JP2020132630A - Transition metal compound, catalyst for olefin polymerization and method for producing olefin polymer - Google Patents

Abstract

To provide a transition metal compound that, when used as a component of a catalyst for olefin polymerization, has high olefin polymerization activity even at a polymerization temperature suitable in commercial production, and allows production of a high molecular weight polymer.SOLUTION: A transition metal compound represented by formula A-1 or the like.SELECTED DRAWING: None

Description

The present invention relates to a transition metal compound, a catalyst for olefin polymerization, and a method for producing an olefin polymer using the same.

Conventionally, as a catalyst for producing an olefin polymer such as an ethylene polymer and an ethylene / α-olefin copolymer, it is composed of a titanium-based catalyst composed of a titanium compound and an organoaluminum compound, and a vanadium compound and an organoaluminum compound. Vanadium-based catalysts are known.

Further, as a catalyst capable of producing an olefin polymer with high polymerization activity, a metallocene-based catalyst composed of a metallocene compound such as zirconocene and an organoaluminum oxy compound (aluminoxane) is known.

On the other hand, the applicant has proposed a catalyst for olefin polymerization containing a transition metal compound having a salicylaldoimine ligand (see, for example, Patent Document 1). The catalyst for olefin polymerization containing the transition metal compound represented by the general formula (I) of Patent Document 1 is known to exhibit high olefin polymerization activity, but further improvement of the polymerization activity is required. Further, although the catalyst for olefin polymerization containing the transition metal compound can copolymerize two or more kinds of olefins, further improvement in polymerization activity and copolymerizability has been required.

In addition, the applicant has proposed a transition metal compound represented by the general formula (I) of Patent Document 2 and a transition metal compound represented by the general formula (I) of Patent Document 3. The olefin polymerization catalyst containing the transition metal compound exhibits superior olefin polymerization activity when homopolymerizing the olefin, as compared with the catalyst containing the transition metal compound represented by the general formula (I) of Patent Document 1. It has also been found that the polymerization activity, copolymerizability and thermal stability when copolymerizing two or more kinds of olefins are improved.

Japanese Unexamined Patent Publication No. 11-315109 Japanese Unexamined Patent Publication No. 2011-016789 Japanese Unexamined Patent Publication No. 2014-224053

Generally, when the polymerization temperature is raised, the molecular weight of the obtained polymer tends to decrease. Depending on the structure of the catalyst, the molecular weight may decrease extremely as the polymerization temperature increases. Therefore, it is important to develop an olefin polymerization catalyst capable of producing a high molecular weight polymer even at a high temperature suitable for commercial production.

The present invention has been made in view of the above-mentioned problems in the prior art, is a transition metal compound that can be used as a component of a catalyst for olefin polymerization, and is an olefin even at a polymerization temperature suitable for commercial production. Provided are a transition metal compound capable of producing a polymer having high polymerization activity and a high molecular weight, preferably also having excellent copolymerization performance, a catalyst for olefin polymerization using the same, and a method for producing an olefin polymer. The purpose is.

As a result of diligent research to solve the above problems, the present inventors have found that the above problems can be solved by introducing a substituent at a specific position of the ligand in the transition metal compounds described in Patent Documents 2 and 3. We found and completed the present invention.

The gist of the present invention is as follows.
[1]
The transition metal compound [A] represented by the following general formula [1].

（一般式［１］中、Ｍは、周期表第４族遷移金属原子であり、
ｎは、遷移金属化合物［Ａ］が電気的に中性となるように選択される１〜４の整数であり、
Ｘは、水素原子、ハロゲン原子、炭化水素基、アニオン配位子または孤立電子対で配位可能な中性配位子であり、前記アニオン配位子は、ハロゲン含有基、ケイ素含有基、酸素含有基、硫黄含有基、窒素含有基、リン含有基、ホウ素含有基、アルミニウム含有基または共役ジエン系誘導体基であり、ｎが２以上の場合は、複数存在するＸで示される基は互いに同一でも異なっていてもよく、互いに結合して環を形成してもよく、
Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶、Ｒ⁷、Ｒ⁸、Ｒ⁹、Ｒ¹⁰、Ｒ¹¹、Ｒ¹²およびＲ¹³は、それぞれ独立に、水素原子、ハロゲン原子、炭素数１〜４０の炭化水素基、ハロゲン含有基、ケイ素含有基、酸素含有基、窒素含有基または硫黄含有基であり、
ただし、Ｒ⁵およびＲ⁶のうち少なくとも１つは、水素原子ではなく、
Ｒ¹〜Ｒ¹³のうちの隣接した置換基同士は、互いに結合して置換基を有していてもよい環を形成してもよい。）

(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 anionic 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, and when n is 2 or more, a plurality of groups represented by X are the same. But they may be different, they may combine with each other to form a ring,
R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² and R ¹³ are independent hydrogen and halogen atoms, respectively. It is 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.
However, at least one of R ⁵ and R ⁶ is not a hydrogen atom,
Adjacent substituents of R ^{1 to} R ¹³ may be bonded to each other to form a ring which may have a substituent. )

[2]
In the general formula [1], R ¹ , R ² , R ³ , R ⁴ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² and R ¹³ are each independently hydrogen. Atomic, hydrocarbon group with 1 to 40 carbon atoms, halogen atom, halogen-containing group, silicon-containing group, oxygen-containing group, nitrogen-containing group or sulfur-containing group, R ⁵ is a hydrogen atom, hydrocarbon with 1 to 40 carbon atoms The transition metal compound [A] of the above [1], which is a hydrogen group, a halogen-containing group, a silicon-containing group, an oxygen-containing group, a nitrogen-containing group or a sulfur-containing group.

[3]
In the general formula [1], R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² and R ¹³ are independent of each other. The transition metal compound [A] according to the above [1], which is a hydrogen atom, a hydrocarbon group having 1 to 40 carbon atoms, a halogen-containing group, a silicon-containing group, an oxygen-containing group, a nitrogen-containing group or a sulfur-containing group.

[4]
In the general formula [1],
X is independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 10 carbon atoms, a silicon-containing hydrocarbon group, or an oxygen-containing hydrocarbon group.
R ⁴ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ and R ¹² are hydrogen atoms,
R ¹ , R ² , R ³ , R ¹¹ and R ¹³ independently have a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group having 1 to 20 carbon atoms, and oxygen having 1 to 20 carbon atoms. The transition metal compound [A] according to any one of the above [1] to [3], which is a containing group or a nitrogen-containing group having 1 to 20 carbon atoms.

[5]
In the general formula [1],
R ⁵ is a hydrocarbon group having 1 to 10 carbon atoms or a halogen-containing group having 1 to 10 carbon atoms.
The transition metal compound [A] of the above [4], wherein R ¹¹ and R ¹³ are each independently a hydrocarbon group having 1 to 10 carbon atoms.

[6]
In the general formula [1],
M is a titanium atom,
n is 2 or 3
X is a neutral ligand coordinated with a lone pair of electrons on a halogen or oxygen atom.
The transition metal compound [A] of the above [5], wherein R ⁵ is an aromatic hydrocarbon group having 10 or less carbon atoms.

[7]
A catalyst for olefin polymerization containing the transition metal compound [A] according to any one of [1] to [6].

[8]
Furthermore, [B] [B-1] organometallic compounds,
[B-2] Organoaluminium oxy compounds and
[B-3] The catalyst for olefin polymerization according to the above [7], which comprises at least one compound selected from the group consisting of compounds that react with the transition metal compound [A] to form an ion pair.

[9]
The method for producing an olefin polymer, which comprises a step of polymerizing an olefin in the presence of the catalyst for olefin polymerization according to the above [7] or [8].

[10]
The olefin polymer of the above [9], wherein the step of polymerizing the olefin is a step of homopolymerizing ethylene, a step of homopolymerizing propylene, or a step of copolymerizing ethylene with an α-olefin having 3 or more and 20 or less carbon atoms. Manufacturing method.

When the transition metal compound of the present invention is used as a component of a catalyst for olefin polymerization, it is possible to produce a polymer having high olefin polymerization activity and high molecular weight even at a polymerization temperature suitable for commercial production.

Hereinafter, the transition metal compound and the like according to the present invention will be described in more detail.
[Transition metal compound [A]]
The transition metal compound [A] according to the present invention (hereinafter, may be referred to as “component (A)”) is represented by the following general formula [1].

<< M, n, X >>
In the general formula [1], M is a Group 4 transition metal atom of the periodic table, preferably a titanium atom.
n is an integer of 1 to 4, preferably 2 or 3, in which the transition metal compound [A] is selected to be 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 anionic 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 10 carbon atoms, a silicon-containing hydrocarbon group or an oxygen-containing hydrocarbon group, and more preferably a lone electron pair on the halogen atom or the oxygen atom. It is a neutral ligand that is located.

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. 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
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 (butane-2- Il group), tert-butyl group (2-methylpropan-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), siamil group (1,2-dimethylpropyl group), iso-hexyl group (4-methylpentyl group), 2,2-dimethylbutyl group, 2 , 3-dimethylbutyl group, 3,3-dimethylbutyl group, texyl group (2,3-dimethylbut-2-yl group), 4,4-dimethylpentyl group and other linear or branched alkyl groups;
Vinyl group, allyl group, propenyl group (propa-1-ene-1-yl group), iso-propenyl group (propa-1-en-2-yl group), allenyl group (propa-1,2-diene-1) -Il group), porcine-3-ene-1-yl group, crotyl group (but-2-en-1-yl group), porcine-3-en-2-yl group, metalyl group (2-methylallyl group) , Buta-1,3-dienyl group, penta-4-ene-1-yl group, penta-3-en-1-yl group, penta-2-en-1-yl group, iso-pentenyl group (3- Methylbuta-3-ene-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 group) or an unsaturated double bond-containing group;
Linear or branched alkynyl groups such as ethynyl group, propa-2-in-1-yl group, propargyl group (propa-1-in-1-yl group) or unsaturated triple bond-containing group;
Benzyl group, 2-methylbenzyl group, 4-methylbenzyl group, 2,4,6-trimethylbenzyl group, 3,5-dimethylbenzyl group, Kuminyl 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, tolyl group (methylphenyl group), xsilyl 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 above 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) silyl 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 methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an allyloxy group, an n-butoxy group, a sec-butoxy group, an iso-butoxy group, a tert-butoxy group and a benzyloxy group. Group, methoxymethoxy group, phenoxy group, 2,6-dimethylphenoxy group, 2,6-di-iso-propylphenoxy group, 2,6-di-tert-butylphenoxy group, 2,4,6-trimethylphenoxy group , 2,4,6-tri-iso-propylphenoxy group, acetoxy group, pivaloyloxy group, benzoyloxy group, trifluoroacetoxy group, perchlorate anion, 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), and a nonaflate group (nonaflatebutanesulfonyl group). Examples thereof include a mesylate group (methanesulfonate group), a tosylate group (p-toluenesulfonate group), a triflate group (trifluoromethanesulfonate group), and a nonaflate group (nonaflatebutanesulfonate group).

Among the sulfur-containing groups, a triflate group (trifluoromethanesulfonate group) 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 morpholic 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 is an aryl group or halogen atom which may independently have a hydrogen, an alkyl group, a substituent, etc. The groups represented by) are mentioned.

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

を形成可能な、ＡｌＲ₄（Ｒは水素、アルキル基、置換基を有してもよいアリール基またはハロゲン原子等を示す）で表される基が挙げられる。

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 metallocyclopentene groups can be mentioned.

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 lutidine. Heterocyclic compounds such as oxazoline, oxazole, thiazole, imidazole and thiophene, and organic phosphorus compounds such as triphenylphosphine, tricyclohexylphosphine and tri-tert-butylphosphine can be mentioned, with tetrahydrofuran being preferred.

《R ^{1 to} R ¹³ 》
In the general formula [1], R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² and R ¹³ are independent of each other. A hydrogen atom, a hydrocarbon group having 1 to 40 carbon atoms, a halogen atom, 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 of R ⁵ and R ^6. Is a similar substituent other than the hydrogen atom.

Examples of the hydrocarbon groups having 1 to 40 carbon atoms as R ^{1 to} R ¹³ include hydrocarbon groups having 1 to 20 carbon atoms, and more specific examples thereof include the above-mentioned example of X. Specific examples of hydrocarbon groups can be given.

