or acrylic acid, methacrylic acid, fumaric acid, maleic anhydride, etc.; methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, etc., as long as the effects of the present invention are not impaired. A polar monomer such as methacrylic acid may be supplied.

<Olefin polymer>
As one aspect of the olefin polymer produced by the production method of the present invention, an ethylene-based polymer containing an ethylene-derived structural unit in the range of preferably 60 to 100 mol%, more preferably 80 to 100 mol% can be mentioned. Be done. In the case of a copolymer, the ethylene-based polymer contains a structural unit derived from an α-olefin having 3 to 20 carbon atoms, preferably in the range of 1 to 40 mol% in total, and more preferably 2 to 20 mol%. However, the total of the content of the constituent unit derived from ethylene and the content of the constituent unit derived from α-olefin having 3 to 20 carbon atoms is 100 mol%.

Among these polymers, ethylene homopolymers, ethylene / propylene copolymers, ethylene / 1-butene copolymers, ethylene / propylene / 1-butene copolymers, ethylene / 1-octene polymers, ethylene / 1 -Hexen polymer, ethylene / 4-methyl-1-pentene polymer, ethylene / propylene / 1-octene polymer, ethylene / propylene / 1-hexene polymer, ethylene / propylene / 4-methyl-1-pentene polymer Is preferable. Further, a so-called block copolymer (impact copolymer) obtained by mixing or continuously producing two or more kinds selected from these polymers may be used.

<Use of olefin polymer>
From the olefin polymer produced by the production method of the present invention, a film can be obtained by molding processes such as air-cooled inflation molding, air-cooled two-stage cooling inflation molding, high-speed inflation molding, T-die film molding, and water-cooled inflation molding.

The film obtained from the olefin polymer according to the present invention is suitable for various packaging films such as standard bags, sugar bags, oil packaging bags, water packaging bags, agricultural materials and the like. It can also be used as a multilayer film by laminating it with a base material such as nylon or polyester.

The olefin polymer according to the present invention includes weathering stabilizers, heat stabilizers, antistatic agents, antislip agents, antiblocking agents, antifogging agents, lubricants, pigments and dyes as long as the object of the present invention is not impaired. , Nuclear agents, plasticizers, antioxidants, hydrochloric acid absorbers, antioxidants and the like may be blended as necessary.

The present invention will be described in more detail with reference to the following examples. However, the present invention is not limited to the description of the following examples.

[Transition metal compounds]
The transition metal compounds (A) [component (A)] used in 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. did. ]

[Stabilizer]
The amine compound (D) [component (D)] as the stabilizer used in the examples and comparative examples is as follows.
"D-1": Lauryl diethanolamine [Electro Stripper (registered trademark) EA, manufactured by Kao Corporation]
"D-2": Stearyldiethanolamine [CAS No. 10213-78-2, manufactured by Tokyo Chemical Industry Co., Ltd.]
"D-3": Polyoxyalkylene alkylamine compound [Amit (registered trademark) 102, manufactured by Kao Corporation] (Analysis results of the types and composition ratios of the contained compounds are disclosed in Japanese Patent Application Laid-Open No. 2019-157019). It is disclosed in Table 1 of.)
"D-4": Polyoxyalkylene alkylamine compound [Amit (registered trademark) 105, manufactured by Kao Corporation]
"D-5": Alkyldiethanolamine compound [Atmer (registered trademark) 163, manufactured by Claude Japan Co., Ltd.] (Analysis results of the types and composition ratios of the contained compounds are shown in the table of Patent Document (Japanese Patent Laid-Open No. 2019-157019). It is disclosed in 1.)
"D-6": Alkyl (C16-C18) diethanolamine compound [ARMOSTAT (registered trademark) 1800, manufactured by AkzoNobel Co., Ltd.]

[Preparation Example 1] (Preparation of solid catalyst component (X-1))
Using a reactor with a stirrer with an internal volume of 270 L, silica gel (manufactured by Fuji Silysia Chemical Ltd., average particle size 70 μm, specific surface area 340 m ² / g, pore volume 1.3 cm ³ / g, pore volume 1.3 cm 3 / g, 10 at 250 ° C. (Time drying) 10 kg was suspended in 77 L of toluene and then cooled to 0-5 ° C. While maintaining the in-system temperature at 0 to 5 ° C., 19.4 L of a toluene solution of methylaluminoxane (3.5 mol / L in terms of Al atom) was added dropwise to this suspension over 30 minutes. Then, after contacting each added component for 30 minutes, the temperature inside the system was raised to 95 ° C. over 1.5 hours, and then contacted at 93 to 97 ° C. for 4 hours. Then, the temperature was lowered to room temperature, the supernatant was removed by decantation, and the residue was further washed twice with toluene to obtain a toluene slurry of a solid carrier carrying a total amount of 115 L of methylaluminoxane. When a part of this slurry was collected and analyzed, the solid content concentration was 123 g / L.