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 , Tert-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, heptane-4 -Il group, 2,4-dimethylpentane-2-yl group, 3-ethylpentane-3-yl group, 4,4-dimethylpentyl group, 4-methylheptane-4-yl group, 4-propylheptane-4 A linear or branched alkyl group having 1 to 40 carbon atoms, such as a −yl group, 2,3,3-trimethylbutan-2-yl group, and 2,4,4-trimethylpentan-2-yl group. ;
Vinyl group, allyl group, propenyl group, iso-propenyl group, allenyl group, buta-3-ene-1-yl group, crotyl group, buta-3-en-2-yl group, metallicyl group, pig-1,3 -Dienyl group, penta-4-ene-1-yl group, penta-3-en-1-yl group, penta-2-en-1-yl group, iso-pentenyl group, 2-methylbuta-3-ene- 1-yl group, penta-4-en-2-yl group, prenyl group, 2-methyl-but-2-ene-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-diene-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-ene- 1-yl group, 3-methyl-penta-4-ene-1-yl group, 2-methyl-penta-4-ene-1-yl group, hexa-5-en-2-yl group, 4-methyl- Penta-3-ene-1-yl group, 3-methyl-penta-3-ene-1-yl group, 2,3-dimethyl-but-2-ene-1-yl group, 2-methylpenta-4-ene -2-Il group, 3-ethylpenta-1-ene-3-yl group, hexa-3,5-diene-1-yl group, hexa-2,4-diene-1-yl group, 4-methylpenta-1 , 3-Diene-1-yl group, 2,3-dimethyl-buta-1,3-diene-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, porcine-1-in-1-yl group, porcine-2-in-1-yl group, porcine-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 triplet 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-phenylpropan-2-yl group), 2- (4-methylphenyl) ) Propyl-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-3-ene-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-phenylpropan-2-yl group, 3-phenylpropi Lu group, cinnamyl group (3-phenylallyl group), neofil 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) ) Propyl-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-azulenyl) propan-2-yl group, (1-azulenyl) diphenylmethyl group, 2- Aromatic-containing linear or branched alkyl groups having 7 to 40 carbon atoms such as (1-azulenyl) ethyl groups and unsaturated double bond-containing groups;
Cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclopentenyl group, cyclopentadienyl group, dimethylcyclopentadienyl group, n-butylcyclopentadienyl group, n-butyl-methylcyclopentadienyl group, tetramethylcyclo Pentazienyl group, 1-methylcyclopentyl group, 1-allylcyclopentyl group, 1-benzylcyclopentyl group, cyclohexyl group, cyclohexenyl group, cyclohexadienyl group, 1-methylcyclohexyl group, 1-allylcyclohexyl group, 1-benzyl Cyclohexyl group, cycloheptyl group, cycloheptenyl group, cycloheptatrienyl group, 1-methylcycloheptyl group, 1-allylcycloheptyl group, 1-benzylcycloheptyl group, cyclooctyl group, cyclooctenyl group, cyclooctadienyl group, Cyclooctatrienyl group, 1-methylcyclooctyl group, 1-allylcyclooctyl group, 1-benzylcyclooctyl group, 4-cyclohexyl-tert-butyl group, norbornyl group, norbornenyl group, norbornadienyl group, 2- Methylbicyclo [2.2.1] heptane-2-yl group, 7-methylbicyclo [2.2.1] heptane-7-yl group, bicyclo [2.2.2] octane-1-yl group, bicyclo [2.2.2] Octane-2-yl group, 1-adamantyl group, 2-adamantyl group, 1- (2-methyladamantyl), 1- (3-methyladamantyl), 1- (4-methyladamantyl) , 1- (2-phenyladamantyl), 1- (3-phenyladamantyl), 1- (4-phenyladamantyl), 1- (3,5-dimethyladamantyl), 1- (3,5,7-trimethyladamantyl) ), 1- (3,5,7-triphenyladamantyl), pentarenyl group, indenyl group, fluorenyl group, indasenyl group, tetrahydroindacenyl group, benzoindenyl group, azulenyl group, etc. have 3 to 40 carbon atoms. Cyclic saturated and unsaturated hydrocarbon groups;
Phenyl group, trill group, xsilyl 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 (for example, [1,1': 3', 1 "-terphenyl] -2 '-Il group), binaphthyl group, acenaphthalenyl group, phenylenyl group, anthracenyl group, pyrenyl group, ferrocenyl group and other aromatic substituents having 6 to 40 carbon atoms can be mentioned.

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-methylheptan-4-yl group, 4-propylheptan-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. A -2-yl group and a 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-ene-1-yl group, crotyl group and metallicl Group, penta-4-ene-1-yl group, prenyl group, penta-1,4-diene-3-yl group, hexa-5-ene-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-ene-1-yl group and penta. A -4-ene-1-yl group, a prenyl group, and a hexa-5-ene-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, ethynyl group, propa-2-in-1-yl group, propargyl group, buta-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 preferred are an in-1-yl group, a propargyl group, a buta-2-in-1-yl group and a buta-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, cumyl group, 2,4,6-tri-iso-propylbenzyl group, 4-tert-butylbenzyl group, 3,5-di-tert-butylbenzyl Group, benzhydryl group, cumyl group, 1,1-diphenylethyl group, trityl group, 2-phenylethyl group, 2- (4-methylphenyl) ethyl group, 2- (2,4,6-trimethylphenyl) ethyl group , 2- (3,5-dimethylphenyl) ethyl group, 2- (2,4,6-tri-iso-propylphenyl) ethyl group, 2- (4-tert-butylphenyl) ethyl group, 2- (3) , 5-Di-tert-butylphenyl) ethyl group, styryl group, 2-methyl-1-phenylpropan-2-yl group, 3-phenylpropyl group, cinnamyl group, neofil group, cyclopentadienyldiphenylmethyl group, 2- (1-indenyl) propan-2-yl group, (1-indenyl) diphenylmethyl group, 2- (1-indenyl) ethyl group, 2- (9-fluorenyl) propan-2-yl group, (9- Fluolenyl) 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] Heptan-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. More preferably, a cyclopentenyl group, a 1-methylcyclopentyl group, a cyclohexyl group, a cyclohexenyl group, a 1-methylcyclohexyl group and a 1-adamantyl group.

Among the aromatic 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 are preferable, and 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, 4-adamantylphenyl group, naphthyl group, biphenyl group, phenanthryl group, anthracenyl group preferable.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Of these, fluorine atoms and chlorine atoms 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 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, and the like.

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. More preferably, a methyl group, a fluorophenyl group, a pentafluorophenyl group, a trifluoromethylphenyl group, a bistrifluoromethylphenyl group, a pentafluorobiphenyl group, a trifluoromethoxy group, and a pentafluorophenoxy group.

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.

Examples of the oxygen-containing group include a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an allyloxy group, an n-butoxy group, a sec-butoxy group, an iso-butoxy group, a tert-butoxy group, and a metallicyloxy group. , Plenyloxy group, benzyloxy group, methoxymethoxy group, methoxyethoxy group, phenoxy group, naphthoxy group, toluyloxy group, iso-propylphenoxy group, allylphenoxy group, tert-butylphenoxy group, methoxyphenoxy group, iso-propoxy Phenoxy 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, phenoxyvinyl group, methoxyallyl group, allyloxyallyl group, benzyloxyallyl Group, phenoxyallyl group, dimethoxymethyl group, di-iso-propoxymethyl group, dioxolanyl group, tetramethyldioxolanyl group, dioxanyl group, methoxyphenyl group, iso-propoxyphenyl group, allyloxyphenyl group, phenoxyphenyl group, Methylenedioxyphenyl group, 3,5-dimethyl-4-methoxyphenyl group, 3,5-di-tert-butyl-4-methoxyphenyl group, frill group, methylfuryl group, tetrahydrofuryl group, pyranyl group, tetrahydropyrani Examples thereof include a ru group, a flofuryl group, a benzofuryl group, and a dibenzofuryl group.

Among the oxygen-containing groups, an alkoxy group having 1 to 20 carbon atoms (preferably 1 to 10) is preferable, and specifically, a methoxy group, an ethoxy group, an iso-propoxy group, an allyloxy group, an n-butoxy group, and a 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, benzyloxyallyl group, phenoxyallyl group, dimethoxymethyl group, dioxolanyl group, tetramethyldioxolanyl group, dioxanyl group, dimethyldi Oxanyl 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 group, dibenzofuryl group and the like are preferable, and methoxy group, iso-propoxy group, tert-butoxy group, allyloxy group and phenoxy are preferable. Group, dimethoxymethyl group, dioxolanyl group, methoxyphenyl group, iso-propoxyphenyl group, allyloxyphenyl group, phenoxyphenyl group, 3,5-dimethyl-4-methoxyphenyl group, 3,5-di-tert-butyl- 4-Methoxyphenyl group, frill group, methyl frill group, benzofuryl group and dibenzofuryl group are more preferable.

Examples of the nitrogen-containing group include an amino group, a dimethylamino group, a diethylamino group, an allylamino group, a diallylamino group, a didecylamino group, a benzylamino group, a dibenzylamino group, a pyrrolidinyl group, a piperidinyl group, a morpholic group and an azepinyl group. Didimethylaminomethyl group, dibenzylaminomethyl group, pyrrolidinylmethyl group, dimethylaminoethyl group, benzylaminomethyl group, benzylaminoethyl group, pyrrolidinylethyl group, dimethylaminovinyl group, benzylaminovinyl group, pyrrolidini Ruvinyl 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, pyrrolidinylphenyl group, pyrrolylphenyl group, pyridylphenyl group, Kinolylphenyl group, isoquinolylphenyl group, indolinylphenyl group, indolylphenyl group, carbazolylphenyl group, di-tert-butylcarbazolylphenyl group, pyrrolyl group, methylpyrrolill group, phenylpyrrolill group, pyridyl Group, quinolyl group, tetrahydroquinolyl group, iso-quinolyl group, tetrahydro-iso-quinolyl group, indolyl group, indolinyl group, carbazolyl group, di-tert-butylcarbazolyl group, imidazolyl group, dimethylimidazolidinyl group, Examples thereof include a benzoimidazolyl group, an oxazolyl group, an oxazolidinyl group, and a benzoxazolyl group.

Among the nitrogen-containing groups, an amino group having 1 to 20 carbon atoms (preferably 1 to 10) is preferable, and specifically, an amino group, a dimethylamino group, a diethylamino group, an allylamino group, a benzylamino group, and a dibenzylamino group. Group, pyrrolidinyl group, piperidinyl group, morpholic group, dimethylaminomethyl group, benzylaminomethyl group, pyrrolidinylmethyl group, dimethylaminoethyl group, pyrrolidinylethyl group, dimethylaminopropyl group, pyrrolidinylpropyl group, dimethyl Aminoallyl group, pyrrolidinyl allyl group, aminophenyl group, dimethylaminophenyl group, 3,5-dimethyl-4-dimethylaminophenyl group, 3,5-di-iso-propyl-4-dimethylaminophenyl group, durolidinyl Group, tetramethyldurolidinyl group, pyrrolidinylphenyl group, pyrrolylphenyl group, carbazolylphenyl group, di-tert-butylcarbazolylphenyl group, pyrrolyl group, pyridyl group, quinolyl group, tetrahydroquinolyl group , Iso-quinolyl group, tetrahydro-iso-quinolyl group, indolyl group, indolinyl group, carbazolyl group, di-tert-butylcarbazolyl group, imidazolyl group, dimethylimidazolidinyl group, benzoimidazolyl group, oxazolyl group, Oxazoridinyl group, benzoxazolyl group and the like are preferable, and amino group, dimethylamino group, diethylamino group, pyrrolidinyl group, dimethylaminophenyl group, 3,5-dimethyl-4-dimethylaminophenyl group, 3,5-di-iso -Propyl-4-dimethylaminophenyl group, durolidinyl group, tetramethyldurolidinyl group, pyrrolidinylphenyl group, pyrrolyl group, pyridyl group, carbazolyl group and imidazolyl group are more preferable.

Examples of the sulfur-containing group include methylthio group, ethylthio group, benzylthio group, phenylthio group, naphthylthio group, methylthiomethyl group, benzylthiomethyl group, phenylthiomethyl group, naphthylthiomethyl group, methylthioethyl group and benzylthioethyl group. 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 thienotienyl group, a benzothienyl group, a dibenzothienyl group, a thienobenzofuryl group, a benzodithienyl group, a thiazolyl group and a benzothiazolyl group are preferable.

Adjacent substituents of R ^{1 to} R ¹³ may be bonded to each other to form a ring which may have a substituent.
Adjacent substituents of R ^{1 to} R ⁴ and R ^{6 to} R ¹³ (eg R ¹ and R ² , R ² and R ³ , R ³ and R ⁴ , R ⁶ and R ⁷ , R ⁷ and R) ⁸ , R ⁸ and R ⁹ , R ⁹ and R ¹⁰ , R ¹⁰ and R ¹¹ , R ¹¹ and R ¹² and R ¹² and R ¹³ ) are bonded to each other to form the aromatic ring portion of the mother nucleus. A 5- to 8-membered ring composed of a saturated hydrocarbon (excluding the hydrocarbon in the aromatic ring portion of the mother nucleus) or an unsaturated hydrocarbon which is fused to and may have a substituent is preferable. When a plurality of rings are present, they may be the same or different from each other. Although not particularly limited as long as the effects of the present invention are exhibited, the ring is more preferably a 5- or 6-membered ring, and in this case, the structure in which the ring and the aromatic ring portion of the mother nucleus are combined is, for example, a substituent. Naphthalene ring (hereinafter referred to as "substituted naphthalene ring"; the same applies to other rings), substituted tetrahydronaphthalene ring, substituted phenanthrene ring, substituted indan ring, substituted kumaran ring, substituted benzodio. Examples thereof include a xol ring, and a substituted naphthalene ring and a substituted tetrahydronaphthalene ring are preferable. When forming a ring, R ¹ and R ² are bonded to each other, R ² and R ³ are bonded to each other, or R ³ and R ⁴ are bonded to each other to form a ring which may have a substituent. Is preferable.

The ring formed by bonding R ⁴ and R ⁵ to each other may have a substituent which is condensed in the aromatic ring portion of the mother nucleus, and is a saturated hydrocarbon (of the aromatic ring portion of the mother nucleus). A 5-7 membered ring consisting of (excluding hydrocarbons) or unsaturated hydrocarbons is preferred. The ring is more preferably a 5- or 6-membered ring as long as the effect of the present invention is exhibited. In this case, the structure in which the ring and the aromatic ring portion of the mother nucleus are combined is, for example, a substituted indene. Examples thereof include a ring, a substituted indane ring, and a substituted tetralon ring, and a substituted indane ring is preferable.

The ring formed by bonding R ⁵ and R ⁶ to each other may have a substituent which is fused to the aromatic ring portion of the mother nucleus, and is a saturated hydrocarbon (of the aromatic ring portion of the mother nucleus). A 5-8 membered ring consisting of (excluding hydrocarbons) or unsaturated hydrocarbons is preferred. Although not particularly limited as long as the effects of the present invention are exhibited, the ring is more preferably a 5- or 6-membered ring, and in this case, the structure in which the ring and the aromatic ring portion of the mother nucleus are combined is, for example, a substituted indole. Examples thereof include a ring, a substituted quinoline ring, and a substituted dihydroquinoline ring, and a substituted quinoline ring is preferable.

Examples of modes R ^{1 to} R ¹³ include, for example.
R ¹ , R ² , R ³ , R ⁴ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , and R ¹³ are independent hydrogen atoms and 1 to 40 carbon atoms, respectively. Hydrocarbon group, halogen atom, halogen-containing group, silicon-containing group, oxygen-containing group, nitrogen-containing group or sulfur-containing group, and R ⁵ is a hydrogen atom, hydrocarbon group having 1 to 40 carbon atoms, halogen-containing group , a silicon-containing group, an oxygen-containing group, aspect is a nitrogen-containing group or a sulfur-containing group, and ^{R 1, R 2, R 3} , R 4, R 5, R 6, R 7, R 8, R 9, R 10 , R ¹¹ , R ¹² and R ¹³ are independently hydrogen atoms, hydrocarbon groups having 1 to 40 carbon atoms, halogen-containing groups, silicon-containing groups, oxygen-containing groups, nitrogen-containing groups or sulfur-containing groups. Aspects are mentioned.

R ⁴ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ and R ¹² are preferably hydrogen atoms.
R ¹ , R ² , R ³ , R ¹¹ and R ¹³ are independently, preferably hydrogen atoms, hydrocarbon groups having 1 to 20 carbon atoms, silicon-containing groups having 1 to 20 carbon atoms, and carbon atoms 1 to 20. An oxygen-containing group or a nitrogen-containing group having 1 to 20 carbon atoms, more preferably a hydrocarbon group having 1 to 10 carbon atoms, and R ¹¹ and R ¹³ are independently carbonized having 1 to 10 carbon atoms. Most preferably it is a hydrocarbon group.

R ⁵ and R ⁶ are not hydrogen atoms at the same time. Preferably, R ⁵ is not a hydrogen atom (ie, R ⁶ is a hydrogen atom).
Either one or both of R ⁵ and R ⁶ is preferably a group selected from a hydrocarbon group having 1 to 10 carbon atoms, a halogen atom, and a halogen-containing group having 1 to 10 carbon atoms, and more preferably the number of carbon atoms. It is a group selected from 10 or less aromatic hydrocarbon groups or halogen atoms.

<< Preferred Embodiment of Transition Metal Compound [A] >>
A preferred embodiment of the transition metal compound [A] is
In the general formula [1],
X is independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 10 carbon atoms, a silicon-containing hydrocarbon group, or an oxygen-containing hydrocarbon group.
R ⁴ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ and R ¹² are hydrogen atoms,
R ¹ , R ² , R ³ , R ¹¹ and R ¹³ independently have a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group having 1 to 20 carbon atoms, and oxygen having 1 to 20 carbon atoms. A transition metal compound [A-1] which is a containing group or a nitrogen-containing group having 1 to 20 carbon atoms can be mentioned, and a more preferable embodiment is
In the general formula [1],
R ⁵ is a hydrocarbon group having 1 to 10 carbon atoms or a halogen-containing group having 1 to 10 carbon atoms.
A transition metal compound [A-2] in which R ¹¹ and R ¹³ are hydrocarbon groups having 1 to 10 carbon atoms can be mentioned independently.

As a more preferable embodiment of the transition metal compound [A-2],
In the general formula [1], M is a titanium atom.
n is 2 or 3
X is a neutral ligand coordinated with a lone pair of electrons on a halogen or oxygen atom.
Examples thereof include a transition metal compound [A-3] in which R ⁵ is an aromatic hydrocarbon group having 10 or less carbon atoms.

<< Example of Transition Metal Compound [A] >>
Specific examples of the transition metal compound [A] will be shown below, but the scope of the present invention is not particularly limited by this.

For convenience, the ligand structure of the transition metal compound [A] excluding the portion represented by MXn (metal moiety) is aniline-derived ring moiety, aniline ring ortho-bonded phenol ring moiety, salicylic acid-derived ring moiety, R ^{1 to} R. ^It is divided into 5 groups, ⁴ and R ^{6 to} R ¹³ substituents, and R ⁵ substituents.

The abbreviation for the aniline-derived ring portion is α, the abbreviation for the aniline ring ortho-bonded phenol ring portion is β, the abbreviation for the salicylic acid-derived ring portion is γ, and the abbreviations for the R ^{1 to} R ⁴ and R ^{6 to} R ¹³ substituents are δ and R. ⁵ The abbreviation of the substituent is ε, and the abbreviation of each substituent is shown in [Table 1] to [Table 5].

なお、前記［表１］中の波線はアニリン環オルト位結合フェノール環部分βとの結合部位を示す。

The wavy line in the above [Table 1] indicates the binding site with the aniline ring ortho-bonded phenol ring portion β.

なお、前記［表２］中の波線はアニリン由来環部分αとの結合部位を示す。

The wavy line in [Table 2] indicates the binding site with the aniline-derived ring portion α.

Ｒ¹〜Ｒ⁴およびＲ⁶〜Ｒ¹³置換基の例としては、δ−１〜δ−６０に加え、さらに以下のδ−６１も挙げることができる。

Examples of R ^{1 to} R ⁴ and R ^{6 to} R ¹³ substituents include, in addition to δ-1 to δ-60, the following δ-61.

Specific examples of the metal portion MXn _{is, TiF 2, TiCl 2, TiBr} 2, TiI 2, Ti (Me) 2, Ti (Bn) 2, Ti (Allyl) 2, Ti (CH 2 -tBu) 2, Ti (1,3-butadienyl), Ti (1,3-pentadienyl), Ti (2,4-hexadienyl), Ti _{(1,4-diphenyl-1,3-pentadienyl), Ti (CH 2 -Si (} Me ) ₃ ) ₂ , Ti (ОMe) ₂ , Ti (ОiPr) ₂ , Ti (NMe ₂ ) ₂ , Ti (ОMs) ₂ , Ti (ОTs) ₂ , Ti (ОTf) ₂ , ZrF ₂ , ZrCl ₂ , ZrBr _{2 , ZrI 2, Zr (Me)} 2, Zr (Bn) 2, Zr (Allyl) 2, Zr (CH 2 -tBu) 2, Zr (1,3- butadienyl), Zr (1,3-pentadienyl), Zr (2,4-hexadienyl), Zr _{(1,4-diphenyl-1,3-pentadienyl), Zr (CH 2 -Si (} Me) 3) 2, Zr (ОMe) 2, Zr (ОiPr) 2, Zr ( _{NMe 2) 2, Zr (ОMs} ) 2, Zr (ОTs) 2, Zr (ОTf) 2, HfF 2, HfCl 2, HfBr 2, HfI 2, Hf (Me) 2, Hf (Bn) 2, Hf (Allyl ) ₂ , Hf (CH _2- tBu) ₂ , Hf (1,3-butadienyl), Hf (1,3-pentadienyl), Hf (2,4-hexadienyl), Hf (1,4-diphenyl-1,3) -Pentadienyl), Hf (CH _2- Si (Me) ₃ ) ₂ , Hf (ОMe) ₂ , Hf (ОiPr) ₂ , Hf (NMe ₂ ) ₂ , Hf (ОMs) ₂ , Hf (ОTs) ₂ , Hf ( ОTf) _{2 and the} like. Me is a methyl group, Bn is a benzyl group, tBu is a tert-butyl group, Si (Me) ₃ is a trimethylsilyl group, ОMe is a methoxy group, ОiPr is an iso-propoxy group, NMe ₂ is a dimethylamino group, and ОMs is a methanesulfonate. The group, ОTs is a p-toluenesulfonate group, and ОTf is a trifluoromethanesulfonate group.

According to the above notation, the aniline-derived ring portion is α-1 in [Table 1], and the R ⁶ , R ⁷ , R ⁸ and R ⁹ substituents in the aniline-derived ring portion are all δ in [Table 4]. -1, beta-1 aniline ring ortho bonded phenolic ring moiety in Table 2], [delta]-1 of R ¹⁰ and R ¹² substituents of the aniline ring ortho bonded phenolic ring moiety in both Table 4 , R ¹¹ substituents are δ-15 in [Table 4], R ¹³ substituents are δ-12 in [Table 4], salicylic acid-derived ring portions are γ-1, salicylic acid-derived ring portions in [Table 3]. The R ¹ substituents in [Table 4] are δ-43, R ² , R ³ and R ⁴ substituents are all in [Table 4], and the δ-1, R ⁵ substituents are in [Table 5]. When it is composed of a combination of ε-1 and the MXn of the metal portion is TiCl ₂ , the compound represented by the following formula [4] is exemplified.

The aniline-derived ring moiety is α-2 in [Table 1], and the R ⁶ and R ⁷ substituents in the aniline-derived ring moiety are all δ-1 in [Table 4], and the aniline ring ortho-bonded phenol ring moiety. Is β-2 in [Table 2], δ-1 in [Table 4] is the R ¹² substituent in the aniline ring ortho-bonded phenol ring portion, and δ-35 in [Table 4] is the R ¹³ substituent. The salicylic acid-derived ring portion is γ-1 in [Table 3], and the R ¹ substituent in the salicylic acid-derived ring portion is δ-47, R ² and R ⁴ substituents in [Table 4]. When the δ-1, R ³ substituent is composed of a combination of δ-2 and R ⁵ substituent in [Table 4] and ε-6 in [Table 5], and the MXn of the metal portion is TiBn ₂ . , The compound represented by the following formula [5] is illustrated.