Of the obtained slurry, 12.2 L (1.50 kg as a solid content) was charged into a reactor with a stirrer having an internal volume of 114 L under a nitrogen atmosphere, and toluene was further added so that the total amount became 28 L. Next, 22.0 g (54.2 mmol in terms of Zr atom) of (n-butylcyclopentadienyl) (tetramethylcyclopentadienyl) zirconium dichloride (A-1) as the component (A) was added to 5.0 L of toluene. The dissolved solution was pressure-fed to the above reactor and contacted at a system temperature of 20 to 25 ° C. for 1 hour. The supernatant was decanted and the residue was washed 3 times with hexane. Then, hexane was further added to the washed product to make the total amount 30 L, and a hexane slurry of the solid catalyst component (X-1) was obtained.

[Preparation Example 2] (Preparation of Prepolymerized Solid Catalyst Component (XP-1))
30 L of the 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. Ethylene was continuously supplied into the system for several minutes under normal pressure while maintaining the temperature in the system at 10 to 15 ° C., and then 70 ml of 1-hexene was added. After that, ethylene supply was started at 1.46 kg / h, and prepolymerization was performed at an in-system temperature of 32 to 37 ° C. 70 ml of 1-hexene was added 5 times every 30 minutes after the start of the prepolymerization, and the ethylene supply was stopped when the ethylene supply reached 4.37 kg 180 minutes after the start of the prepolymerization. Then, the supernatant was removed by decantation, and the residue was washed 4 times with hexane. Then, hexane was further added to the washed product to make the total amount 30 L, and a hexane slurry as a prepolymerized solid catalyst component was obtained.

Next, the hexane slurry was inserted into an evaporation dryer with an internal volume of 43 L under a nitrogen atmosphere, decompressed to -68 kPaG over about 60 minutes, and vacuum dried when it reached -68 kPaG for about 4.3 hours. , Hexane and volatiles were removed. Further, the pressure was reduced to −100 kPaG, and when the pressure reached −100 kPaG, the mixture was vacuum dried for 8 hours to obtain 6.20 kg of the prepolymerized solid catalyst component (XP-1).

[Preparation Example 3] (Preparation of Prepolymerized Solid Catalyst Component (XP-2))
10.0 g of the prepolymerized solid catalyst component (XP-1) obtained in Preparation Example 2 was charged into a reactor with a stirrer having an internal volume of 200 ml under a nitrogen atmosphere, and hexane was added so that the total volume became 50 ml. Next, the temperature in the system was raised to 35 ° C., and then 100.0 mg of lauryldiethanolamine (D-1) as the component (D) was diluted with 5 ml of toluene and added, followed by contact at 32 to 37 ° C. for 2 hours. Then, a hexane slurry of a prepolymerized solid catalyst component was obtained. This hexane slurry is transferred to a glass Schlenk tube having an internal volume of 100 ml, and hexane and toluene are distilled off under reduced pressure at 25 ° C. under reduced pressure to obtain a prepolymerized solid catalyst component (“prepolymerized solid catalyst for olefin polymerization” in the present invention. ) (XP-2) 10.1 g was obtained.

[Example 1] (Production of ethylene / 1-hexene copolymer)
(Polymerization evaluation (i): Evaluation of the wall state of the autoclave during polymerization)
500 ml of n-heptane was charged into a 1 L stainless steel autoclave sufficiently substituted with nitrogen, the nitrogen in the system was replaced with ethylene, 10 ml of 1-hexene, and the prepolymerized solid catalyst component (XP-) obtained in Preparation Example 3 were charged. 2) 250 mg was added and the temperature was raised to 55 ° C. It took about 10 minutes from the addition of the prepolymerized solid catalyst component (XP-2) to the temperature of 55 ° C. Then, 200 mg of the prepolymerized solid catalyst component (XP-2) was further added to raise the temperature in the system to 73 ° C. Then, the polymerization was started by introducing ethylene, and the pressure was maintained at 8.0 kgf / cm ² -G while continuously supplying ethylene, and the polymerization was carried out for 90 minutes. After the completion of the polymerization, the pressure was depressurized, the polymer was removed, and the condition of the autoclave was confirmed. As a result, no adhesion of the polymer was observed on the wall of the autoclave or the stirring blade.