The aniline-derived ring moiety is α-1, and the aniline-derived ring moiety is R ⁶ , R ⁷ , R ⁸ and R ⁹ substituents are all δ-1, aniline ring in [Table 4]. The ortho-linked phenol ring moiety is β-1 in [Table 2], and the R ¹⁰ and R ¹² substituents in the aniline ring ortho-linked phenol ring moiety are all δ-1, R ¹¹ substituents in [Table 4]. Is δ-11 in [Table 4], R ¹³ substituent is δ-59 in [Table 4], γ-1 in [Table 3] is γ-1, and R ¹ substituent in [Table 3]. Is a combination of δ-53, R ² , R ³ and R ⁴ substituents in [Table 4] δ-1, R ^{5 in} [Table 4] and ε-8 in [Table 5]. When the MXn of the metal portion is Time ₂ , the compound represented by the following formula [6] is exemplified.

The aniline-derived ring moiety is α-1, and the aniline-derived ring moiety is R ⁶ , R ⁷ , R ⁸ and R ⁹ substituents are all δ-1, aniline ring in [Table 4]. The ortho-bonded phenol ring moiety is β-1 in [Table 2], and the R ¹⁰ and R ¹² substituents in the aniline ring ortho-linked phenol ring moiety are all δ-1, R ¹¹ substituents in [Table 4]. Is δ-14 in [Table 4], R ¹³ substituent is δ-22 in [Table 4], γ-2 in [Table 3] is γ-2 in [Table 3], and R ¹ substituent in [Table 3]. There [Table 4] [delta]-58, R ⁴ substituents in the is [delta]-1, R ⁵ substituent in Table 4 is a combination of epsilon-14 in Table 5, the metal portion MXn When is Ti (1,3-pentadienyl), the compound represented by the following formula [7] is exemplified.

Further, the transition metal compound [A] has two types of structures represented by the following general formulas [8a] or [8b] centered on the bond axis between the aniline-derived ring portion and the aniline ring ortho-bonded phenol ring portion. Isomers may be present.

Similarly, when the salicylic acid-derived ring moiety R ¹ substituent is an aromatic ring, two types represented by the following general formula [9a] or [9b] centered on the bond axis between the salicylic acid-derived ring moiety and the R ¹ substituent. Structural isomers may be present.

In the above general formulas [9a] and [9b], the R ^a and R ^b substituents are the same substituents as those shown in R ^{1 to} R ¹³ , and are the R ^a substituent and the R ^b substituent. Is a different substituent.
Purification, preparative production, or selective production of structural isomers of these structural isomer mixtures is possible by known methods, and the production method is not particularly limited. As a known production method, a production method using an optically active material as a raw material can be mentioned.

Within the range of the transition metal compound [A], one type of transition metal compound may be used alone, two or more types may be used in combination, a mixture of structural isomers may be used, and structural isomers may be used. May be used alone, or a mixture of two or more structural isomers may be used.

<< Production method of transition metal compound [A] >>
The transition metal compound [A] can be produced by using a conventionally known method, and the production method is not particularly limited. Examples of typical synthetic routes include the following production methods [Formula 1] disclosed in JP-A-2011-016789, JP-A-2014-224053, and the like. In the following [Equation 1] to [Equation 5], R ^{1 to} R ¹³ have the same meaning as those described in the above general formula [1].

前記［式１］中、Ｘはハロゲン原子を示し、Ｂはボロン酸、ボロン酸エステル、アルキルボランまたはテトラフルオロボレート塩などのホウ素官能基を示している。

In the above [Formula 1], X represents a halogen atom, and B represents a boron functional group such as boronic acid, boronic acid ester, alkylborane or tetrafluoroborate salt.

Further, as another method for synthesizing the precursor compound (ligand) of the transition metal compound [A], the following [Formula 2] using the imidoyl chloride compound disclosed in "Organomet. 2003, 22, 2542." ] Is also mentioned.

前記［式２］中のイミドイルクロリド化合物は、前記［式１］中の＜Ｚ＞と対応するカルボン酸誘導体より調製されるアミド化合物を、五塩化リンやシュウ酸塩化物で処理することによって調製することができるが、特に製造法が限定されるわけではない。

The imideyl chloride compound in the above [formula 2] is obtained by treating an amide compound prepared from a carboxylic acid derivative corresponding to <Z> in the above [formula 1] with phosphorus pentachloride or a oxalate chloride. It can be prepared, but the production method is not particularly limited.

Further, as a method for synthesizing a substituted 2-hydroxyaromatic diketone compound which is a precursor compound of the transition metal compound [A] precursor compound (ligand), it is disclosed in "Chem. Lett. 1996, 823." The following production method [Formula 3] using the substituted 2-hydroxybenzaldehyde compound as a starting material can also be mentioned.

In the above [Equation 3], Pd-cat. Indicates a palladium catalyst, Ar represents a substituted aromatic substituent, and X represents a halogen atom. Examples of the palladium catalyst include, but are not limited to, palladium chloride, palladium acetate, π-allylpalladium chloride dimer, trisdibenzidene acetone palladium, tetrakistriphenylphosphine palladium and the like, but are not limited to this. -Ligands such as heterocyclic carbene compounds may be used. The transition metal compound [A] precursor compound (ligand) can be produced from the substituted 2-hydroxyaromatic diketone compound and <Z> in the above [Formula 1] by the method shown in the above [Formula 1]. is there.

[Catalyst for olefin polymerization]
The catalyst for olefin polymerization of the present invention contains the transition metal compound [A] of the present invention.
A typical example of the catalyst for olefin polymerization of the present invention is a catalyst for ethylene polymerization.

(Compound [B])
The catalyst for olefin polymerization of the present invention is preferably further [B-1] an organometallic compound, preferably an organometallic represented by the following general formulas (B-1a), (B-1b) or (B-1c). Compound (hereinafter also referred to as "component (B-1)"),
R ^a _m Al (OR ^b ) _n H _p X _q … (B-1a)
[In the general formula (B-1a), R ^a and R ^b 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 is 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), M ^a represents a Li, Na or K, 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 and 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. ]
[B-2] Organoaluminium oxy compound (hereinafter also referred to as "component (B-2)") and [B-3] Compound that reacts with transition metal compound (A) to form an ion pair (hereinafter "component" (B-3) ”), which includes at least one compound [B] (hereinafter, may be referred to as“ component (B) ”) selected from the group consisting of).

As the organometallic compound [B-1], the compound disclosed in JP-A-11-315109 and EP0874005A by the applicant 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 and tri2-ethylhexylaluminum, dimethylaluminum chloride, diethylaluminum chloride, diisopropylaluminum chloride, diisobutylaluminum chloride, dialkylaluminum halide such as dimethylaluminum bromide, methylaluminum sesquichloride, ethylaluminum sesquichloride, isopropyl Alkylaluminum sesquihalide such as aluminum sesquichloride, butylaluminum sesquichloride, ethylaluminum sesquibramide, methylaluminum dichloride, ethylaluminum dichloride, isopropylaluminum dichloride, alkylaluminum dihalide such as 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 hydride such as hydride, dimethylaluminum ethoxide, diethylaluminum ethoxide, diisopropylaluminum methoxide, and dialkylaluminum alcoxyside such as diisobutylaluminum ethoxide.

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 an organoaluminum oxy compound 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] that reacts with the transition metal compound (A) to form an ion pair include Japanese Patent Application Laid-Open No. 1-501950, Japanese Patent Application Laid-Open No. 1-502036, and Japanese Patent Application Laid-Open No. 3-179005. Lewis acid, ionic compounds, borane compounds and carborane compounds described in Kaihei 3-179006, JP-A-3-207703, JP-A-3-207704, US Pat. No. 5,321,106, and the like, and further. Can use heteropoly compounds and isopoly compounds without limitation.

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

(Solid support [S])
The catalyst for olefin polymerization of the present invention preferably contains a solid support [S] (hereinafter, may be referred to as “carrier [S]” or “component (S)”).
The solid support [S] is an inorganic compound or an organic compound, and is a solid in the form of granules or fine particles.
As the inorganic compound, a porous oxide, a solid aluminoxane compound, an inorganic halide, clay, a clay mineral or an ion-exchange layered compound is preferable.

Specific examples of the porous oxide include SiO ₂ , Al ₂ O ₃ , MgO, ZrO, TiO ₂ , B ₂ O ₃ , CaO, ZnO, BaO, ThO _{2, and the} like, or a composite or mixture containing these. It can also be used, for example natural or synthetic zeolite, SiO _2- MgO, SiO _2- Al ₂ O ₃ , SiO _2- TIO ₂ , SiO _2- V ₂ O ₅ , SiO _2- Cr ₂ O ₃ , SiO _2- TiO _2- MgO or the like can be used. Of these, as the porous oxide, those containing SiO ₂ and / or Al ₂ O ₃ as main components are preferable.

The porous oxides are a small amount of Na ₂ CO ₃ , K ₂ CO ₃ , CaCO ₃ , Mg CO ₃ , Na ₂ SO ₄ , Al ₂ (SO ₄ ) ₃ , BaSO ₄ , KNO ₃ , Mg (NO ₃ ) _2. , Al (NO ₃ ) ₃ , Na ₂ O, K ₂ O, Li ₂ O and other carbonates, sulfates, nitrates and oxide components may be contained.

Although the properties of the porous oxide differ depending on the type and manufacturing method, the porous oxide preferably used in the present invention has a particle size of 10 to 300 μm, preferably 20 to 200 μm, and a specific surface area of 50 to 1000 m ^2. It is in the range of / g, preferably 100 to 700 m ² / g, and the pore volume is in the range of 0.3 to 3.0 cm ³ / g. Such a porous oxide is used by firing at 100 to 1000 ° C., preferably 150 to 700 ° C., if necessary.

Examples of the solid aluminoxane compound include aluminoxane having a structure represented by the following general formula (Sa) or (Sb), a repeating unit represented by the following general formula (Sc), and the following general formula ( Examples thereof include aluminoxane selected from at least one aluminoxane having a repeating unit represented by Sd) as a structure.

In the general formulas (S-a) to (S-d), ^Re is independently a hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms, and specifically, a methyl group and an ethyl. Group, propyl group, isopropyl group, isopropenyl group, n-butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, octyl group, decyl group, dodecyl group, tridecyl group, tetradecyl group, hexadecyl group , Octadecyl group, eicosyl group, cyclohexyl group, cyclooctyl group, phenyl group, tolyl group, ethylphenyl group and other hydrocarbon groups can be exemplified, and methyl group, ethyl group and isobutyl group are preferable, and methyl group is particularly preferable. preferable. A part of R ^e is chlorine, substituted with a halogen atom such as bromine, and halogen content may be not more than 40 wt%, based on the R ^e. A straight line in (Sc) and (Sd) where one is not connected to an atom indicates a bond with another atom (not shown).

In the general formulas (S-a) and (S-b), r represents an integer of 2 to 500, preferably in the range of 6 to 300, particularly preferably 10 to 100. In the general formulas (Sc) and (Sd), s and t each represent an integer of 1 or more. r, s and t are selected such that the aluminoxane can remain substantially solid in the reaction environment in which it is used.

Unlike conventionally known carriers for olefin polymerization catalysts, the solid aluminoxane compound does not contain inorganic solid components such as silica and alumina and organic polymer components such as polyethylene and polystyrene, and is solidified with an alkylaluminum compound as a main component. It is a thing. "Solid" means that the aluminoxane component remains substantially solid in the reaction environment in which it is used. More specifically, as described later, when the transition metal compound [A] is brought into contact with the aluminoxane component to prepare an olefin polymerization catalyst (eg, an ethylene polymerization catalyst), and the prepared olefin polymerization catalyst When the polymerization of an olefin (eg, ethylene) (for example, suspension polymerization) is carried out using the above, the aluminoxane component maintains a substantially solid state.

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

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

The dissolution ratio was determined by adding 2 g of a solid aluminoxane compound carrier to 50 ml of n-hexane maintained at 25 ° C., stirring for 2 hours, and then separating the solution portion using a G-4 glass filter. , Obtained by measuring the aluminum concentration in this filtrate. Therefore, the dissolution ratio is determined as the ratio of aluminum atoms present in the filtrate to the amount of aluminum atoms corresponding to 2 g of aluminoxane used.

As the solid aluminoxane compound, known solid aluminoxane can be used endlessly, and for example, the solid polyaluminoxane composition described in International Publication No. 2014/123212 can also be used. As known manufacturing methods, 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, Japanese Patent Application Laid-Open No. 2000 Examples thereof include the production methods described in Japanese Patent Application Laid-Open No. −38410, Japanese Patent Application Laid-Open No. 2000-95810, and International Publication No. 2010/55652.

The average particle size of the solid aluminoxane compound is generally in the range of 0.01 to 50,000 μm, preferably 1 to 1000 μm, and particularly preferably 1 to 200 μm. The average particle size of the solid aluminoxane compound is determined by observing the particles with a scanning electron microscope, measuring the particle size of 100 or more particles, and averaging the weight. First, the particle size of each particle is calculated by the following formula after measuring the length of the particle image with two parallel lines in each of the horizontal and vertical directions.
Grain size = ((horizontal length) ² + (vertical length) ² ) ^0.5

Next, the weight average particle size of the solid aluminoxane compound is calculated by the following formula using the particle size obtained above.
Average particle size = Σnd ⁴ / Σnd ³
(N; number of particles, d; particle size)
The solid aluminoxane compound preferably has a specific surface area of 50 to 1000 m ² / g, preferably 100 to 800 m ² / g, and a pore volume of 0.1 to 2.5 cm ³ / g.

As the inorganic halide, MgCl ₂ , MgBr ₂ , MnCl ₂ , MnBr _{2 and the} like are used. The obtained inorganic halide may be used as it is, or may be used after being pulverized by a ball mill or a vibration mill. It is also possible to use an inorganic halide dissolved in a solvent such as alcohol and then precipitated in the form of fine particles with a precipitant.

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

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

Furthermore, as clays and clay minerals, kaolin, bentonite, wood knot clay, gailome clay, allophane, hisingel stone, pyrophyllite, ummo group, montmorillonite group, vermiculite, ryokudei stone group, parigolskite, kaolinite, nacrite, dicite, etc. Halloy site etc.
The ion-exchange layered _{compounds, α-Zr (HAsO 4)} 2 · H 2 O, α-Zr (HPO 4) 2, α-Zr (KPO 4) 2 · 3H 2 O, α-Ti (HPO 4) ₂ , α-Ti (HAsO ₄ ) ₂ · H ₂ O, α-Sn (HPO ₄ ) ₂ · H ₂ O, γ-Zr (HPO ₄ ) ₂ , γ-Ti (HPO ₄ ) ₂ , γ-Ti ( Examples include crystalline acidic salts of polyvalent metals such as NH ₄ PO ₄ ) ₂ and H ₂ O.

Such clays, clay minerals or ion-exchange layered compounds preferably have a pore volume of 0.1 cc / g or more, preferably 0.3 to 5 cc / g, as measured by a mercury intrusion method and having a radius of 20 Å or more. Is particularly preferred. Here, the pore volume is measured in a pore radius range of 20 to 30,000 Å by a mercury intrusion method using a mercury porosimeter.

When a carrier having a radius of 20Å or more and a pore volume smaller than 0.1 cc / g is used as a carrier, it tends to be difficult to obtain high polymerization activity.
It is also preferable to chemically treat the clay and clay minerals. As the chemical treatment, any of a surface treatment for removing impurities adhering to the surface and a treatment for affecting the crystal structure of clay can be used. Specific examples of the chemical treatment include acid treatment, alkali treatment, salt treatment, and organic substance treatment. The acid treatment removes impurities on the surface and increases the surface area by eluting cations such as Al, Fe, and Mg in the crystal structure. Alkaline treatment destroys the crystal structure of clay, resulting in a change in the structure of 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. Further, 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 ] ⁺ and other metal hydroxide ions And so on. These compounds are used alone or in combination of two or more. In addition, when these compounds are intercalated, metal alkoxides such as Si (OR) ₄ , Al (OR) ₃ , and Ge (OR) ₄ (R indicates a hydrocarbon group or the like) are hydrolyzed. The obtained polymer, a colloidal inorganic compound such as SiO ₂ can coexist. In addition, examples of pillars include oxides produced by intercalating the above metal hydroxide ions between layers and then heating and dehydrating them.

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

Of these, preferred are clays or clay minerals, with particularly preferred being montmorillonite, vermiculite, pectolite, teniolite and synthetic mica.
Examples of the organic compound that can be used as the carrier [S] include granular or fine particle solids having a particle size in the range of 1 to 300 μm. Specifically, a polymer produced mainly from an α-olefin having 2 to 14 carbon atoms such as ethylene, propylene, 1-butene, 4-methyl-1-pentene, or vinylcyclohexane or styrene as a main component. The polymers produced as, and their variants can be exemplified.

<Usage and order of addition of each component>
The catalyst for olefin polymerization according to the present invention can be prepared by mixing and contacting the component (A), optionally the component (S), and optionally the component (B) in an inert hydrocarbon.

As a method of contacting each component, paying attention to the order of contact, for example,
(I) Method of contacting component (B) with component (A) (ii) Method of contacting component (A) with component (S) (iii) Contacting component (S) with component (B), then component Method of contacting (A) (iv) Method of contacting component (B) with component (A) and then contacting component (S) (v) Contacting component (S) with component (B), then component A method of contacting a mixture of (A) and component (B),
(Vi) Examples thereof include a method in which the component (B) is brought into contact with the component (S), the component (B) is further brought into contact with the component (S), and then a mixture of the component (A) and the component (B) is brought into contact with the component (S). 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), (ii), (iii) and (iv) are preferable.

In each of the methods showing the contact sequence form, in the step including the contact between the component (S) and the component (B) and the step including the contact between the component (S) 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 used. , 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 olefin polymerization catalyst according to the present invention include an inert hydrocarbon solvent, and specifically, fats such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene. Alicyclic hydrocarbons such as group hydrocarbons, cyclopentane, cyclohexane and methylcyclopentane, aromatic hydrocarbons such as benzene, toluene and xylene, halogenated hydrocarbons such as ethylene chloride, chlorobenzene and dichloromethane, or mixtures thereof. The olefin itself can be used as a solvent depending on the type of olefin to be polymerized.

In the contact between the component (B) and the component (S), the reaction site in the component (B) and the reaction site in the component (S) are chemically bonded to each other, and the component (B) and the component (S) are chemically bonded. ) Is formed. The contact time between the component (B) and the component (S) 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 (S) is suddenly performed, the component (S) collapses due to the reaction heat generation and the reaction energy, 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 (S), 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 initial contact temperature is reacted at a sustainable rate. Is preferable. The same applies to the case where the component (B) and the component (S) 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 (S) (weight of the component (B) / weight of the component (S)) 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 (S) [= weight of the component (B) / weight of the component (S)] is preferably 0.05 to 3.0, particularly preferably 0.1 to 2. It is 0.0.
When the contact material between the component (B) and the component (S) 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 all the transition metal atoms (M) in the component (A) is usually 0.01 to 100, It is used in an amount such that it is 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 (A) is usually 10 (in terms of aluminum atom). It is used in an amount of ~ 500,000, preferably 200-100,000.

The molar ratio [(B-3) / M] of the component (B-3) to all the transition metal atoms (M) in the component (A) is usually 1 to 10, preferably 1. It is used in an amount such that it becomes 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).

The olefin polymerization catalyst according to the present invention can be used as it is for olefin polymerization, but it can also be used after prepolymerizing an olefin with the olefin polymerization catalyst to form a prepolymerized solid catalyst component.

The prepolymerized solid catalyst component can be prepared by prepolymerizing an olefin (eg, ethylene) or the like in an inert hydrocarbon solvent in the presence of the catalyst for olefin polymerization according to the present invention. It can be carried out by either a semi-continuous method or a continuous method, and can 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.

The prepolymerized solid catalyst component produced in the inert hydrocarbon solvent is separated from the suspension, then suspended again in the inert hydrocarbon, and an olefin (eg, ethylene) is introduced into the obtained suspension. Alternatively, an olefin (eg, ethylene) 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. An olefin containing ethylene as a main component is preferably used for the prepolymerization.

As the form of the solid catalyst component used for the prepolymerization, those already described can be used without limitation. In addition, the component (B) is used 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) is the molar ratio (Al / M) of the aluminum atom (Al) in the component (B) and the transition metal atom (M) in the transition metal compound [A]. ) Is used in an amount of 0.1 to 10000, preferably 0.5 to 5000.

The concentration of the olefin polymerization catalyst according to the present invention in the prepolymerization system is usually 1 to 1000 g / liter, more preferably 10 to 500 g / liter in terms of the olefin polymerization catalyst / polymerization volume ratio. At the time of prepolymerization, the above component (G) may coexist for the purpose of suppressing fouling or improving particle properties.

Further, for the purpose of improving the fluidity of the prepolymerized solid catalyst component, heat spot seating during polymerization, and suppressing the generation of polymer lumps, the component (G) is brought into contact with the prepolymerized solid catalyst component once generated by prepolymerization. May be good.

The temperature at which the component (G) is brought into contact is usually −50 to 50 ° C., preferably -20 to 50 ° C., and the contact time is usually 1 minute to 20 hours, preferably 5 minutes to 10 hours. ..
When the olefin polymerization catalyst according to the present invention is brought into contact with the component (G), the component (G) is 0.1 to 20 parts by weight, preferably 0.1 to 20 parts by weight, based on 100 parts by weight of the olefin polymerization catalyst according to the present invention. It is used in an amount of 0.3 to 10 parts by weight, more preferably 0.4 to 5 parts by weight.

The mixed contact between the olefin polymerization catalyst according to the present invention and the component (G) can be carried out in an inert hydrocarbon solvent, and examples of the inert hydrocarbon solvent include the same as described above.
In the method for producing an olefin-based polymer according to the present invention, a dried prepolymerized solid catalyst component (hereinafter, also referred to as “dry prepolymerized catalyst”) can be used as the catalyst for olefin polymerization. The drying of the prepolymerized solid catalyst component is usually carried out after removing hydrocarbons as a dispersion medium from the obtained suspension of the prepolymerized catalyst by filtration or the like.

The drying of the prepolymerized solid catalyst component is carried out by keeping the prepolymerized solid catalyst component at a temperature in the range of 70 ° C. or lower, preferably 20 to 50 ° C. under the flow of an inert gas. The amount of the volatile component of the obtained dry prepolymerization catalyst is preferably 2.0% by weight or less, preferably 1.0% by weight or less. The smaller the amount of the volatile component of the dry prepolymerization catalyst, the better, and there is no particular lower limit, but practically it is 0.001% by weight. The drying time is usually 1 to 48 hours, although it depends on the drying temperature.

Since the dry prepolymerization catalyst has excellent fluidity, it can be stably supplied to the polymerization reactor. Further, when the dry prepolymerization catalyst is used, stable polymerization can be performed because it is not necessary to accompany the solvent used for suspension in the gas phase polymerization system.

[Method for producing olefin polymer]
The method for producing an olefin polymer of the present invention is characterized by polymerizing an olefin in the presence of the catalyst for olefin polymerization of the present invention.
As a preferred embodiment of the method for producing an olefin polymer of the present invention, ethylene is copolymerized, propylene is copolymerized, or ethylene and an α-olefin having 3 or more and 20 or less carbon atoms in the presence of the olefin polymerization catalyst of the present invention. Examples thereof include a method for producing an olefin polymer, which comprises a step of copolymerizing with.

Examples of the polymerization method include a liquid phase polymerization method such as solution polymerization and suspension polymerization and a vapor phase polymerization method, and the suspension polymerization method and the vapor phase polymerization method 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. Aliphatic hydrocarbons such as benzene, toluene, xylene and the like; halogenated hydrocarbons such as ethylene chloride, chlorobenzene, dichloromethane and the like, or mixtures thereof.

When polymerizing an olefin (eg, ethylene) using the catalyst for olefin polymerization according to the present invention, the component (A) is usually 1 × 10 ^-12 to 1 × 10 ^-1 mol, preferably 1 × 10 ^-12 to 1 × 10 ^-1 mol, per liter of the reaction volume. Is used in an amount such that it is 1 × 10 ^-8 to 1 × 10 ⁻² mol. Further, the component (B) is used, and preferably the compound represented by the general formula (B-1a) or the component (B-2) is used.