(Polymerization evaluation (ii): Polymerization activity evaluation)
500 ml of n-heptane was placed in a 1 L stainless steel autoclave sufficiently substituted with nitrogen, the inside of the system was replaced with ethylene, 20 ml of 1-hexene and 0.06 ml of a decane solution of triisobutylaluminum (1.0 mol / L). Was charged and kept at room temperature for 5 minutes. Then, 180 mg of the prepolymerized solid catalyst component (XP-2) was added to raise the temperature in the system to 73 ° C. Then, the polymerization was started by introducing ethylene, and the pressure was maintained at 8.0 kgf / cm ² -G while continuously supplying ethylene, and the polymerization was carried out for 90 minutes. After completion of the polymerization, the polymer was depressurized, the polymer was filtered and washed, and dried at 80 ° C. under reduced pressure for 10 hours to obtain 112.7 g of the polymer. The polymer yield (polymerization activity) per 1 g of the catalyst 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))
The hexane slurry of the solid catalyst component (X-1) obtained in Preparation Example 1 was charged into a reactor with an internal volume of 200 ml under a nitrogen atmosphere so as to have a solid content of 10.0 g, and the total volume became 50 ml. Hexane was added. Next, the temperature in the system was raised to 35 ° C., and then 100.0 mg of lauryldiethanolamine (D-1) as the component (D) was diluted with 5 ml of toluene and added, followed by contact at 32 to 37 ° C. for 2 hours. To obtain a hexane slurry as a solid catalyst component. This hexane slurry was transferred to a glass Schlenk tube having an internal volume of 100 ml, and hexane and toluene were distilled off under reduced pressure at 25 ° C. under reduced pressure to obtain 10.1 g of a solid catalyst component (X-2).

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

[Preparation Examples 10 to 14] (Preparation of solid catalyst components (X-3) to (X-7))
Preparation Example 4 except that the amine compound (D-2), (D-3), (D-4), (D-5) or (D-6) was used instead of the amine compound (D-1). The solid catalyst components (X-3) to (X-7) were prepared in the same manner as in the above.

[Preparation Example 15] (Preparation of Prepolymerized Solid Catalyst Component (XP-8))
The prepolymerized solid catalyst component (XP-8) was prepared by the same method 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))
The solid catalyst component (X-8) was prepared by the same method 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 to 2] (Production of ethylene / 1-hexene copolymer)
An ethylene / 1-hexene copolymer was 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 evaluation (i) and polymerization evaluation (ii) were carried out. did. The results are shown in Table 1.

As is clear from Table 1, in Example 1 in which the prepolymerization was carried out and the component (D-1) was further used, Comparative Example 1 in which the prepolymerization was not carried out and the component (D-1) were used. Adhesion of the polymer to the instrument wall of the autoclave and the stirring blade was suppressed as compared with Comparative Example 2 which was not used. Furthermore, the powder bulk density of the obtained polymer was also higher than that of Comparative Example 1.

That is, in Example 1, an olefin polymer could be stably produced as compared with Comparative Examples 1 and 2.
Further, even in Examples 2 to 6 in which the components (D-2) to (D-6) are used instead of the component (D-1), the polymer for the instrument wall and the stirring blade of the autoclave is compared with the comparative examples 3 to 7. Adhesion was suppressed.

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

The reason why such a difference in effect occurs due to the difference in the structure of the transition metal compound is presumed as follows.
Polymer adhesion to the autoclave wall surface and stirring blades occurs when the metallocene compound reaches from the solid catalyst component. The solid catalyst component and the metallocene compound interact with each other as an ion pair in which the metallocene compound is a cation and the solid catalyst component is an anion. It is considered that the asymmetric bis-Cp type metallocene compound causes steric distortion due to the asymmetry of the upper and lower ligands, and the ionic bond is weakened as compared with the symmetric bis-Cp type metallocene compound. Therefore, it is considered that the asymmetric bis-Cp type metallocene compound is easy to reach, but it becomes difficult to reach because the surrounding area is covered with the polymer by prepolymerization, and thus to the autoclave wall surface and the stirring blade. It is considered that the polymer adhesion of the above is suppressed. On the other hand, since the symmetric bis-Cp type metallocene compound is more difficult to reach than the asymmetric bis-Cp type metallocene compound, in Reference Example 2, the polymer did not adhere to the autoclave wall surface or the stirring blade without prepolymerization. It is considered to be a thing.

From the above, it can be seen that the production method of the present invention is particularly useful when an asymmetric bis-Cp type 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))
Same as Preparation Examples 1 to 3 except that the transition metal compound (A-3), (A-4), (A-5) or (A-6) was used instead of the transition metal compound (A-1). Prepolymerized solid catalyst components (XP-9) to (XP-12) were prepared by the above method.