When polymerizing an olefin (eg, ethylene), the polymerization temperature has a preferable lower limit of 0 ° C., more preferably 20 ° C., and even more preferably 40 ° C. The higher the temperature, the more advantageous in terms of heat removal and the like 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 particle properties.

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

In addition, polyene can also be used in combination. Specific examples of the polyene include 1,4-hexadiene, 1,5-hexadiene, 1,5-heptadiene, 1,6-heptadiene, 1,6-octadene, 1,7-octadiene, 1,7-nonadien, and 1 , 8-Norbornadiene, 1,8-Decadien, 1,9-Decadien, 1,12-Tetradecadiene, 1,13-Tetradecadiene, 3-Methyl-1,4-Hexadiene, 3-Methyl-1,5 -Hexadiene, 3-ethyl-1,4-hexadiene, 3-ethyl-1,5-hexadiene, 3,3-dimethyl-1,4-hexadiene, 3,3-dimethyl-1,5-hexadiene, 5-ethylidene -2-norbornene, 5-vinyl-2-norbornene, 2,5-norbornadiene, 7-methyl-2,5-norbornadiene, 7-ethyl-2,5-norbornadiene, 7-propyl-2,5-norbornadiene, 7 -Butyl-2,5-norbornene, 7-pentyl-2,5-norbornadiene, 7-hexyl-2,5-norbornene, 7,7-dimethyl-2,5-norbornene, 7,7-methylethyl-2, 5-Norbornadiene, 7-Chloro-2,5-Norbornadiene, 7-Bromo-2,5-Norbornadiene, 7-Fluoro-2,5-Norbornadiene, 7,7-Dichloro-2,5-Norbornadiene, 1-Methyl- 2,5-Norbornadiene, 1-ethyl-2,5-Norbornadiene, 1-propyl-2,5-Norbornadiene, 1-butyl-2,5-Norbornadiene, 1-Chloro-2,5-Norbornadiene, 1-bromo- 2,5-Norbornadiene and the like can be mentioned.

Further, as the polyene, a compound having the following structure can also be mentioned.

ポリエンは、使用される場合には１種以上用いられ、好ましくは、５−エチリデン−２−ノルボルネン、ジシクロペンタジエン、５−ビニル−２−ノルボルネン、２，５−ノルボルナジエンである。

When used, one or more polyenes are used, preferably 5-ethylidene-2-norbornene, dicyclopentadiene, 5-vinyl-2-norbornene, and 2,5-norbornadiene.

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.

By using the transition metal compound of the present invention, the olefin can be polymerized with high activity. Further, even at a relatively high polymerization temperature, an olefin polymer having a relatively high molecular weight can be obtained. The reason for this is not clear at this time, but the present inventors speculate as follows.

The transition metal compound of the present invention has a substituent instead of a hydrogen atom at a specific position (at least one of R ⁵ and R ⁶ ) of the ligand. This structure can be expected to have the effect of restricting the movement (rotation, etc.) of a specific site of the ligand constituting the transition metal compound of the present invention. Since the fluctuation of the ligand structure based on this movement is small, the difference in the molecular weight of the polymer obtained in a relatively wide polymerization temperature region is small, that is, the weight of the high molecular weight obtained at a low temperature even at a relatively high polymerization temperature. I think that a polymer with a molecular weight close to that of coalescence can be obtained.

In the present invention, as described above, it is preferable that R ⁵ is a group other than a hydrogen atom. This is because R ⁵ takes a structure other than hydrogen to form a stable structure such as a ketimine structure, so that the molecular weight of the obtained polymer is not easily affected by the polymerization temperature as described above. It is considered possible. This point is an advantageous feature for stable production of the polymer.

Further, when copolymerization of olefins is carried out, since the copolymerization reactivity is good, it is considered to be advantageous in stably producing a copolymer having a narrow composition distribution for the following reasons. The reason for these effects is unknown at this time, but the present inventors speculate as follows.

When copolymerization of olefins is carried out, for example, by continuous polymerization, unreacted olefins may be recovered and reused for polymerization. In this case, the copolymerization of ethylene and propylene is taken as an example, but if the copolymerization reactivity of ethylene and propylene is almost equal, the composition of the mixture of unreacted olefins is almost the same as the composition of the olefin to be fed. Can be expected to be. Therefore, it is not necessary to adjust the composition of the olefin when the unreacted gas is reused, and even if it is done, the steady state can be realized with a slight adjustment. On the other hand, it is generally known that ethylene is often considerably more reactive than α-olefins such as propylene. The feature of the transition metal compound of the present invention can be said to be an excellent function from that viewpoint.

The transition metal compound of the present invention is expected to have a wide coordination space due to its structure, but it is speculated that the specific substituent may be involved in the formation of its stabilizing reaction field. There is. Since such a special environment can be formed, the transition metal compound of the present invention exhibits high polymerization reactivity even with an α-olefin having a higher bulk than ethylene, so that a catalyst having good copolymerizability can be used. It is thought that it can be formed.

The transition metal compound of the present invention is expected to have a wide coordination space due to its structure, but it is speculated that the specific substituent may be involved in the formation of its stabilizing reaction field. There is. Since such a special environment can be formed, the transition metal compound of the present invention exhibits high polymerization reactivity even if it is an α-olefin having a higher bulk than ethylene, and the polymerization reaction proceeds quickly. It is considered that a catalyst having good copolymerizability can be formed.

[Olefin polymer]
The ethylene-based polymer produced by the method for producing an olefin polymer according to the present invention preferably satisfies the following requirements (1) and (2). (1) The ultimate viscosity [η] measured at 135 ° C. in decalin is 0.5 to 10 dl / g. A more preferable lower limit value is 0.6 dl / g, and even more preferably 0.7 dl / g. On the other hand, a more preferable upper limit value is 8 dl / g, more preferably 5.0 dl / g, and particularly preferably 4.0 dl / g. (2) density of 875kg / m ³ or more 965 kg / m ³ or less, preferably 885kg / m ³ or more 945 kg / m ³ or less.

The olefin polymer produced by the catalyst for olefin polymerization containing the transition metal compound of the present invention (eg, an ethylene polymer) may be pelletized.
The olefin polymer produced by the present invention (eg, ethylene-based polymer) includes a weather resistance stabilizer, a heat stabilizer, an antistatic agent, an antislip agent, and an antiblocking agent as long as the object of the present invention is not impaired. , Anti-fog agents, lubricants, pigments, dyes, nucleating agents, plasticizers, anti-aging agents, hydrochloric acid absorbers, antioxidants and the like may be added as necessary.

The above-mentioned olefin polymer can be made into a molded product by using a conventionally known molding method. For example, a container such as a film, a sheet, a bottle, various structural members, etc. can be obtained by using a known method such as an extrusion molding method, a blow molding method, an inflation molding method, a press molding method, an injection molding method, or a vacuum forming method. You can.

Hereinafter, the present invention will be described in more detail based on Examples, but the present invention is not limited to these Examples.
The structures of the compounds obtained in the synthetic examples and the examples were determined by using 270 MHz 1H NMR (JEOL GSH-270), FD-mass spectrometry (JEOL SX-102A), and the like.

[Measurement of various physical properties]
The method for measuring the physical properties of the olefin polymer is shown below.
<Ultimate viscosity [η]>
About 20 mg of the measurement sample was dissolved in 15 ml of decalin, and the specific viscosity η _sp was measured in an oil bath at 135 ° C. After diluting with 5 ml of a decalin solvent added to this decalin solution, the specific viscosity η _sp was measured in the same manner. This dilution operation was repeated twice more, and the value of η _sp / C when the concentration (C) was extrapolated to 0 was determined as the ultimate viscosity [η] (unit: dl / g) as shown in the following formula.
[Η] = lim (η _sp / C) (C → 0)

<Number average molecular weight (Mn), weight average molecular weight (Mw), molecular weight distribution (Mw / Mn)>
The measurement was carried out as follows using an Agilent GPC-viscosity detector (GPC-VISCO) PL-GPC220.
Two Agent PLgel Olexis were used for the analysis column, a differential refractometer and a 3-capillary viscometer were used for the detector, the column temperature was 145 ° C., o-dichlorobenzene was used as the mobile phase, and the flow rate was 1.0 ml. The sample concentration was 0.1% by weight. As the standard polystyrene, one manufactured by Tosoh Corporation was used. In the molecular weight calculation, the measured viscosity was calculated from a viscometer and a refractometer, and the number average molecular weight (Mn), the weight average molecular weight (Mw), and the molecular weight distribution (Mw / Mn) were obtained from the measured universal calibration.

<Comonomer content>
The content of the copolymer comonomer obtained in the examples was measured by IR (JASCO FT / IR-4200).
For IR, the copolymer obtained in the examples was melted and stretched by a hot press heated to 180 ° C., and then the film obtained by pressure cooling at room temperature was used as a measurement sample, and the light source wavelength was 5000 cm ^-1. Measured between ~ 400 cm- ¹ . The propylene content is based on propylene-based C-CH ₃ skeletal vibration (1150 cm ^-1 ) as the key band, and the absorbance of the key band (D1150) and the internal standard band (4320 cm ^-1 : CH expansion and contraction vibration and methylene and methyl deflection) It was determined by the ratio [D1150 / D4320] of the combined sound of vibration to the absorbance (D4320). The hexene content is based on hexene-based C-CH ₃ skeletal vibration (1378 cm ^-1 ) as a key band, and the absorbance of the key band (D1378) and the internal standard band (4320 cm ^-1 : CH expansion and contraction vibration and methylene and methyl eccentricity). It was determined by the ratio [D1378 / D4320] of the combined sound of vibration to the absorbance (D4320).

<Synthesis of transition metal compound (A)>
[Synthesis Example 1-1]
3-tert-Butyl-2-hydroxybenzophenone (hereinafter referred to as "Compound (A-1a)") is described in Chem. Lett. 1996, 823. The method described and Bull. Chem. Soc. Jpn. 1998, 71, 2239. It was synthesized as follows according to the method described.

1.79 g (10.0 mmol) of 3-tert-butyl-2-hydroxybenzaldehyde, 0.12 g (0.52 mmol) of palladium acetate, 6.62 g of cesium carbonate (20) in a 200 mL reactor that has been sufficiently dried and replaced with nitrogen. .3 mmol), 2.25 mL (20.2 mmol) of iodobenzene, and 50.0 mL of dimethylformamide were charged and heated at an internal temperature of 110 ° C. for 7 hours. The reaction mixture was cooled to room temperature, an aqueous ammonium chloride solution was added, and the mixture was diluted with ethyl acetate. The organic phase was separated, washed with saturated brine, and dried over anhydrous magnesium sulfate. After filtering magnesium sulfate, the residue obtained by distilling off the filtrate is purified by silica gel column chromatography to obtain 2.30 g (yield 91%) of the target product represented by the following formula (A-1a). Obtained.
^{1 1} H NMR (270 MHz, CDCl ₃ ) δ 12.88 (1 H, d, J = 0.5 Hz, -OH), 7.73-7.62 (2 H, m, Ar-H), 7.62-7 .38 (5H, m, Ar-H), 6.78 (1H, t, J = 7.8Hz, Ar-H), 1.47 (9H, s, -C (CH ₃ ) ₃ ) ppm

[Synthesis Example 1-2]
0.77 g (3.02 mmol) of the compound (A-1a) obtained in Synthesis Example 1-1 was synthesized in a fully dried and nitrogen-substituted 100 mL reactor by the method described in JP-A-2014-224053. 2'-amino-3,5-di-tert-butyl-2-hydroxy-1,1'-biphenyl 0.94 g (3.16 mmol), small amount of p-toluenesulfonic acid, small amount of molecular sieve 4A, xylene 7 0.0 mL was charged and stirred under heating and reflux for 35 hours. The residue obtained by distilling off the solvent was purified by silica gel column chromatography and then washed with methanol to give the desired product represented by the following formula (A-1L) (hereinafter, "Compound (A-1L)"). ”) Was obtained in an amount of 0.45 g (yield 28%).
_{^{1 H NMR (270MHz, CDCl 3}} ) δ 14.51 (1H, s, -OH), 7.31 (1H, dd, J = 7.6and1.6Hz, Ar-H), 7.28-7.21 (5H, m, Ar-H), 7.17 (1H, dt, J = 7.7 and 1.7Hz, Ar-H), 7.08 (1H, dt, J = 7.4and 1.4Hz, Ar-H) ), 7.02 (1H, d, J = 2.4Hz, Ar-H), 6.92-6.82 (3H, m, Ar-H), 6.71 (1H, dd, J = 8. 0and 1.7Hz, Ar-H), 6.55 (1H, t, J = 7.8Hz, Ar-H), 4.77 (1H, s, -OH), 1.43 (9H, s, -C) (CH ₃ ) ₃ ), 1.40 (9H, s, -C (CH ₃ ) ₃ ), 1.26 (9H, s, -C (CH ₃ ) ₃ ) ppm

[Example 1A]
0.22 g (0.40 mmol) of the compound (A-1L) obtained in Synthesis Example 1-2 and 15 mL of a toluene solution were charged into a 100 mL reactor that had been sufficiently dried and substituted with argon, and the mixture was stirred. The solution was cooled to −78 ° C., and 0.40 mL (1.00 M, 0.40 mmol) of a toluene solution of titanium tetrachloride was added dropwise. After completion of the dropping, stirring was continued for 15 hours while slowly returning to room temperature. After distilling off the solvent of the reaction solution, 10 mL of n-hexane was added to the obtained solid and irradiated with ultrasonic waves to prepare a suspension. The insoluble matter is filtered off with a glass filter, and the residue is dried under reduced pressure to obtain a brown powder compound represented by the following formula (A-1) (hereinafter, "titanium compound (A-1)" or "transition metal compound (A-)". 1) ”) was obtained in an amount of 0.20 g (yield 77%).
¹ H NMR (270 MHz, CDCl ₃ ) δ 7.60 (1 H, dd, J = 7.4 and 2.0 Hz, Ar-H), 7.33-7.15 (7 H, m, Ar-H), 7. 10-7.01 (1H, m, Ar-H), 6.99 (1H, d, J = 2.5Hz, Ar-H), 6.93-6.76 (3H, m, Ar-H) , 6.24 (1H, d, J = 7.7Hz, Ar-H), 1.56 (9H, s, -C (CH ₃ ) ₃ ), 1.41 (9H, s, -C (CH ₃₎ ) ₃ ), 1.36 (9H, s, -C (CH ₃ ) ₃ ) ppm
FD-Mass Spectrometry (M ⁺ ): 649

[Comparative Example 1A]
The titanium compound (A-2) represented by the following formula (A-2) (hereinafter, also referred to as “transition metal compound (A-1)”) was synthesized by the method described in Japanese Patent Application Laid-Open No. 2011-16789.

[Example 1-1]
<Manufacturing of polyethylene>
250 mL of toluene was charged into a glass reactor having an internal volume of 500 mL sufficiently nitrogen-substituted, and the liquid phase and the gas phase were saturated with 100 liters / hr of ethylene. Then, 0.125 mmol of triisobutylaluminum (TIBA), 0.0025 mmol of the titanium compound (A-1) obtained in Example 1A, and 0 of triphenylcarbenium tetrakis (pentafluorophenyl) borate (TrB). Polymerization was started by adding .003 mmol. Ethylene was continuously supplied at 100 liters / hr, and polymerization was carried out at 25 ° C. for 5 minutes under normal pressure, and then polymerization was stopped by adding a small amount of isobutanol. After completion of the polymerization, the reaction product was added to 1 liter of methanol containing a small amount of hydrochloric acid to precipitate the polymer. After washing with methanol, the mixture was dried under reduced pressure at 80 ° C. for 10 hours to obtain 0.23 g of polyethylene. The polymerization activity was 1,110 g / mmol-Ti · hr, and the ultimate viscosity [η] of the obtained polyethylene was 2.18 dL / g. The results are shown in Table 6.

[Example 1-2]
<Manufacturing of polyethylene>
When ethylene polymerization was carried out in the same manner as in Example 1-1 except that the polymerization temperature was set to 50 ° C., 0.40 g of polyethylene was obtained. The polymerization activity is 1,914 g / mmol-Ti · hr, the ultimate viscosity [η] is 1.10 dL / g, the weight average molecular weight (Mw) is 37,600, and the number average molecular weight (Mn) is 19,000. Met. The results are shown in Tables 6 and 7.

[Example 1-3]
<Manufacturing of polyethylene>
When ethylene polymerization was carried out in the same manner as in Example 1-1 except that the polymerization temperature was 75 ° C., 0.82 g of polyethylene was obtained. The polymerization activity was 3,927 g / mmol-Ti · hr, and the ultimate viscosity [η] was 1.03 dL / g. The results are shown in Table 6.

[Example 1-4]
<Manufacturing of ethylene / propylene copolymer>
250 mL of toluene was charged into a glass reactor having an internal volume of 500 mL sufficiently substituted with nitrogen, and the liquid phase and the gas phase were saturated with a mixed gas of 100 liters / hr of ethylene and 100 liters / hr of propylene. Then, 0.125 mmol of triisobutylaluminum (TIBA), 0.0025 mmol of the titanium compound (A-1) obtained in Example 1A, and 0 of triphenylcarbenium tetrakis (pentafluorophenyl) borate (TrB). Copolymerization was started by adding .003 mmol. Ethylene was continuously supplied at 100 liters / hr and propylene was continuously supplied at 100 liters / hr, and polymerization was carried out at 50 ° C. for 10 minutes under normal pressure, and then polymerization was stopped by adding a small amount of isobutanol. To the obtained polymer suspension, 100 mL of water containing a small amount of hydrochloric acid was added, and the mixture was shaken vigorously, allowed to stand, and then the aqueous layer was removed. After repeating this operation a total of 3 times, the solvent was distilled off under reduced pressure, and the mixture was further dried under reduced pressure at 130 ° C. for 10 hours. The obtained ethylene / propylene copolymer (EPR) weighed 1.69 g. The polymerization activity was 4,056 g / mmol-Ti · hr, the propylene content measured by IR was 57.1 mol%, the ultimate viscosity [η] was 2.16 dL / g, and the weight average molecular weight (Mw) was It was 140,100, and the number average molecular weight (Mn) was 64,400. The results are shown in Table 7.

[Comparative Example 1-1]
<Manufacturing of polyethylene>
Ethylene polymerization was carried out in the same manner as in Example 1-1 except that the compound (A-2) obtained in Comparative Example 1A was used instead of the compound (A-1), and 0.56 g of polyethylene was obtained. Was done. The polymerization activity was 2,674 g / mmol-Ti · hr, and the ultimate viscosity [η] was 1.22 dL / g. The results are shown in Table 6.

[Comparative Example 1-2]
<Manufacturing of polyethylene>
When ethylene polymerization was carried out in the same manner as in Comparative Example 1-1 except that the polymerization temperature was set to 50 ° C., 0.38 g of polyethylene was obtained. The polymerization activity is 1,819 g / mmol-Ti · hr, the ultimate viscosity [η] is 0.84 dL / g, the weight average molecular weight (Mw) is 16,700, and the number average molecular weight (Mn) is 6,700. Met. The results are shown in Tables 6 and 7.

[Comparative Example 1-3]
<Manufacturing of polyethylene>
Ethylene polymerization was carried out in the same manner as in Comparative Example 1-1 except that the polymerization temperature was 75 ° C., and 0.26 g of polyethylene was obtained. The polymerization activity was 1,229 g / mmol-Ti · hr, and the ultimate viscosity [η] was 0.70 dL / g. The results are shown in Table 6.

[Comparative Example 1-4]
<Manufacturing of ethylene / propylene copolymer>
Ethylene / propylene copolymerization was carried out in the same manner as in Example 1-4 except that the compound (A-2) obtained in Comparative Example 1A was used instead of the compound (A-1). 2.82 g of copolymer (EPR) was obtained. The polymerization activity was 6,773 g / mmol-Ti · hr, the propylene content measured by IR was 57.0 mol%, the ultimate viscosity [η] was 1.47 dL / g, and the weight average molecular weight (Mw) was It was 85,400 and the number average molecular weight (Mn) was 42,100. The results are shown in Table 7.

Examples 1-1 to 3 using the transition metal compound [A] of the present invention are in proportion to the increase in the polymerization temperature as compared with Comparative Examples 1-1 to 3 using the imine type transition metal compound. The catalytic activity tended to be clearly higher. Further, in Example 1-3, the value of the ultimate viscosity [η] of polyethylene obtained under high temperature conditions is also higher than that of Comparative Example 1-3, and high molecular weight polyethylene can be produced.

Examples 1-2 and 1-4 using the transition metal compound [A] of the present invention were obtained copolymers as compared with Comparative Examples 1-2 and 1-4 using the imine type transition metal compound. The molecular weight of was clearly high. In addition, Example 1-4 had a high propylene content and showed copolymerizability equivalent to that of Comparative Example 1-4.

That is, by using the transition metal compound [A] of the present invention, a highly active and high molecular weight polymer can be obtained even by polymerization under relatively high polymerization temperature conditions preferable for commercial production. When copolymerizing more than one kind of olefins, it is possible to produce a polymer having a high molecular weight while maintaining the high copolymerizability of the imine type transition metal compound.

<Synthesis of transition metal compound (A)>
[Synthesis Example 2-1]
In a 200 mL reactor that was sufficiently dried and replaced with nitrogen, Angew. Chem. Int. Ed. 1997, 36, 1740. 3.91 g (12.1 mmol) of 6'-phenyl- [1,1': 2', 1 "-terphenyl] -2-ol synthesized by the method described and 17 mL of tetrahydrofuran were charged and stirred under ice cooling. 4.50 mL of ethylmagnesium bromide (diethyl ether solution, 3M, 13.5 mmol) was added dropwise over 30 minutes. After stirring at room temperature for 2 hours, 0.98 g (32.5 mmol) of paraformaldehyde and 2.60 mL of triethylamine (2.60 mL). 18.7 mmol) was added, and the mixture was heated under reflux at 80 ° C. for 2 hours. After cooling the reaction solution to room temperature, the reaction solution was neutralized with 60 mL of 18% hydrochloric acid. The organic phase was separated and washed with saturated brine. The residue obtained by distilling off the filtrate after filtering magnesium sulfate was purified by silica gel column chromatography. The target product represented by the following formula (A-3a) (hereinafter, "Compound (A-3a)") was obtained in 3.62 g (85% yield).
_{^{1 H NMR (270MHz, CDCl 3}} ) δ: 10.91 (1H, s, -OH), 9.68 (1H, s, -CHO), 7.52 (1H, dd, J = 8.8and6.1Hz , Ar-H), 7.44 (1H, d, J = 0.5Hz, Ar-H), 7.41 (1H, d, J = 1.9Hz, Ar-H), 7.24 (1H, dd, J = 7.7and 1.7Hz, Ar-H), 7.20-7.09 (10H, m, Ar-H), 7.05 (1H, dd, J = 7.5and1.4Hz, Ar- H), 6.68 (1H, t, J = 7.6Hz, Ar-H) ppm

[Synthesis Example 2-2]
To a 100 mL reactor that had been sufficiently dried and replaced with nitrogen, 40 mL of a tetrahydrofuran solution of 1.20 g (3.73 mmol) of the compound (A-3a) obtained in Synthesis Example 2-1 was charged and stirred. The solution was cooled to 0 ° C. and charged with 165 mg (4.13 mmol) of sodium hydride. After stirring at the same temperature for 25 minutes, stirring was continued for 2 hours while slowly returning to room temperature. 0.34 mL (4.49 mmol) of chloromethyl methyl ether was added dropwise, stirring was continued for 16 hours, and distilled water was added to stop the reaction. The product was extracted with hexane, washed with water and saturated brine, and dried over anhydrous magnesium sulfate. The solvent was distilled off to obtain 1.37 g of a residue. The residue was dissolved in 40 mL of diethyl ether in a fully dried and nitrogen-substituted 100 mL reactor and stirred. This solution was cooled to 0 ° C., and a hexane solution of n-butyllithium (1.55 M, 4.88 mmol) was added dropwise. After continuing stirring for 19 hours while slowly returning to room temperature, 0.80 g (5.26 mmol) of N, N-dimethylbenzamide was charged, and heating and stirring was continued for 5 hours in an oil bath at 45 ° C. After cooling to room temperature, 40 mL of saturated aqueous ammonium chloride solution was added, and the mixture was stirred for 20 minutes. The product was extracted with hexane, washed with water and saturated brine, and dried over anhydrous magnesium sulfate. The residue obtained by distilling off the solvent was dissolved in 28 mL of water-containing tetrahydrofuran in air at room temperature, and 4 mL of concentrated hydrochloric acid was added dropwise to start stirring. After 16 hours and 23 hours, 2.5 mL and 4 mL of concentrated hydrochloric acid were additionally charged, respectively. After stirring for 40 hours, the product was extracted with ethyl acetate and washed with saturated aqueous sodium hydrogen carbonate, water and saturated brine. After drying over anhydrous magnesium sulfate, the solvent was distilled off, and the obtained residue was purified by silica gel chromatography to find the target product represented by the following formula (A-3b) (hereinafter referred to as "compound (A-3b)"). 00 g (yield 63%) was obtained.
^{1 1} H NMR (270 MHz, CDCl ₃ ) δ: 11.84 (1H, s, -OH), 7.56-7.50 (4H, m, Ar-H), 7.47-7.42 (4H, m, Ar-H), 7.21-7.13 (11H, m, Ar-H), 7.05-7.01 (1H, m, Ar-H), 6.57-6.51 (1H) , M, Ar-H) ppm