[Preparation Examples 21 to 24] (Preparation of solid catalyst components (X-9) to (X-12))
Same as Preparation Examples 1 and 4 except that the transition metal compound (A-3), (A-4), (A-5) or (A-6) was used instead of the transition metal compound (A-1). Solid catalyst components (X-9) to (X-12) were prepared by the above method.

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

As is clear from Table 2, in Examples 7 to 10 in which the prepolymerization was carried out, adhesion of the polymer to the instrument wall and the stirring blade of the autoclave was suppressed as compared with Comparative Examples 8 to 11 in which the prepolymerization was not carried out. rice field. 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 vapor 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 supplied into the polymerization reactor at 4.2 g / hr. Further, as a stabilizer, lauryl diethanolamine was supplied into the circulating gas line so as to be present in an amount of 30 mass ppm with respect to the mass of the polymer. The gas composition in the gas phase polymerizer is ethylene partial pressure = 1.0 MPa, hydrogen / ethylene = 4.8 × 10 ^-4 (molar ratio), 1-hexene / ethylene = 0.022 (molar ratio). Ethylene, hydrogen, 1-hexene and isopentan were continuously supplied to the polymer to produce a polymer at a ratio of 6.0 kg / hr. The residence time was 4 hours. At this time, the polymer density was 916 kg / m ³ and the melt flow rate was 3.8 g / 10 min. The melt flow rate was measured according to ASTMD1238-65T under the conditions of 190 ° C. and a weight of 2.16 kg.

Although the operation was carried out for 48 hours under the above conditions, no heat spots were observed in all the places such as the polymerizer and the piping, and stable polymerization could be carried out.

[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 the operation under these conditions, heat spots were generated in the polymerizer and the like, and the operation could not be continued in 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 the operation under these conditions, heat spots were generated in the polymerizer and the like, and the operation could not be continued in 4 hours.

Claims (2)

(A) The transition metal compound represented by the following general formula (1) and

[In the general formula (1)
M is a Group 4 transition metal atom in the periodic table.
n is an integer of 1 to 4 selected so that the transition metal compound (A) is electrically neutral.
X is a neutral ligand capable of coordinating with a hydrogen atom, a halogen atom, a hydrocarbon group, an anionic ligand or an isolated electron pair, and the anion ligand is a halogen-containing group, a silicon-containing group, or oxygen. It is a containing group, a sulfur-containing group, a nitrogen-containing group, a phosphorus-containing group, a boron-containing group, an aluminum-containing group or a conjugated diene-based derivative group. But they may be different, they may combine with each other to form a ring,
R ¹ is independently a hydrogen atom or a hydrocarbon group having 1 to 2 carbon atoms, and at least two R ^1s are hydrocarbon groups having 1 to 2 carbon atoms, and adjacent R ^1s are adjacent to each other. It may be bonded to form a ring which may have a substituent.
R ² is 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, and at least one R2 is used. Reference numeral ² is a saturated hydrocarbon group having 3 to 10 carbon atoms in the linear portion or a terminal unsaturated hydrocarbon group having 3 to 10 carbon atoms in the linear moiety, and at least two R ^2s are hydrogen atoms. Yes, adjacent R ^2s may be bonded to each other to form a ring that may have a substituent. ]
(B) (B-1) Organometallic compound,
At least one compound selected from the group consisting of (B-2) an organoaluminum oxy compound and (B-3) a compound which reacts with a transition metal compound (A) to form an ion pair.
(C) Step (I) of forming a solid catalyst component by contacting with a fine particle carrier.
Step (II) of prepolymerizing an olefin in the presence of the solid catalyst component to form a prepolymerized solid catalyst component.
The prepolymerized solid catalyst component and the amine compound (D) represented by the following general formula (2)

[In the general formula (2), R ³ is a hydrocarbon group having 1 or more and 30 or less carbon atoms, and R ⁴ is a hydrogen atom or a hydrocarbon group having 1 or more and 20 or less carbon atoms. When there are a plurality of R ⁴ , the plurality of R ^4s are independently defined in the same manner as described above. m and n are each independently an integer of 0 or more, and m + n is 1 or more. ]
A step of forming a prepolymerized solid catalyst for olefin polymerization (III) and a step of polymerizing an olefin in the presence of the prepolymerized solid catalyst for olefin polymerization (IV).
A method for producing an olefin polymer containing. The method for producing an olefin polymer according to claim 1, wherein the step of polymerizing the olefin is a step of homopolymerizing ethylene or a step of copolymerizing ethylene with an α-olefin having 3 or more and 20 or less carbon atoms.