[Synthesis Example 2-3]
0.44 g (1.02 mmol) of the compound (A-3b) obtained in Synthesis Example 2-2 was synthesized in a sufficiently dried and nitrogen-substituted 50 mL reactor by the method described in JP-A-2014-224053. '-Amino-3,5-di-tert-butyl-2-hydroxy-1,1'-biphenyl 0.54 g (1.55 mmol), p-toluenesulfonic acid monohydrate 25 mg (0.13 mmol), toluene 30 mL was charged, and the mixture was intermittently stirred for 24 hours under heating and reflux. After allowing to cool, the solvent was distilled off and the obtained residue was purified by silica gel column chromatography. As a result, the target product represented by the following formula (A-3L) (hereinafter referred to as "compound (A-3L)") was found to be 0. 27 g (yield 37%) was obtained.
^{1 1} H NMR (270 MHz, CDCl ₃ ) δ: 13.34 (1H, s, -OH), 7.47-7.43 (4H, m, Ar-H), 7.32-7.06 (17H, 17H, m, Ar-H), 6.97-6.96 (1H, m, Ar-H), 6.79-6.74 (1H, m, Ar-H), 6.69-6.65 (1H) , M, Ar-H), 6.50-6.47 (1H, m, Ar-H), 6.31-6.25 (1H, m, Ar-H), 4.88 (1H, s, -OH), 1.41 (9H, s, -C (CH ₃ ) ₃ ), 1.26 (9H, s, -C (CH ₃ ) ₃ ) ppm

[Example 2A]
To a 50 mL Schlenk reactor that had been sufficiently dried and replaced with nitrogen, 20 mL of a toluene solution of 0.26 g (0.36 mmol) of the compound (A-3L) obtained in Synthesis Example 2-3 was charged and stirred. This solution was cooled to −78 ° C., and 0.36 mL (1.00 M, 0.36 mmol) of a toluene solution of titanium tetrachloride was added dropwise. After stirring at the same temperature for 2 hours, stirring was continued for 19 hours while slowly returning to room temperature. After distilling off the solvent of the reaction solution, the obtained residue was washed with 15 mL of hexane to form a red-orange powder compound represented by the following formula (A-3) (hereinafter referred to as “titanium compound (A-3)” or. 0.30 g (yield 100%) of "transition metal compound (A-3)") was obtained.
^{1 1} H NMR (270 MHz, CDCl ₃ ) δ: 7.58-7.47 (3H, m, Ar-H), 7.32-6.97 (19H, m, Ar-H), 6.80-6 .77 (1H, m, Ar-H), 6.62-6.60 (2H, m, Ar-H), 6.34-6.25 (2H, m, Ar-H), 1,40 ( 9H, s, -C (CH ₃ ) ₃ ), 1.36 (9H, s, -C (CH ₃ ) ₃ ) ppm
FD-Mass Spectrometry (M ⁺ ): 821.2

<Synthesis of transition metal compound (A)>
[Synthesis Example 3-1]
It was synthesized from 2-bromo-4,6-di-tert-butylphenol and 2-trimethylsilylethanol in a sufficiently dried and prime-substituted 100 mL reactor by the method described in JP-A-2006-545808 (2- (2). -Bromo-4,6-di-tert-butylphenoxy) ethyl) Trimethylsilane 1.24 g (3.21 mmol) and tetrahydrofuran 30 mL were charged and stirred. This solution was cooled to −78 ° C., and a hexane solution of n-butyllithium (1.55 M, 3.41 mmol) was added dropwise. After stirring at the same temperature for 1 hour, 20 mL of a solution of trimethyl borate (1.10 mL (9.69 mmol)) in tetrahydrofuran was charged over 1 hour. After continuing stirring for 18 hours while slowly returning to room temperature, the reaction was stopped with 50 mL of saturated aqueous ammonium chloride solution. The product was extracted with ethyl acetate and washed with water and saturated brine. After drying over anhydrous magnesium sulfate, the solvent is distilled off and the mixture is azeotropically boiled with hexane to obtain 1.05 g (hereinafter referred to as "compound (A-4a)") of the target product represented by the following formula (A-4a). Yield 93%) was obtained.
^{1 1} H NMR (270 MHz, CDCl ₃ ) δ: 7.65 (1H, d, J = 2.7 Hz, Ar-H), 7.48 (1H, d, J = 2.7 Hz, Ar-H), 5 .71-5.68 (2H, m, -OH), 3.90-3.83 (2H, m, -OCH _2- ), 1.40 (9H, s, -C (CH ₃ ) ₃ ), 1.32 (9H, s, -C (CH ₃ ) ₃ ), 1.29-1.22 (2H, m, -SiCH _2- ), 0.02 (9H, s, -Si (CH ₃ ) ₃ ) ) Ppm

[Synthesis Example 3-2]
1.02 g (3.19 mmol) of barium hydroxide octahydrate, 0.43 g (2.89 mmol) of 2-chloro-6-fluoroaniline, Synthesis Example 3-in a 100 mL reactor that has been sufficiently dried and replaced with nitrogen. 1.05 g (3.00 mmol) of the compound (A-4a) obtained in 1 and 30 mL of 2-propanol were charged and stirred. 9 mg (0.02 mmol) of CX21 (manufactured by Yumicore Co., Ltd.) was charged, and the mixture was intermittently heated and stirred in an 80 ° C. oil bath for 12 hours. After allowing to cool, the insoluble material was removed by suction filtration and the filtrate was concentrated. By purifying the residue by silica gel column chromatography, 0.71 g (yield 49%) of the target product represented by the following formula (A-4b) (hereinafter referred to as “compound (A-4b)”) was obtained.
^{1 1} H NMR (270 MHz, CDCl ₃ ) δ: 7.36 (1H, d, J = 2.7 Hz, Ar-H), 7.09 (1H, d, J = 2.7 Hz, Ar-H), 7 .03-6.96 (2H, m, Ar-H), 6.79-6.74 (1H, m, Ar-H), 4.03 (2H, s, -NH ₂ ), 3.58- 3.52 (2H, m, -OCH _2- ), 1.44 (9H, s, -C (CH ₃ ) ₃ ), 1.31 (9H, s, -C (CH ₃ ) ₃ ), 1. 31-1.28 (2H, m, -SiCH _2- ), -0.20 (9H, s, -Si (CH ₃ ) ₃ ) ppm

[Synthesis Example 3-3]
0.71 g (1.46 mmol) of the compound (A-4b) obtained in Synthesis Example 3-2, 0.69 g (4.46 mmol) of cesium fluoride, and N in a 50 mL reactor that was sufficiently dried and replaced with nitrogen. , N-Dimethylformamide (20 mL) was charged, and the mixture was heated and stirred in an oil bath at 60 ° C. for 4 hours. After allowing to cool, the product was diluted with water, extracted with diethyl ether, and washed 3 times with water and 1 time with saturated brine. After drying over anhydrous magnesium sulfate, the solvent was distilled off and the obtained residue was purified by silica gel column chromatography to obtain the target product represented by the following formula (A-4c) (hereinafter, "Compound (A-4c)"). 0.43 g (yield 84%) was obtained.
^{1 1} H NMR (270 MHz, CDCl ₃ ) δ: 7.37 (1H, d, J = 2.2 Hz, Ar-H), 7.10 (1H, d, J = 2.2 Hz, Ar-H), 7 .06-7.01 (2H, m, Ar-H), 6.89-6.84 (1H, m, Ar-H), 6.22 (1H, s, -OH), 3.84 (2H) , S, -NH ₂ ), 1.45 (9H, s, -C (CH ₃ ) ₃ ), 1.32 (9H, s, -C (CH ₃ ) ₃ ) ppm

[Synthesis Example 3-4]
0.33 g (0.94 mmol) of the compound (A-3a) obtained in Synthesis Example 2-1 and the compound (A-) obtained in Synthesis Example 3-3 were placed in a 50 mL reactor sufficiently dried and substituted with nitrogen. 4c) 0.43 g (1.22 mmol), 25 mg (0.13 mmol) of p-toluenesulfonic acid monohydrate, and 20 mL of toluene were charged, and the mixture was heated and stirred intermittently for 31 hours under heating under reflux. After cooling the reactor, the solvent was distilled off to obtain a residue. The residue was passed through a silica gel column to remove unreacted compound (A-4c). The rest was dissolved in 30 mL of toluene in a 50 mL reactor that was thoroughly dried and replaced with nitrogen. 0.1 mL (0.53 mmol) of diphenylsilane and 15 mg (0.02 mmol) of Wilkinson complex were added, and the mixture was heated and stirred in an oil bath at 80 ° C. for 15 hours. By purifying the residue obtained by distilling off the solvent after allowing to cool by silica gel column chromatography, the target product represented by the following formula (A-4L) (hereinafter referred to as “compound (A-4L)”) was obtained. 15 g (yield 24%) was obtained.
_{^{1 H NMR (270MHz, CDCl 3}} ) δ: 12.16 (1H, s, -OH), 8.16 (1H, d, J = 1.6Hz, -CH = N -), 7.50-7. 36 (4H, m, Ar-H), 7.28-7.06 (13H, m, Ar-H), 6.95 (1H, d, J = 2.2Hz, Ar-H), 6.78 (1H, dd, J = 7.3, 1.6Hz, Ar-H), 6.74 (1H, dd, J = 7.3, 2.2Hz, Ar-h), 6.47 (1H, t) , J = 7.3Hz, Ar-H), 4.92 (1H, s, -OH), 1.33 (9H, s, -C (CH ₃ ) ₃ ), 1.22 (9H, s,- C (CH ₃ ) ₃ ) ppm

[Example 3A]
To a 50 mL Schlenk reactor that had been sufficiently dried and replaced with nitrogen, 20 mL of a toluene solution of 0.15 g (0.22 mmol) of the compound (A-4L) obtained in Synthesis Example 3-4 was charged and stirred. The solution was cooled to −78 ° C., and 0.23 mL (1.00 M, 0.23 mmol) of a toluene solution of titanium tetrachloride was added dropwise. Stirring was continued for 19 hours while slowly returning to room temperature, and the solvent of the reaction solution was distilled off. By washing the obtained residue with 15 mL of hexane, the red-pink powder compound represented by the following formula (A-4) (hereinafter referred to as "titanium compound (A-4)" or "transition metal compound (A-4)"". 0.15 g (yield 88%) was obtained.
^{1 1} H NMR (270 MHz, CDCl ₃ ) δ: 8.16 (1H, m, -CH = N-), 7.57-7.05 (20H, m, Ar-H), 6.89-6.83 (1H, m, Ar-H), 1,37 (9H, s, -C (CH ₃ ) ₃ ), 1.31 (9H, s, -C (CH ₃ ) ₃ ) ppm
FD-Mass Spectrometry (M ⁺ ): 763.2

[Example 1-5]
<Manufacturing of ethylene / propylene / ethylidene norbornene copolymer>
Hexane 1030 mL and 5-ethylidene-2-norbornene (ENB) 4 mL were charged into a stainless steel autoclave with an internal volume of 2 L sufficiently substituted with nitrogen, the temperature inside the system was raised to 95 ° C, and then propylene was divided by pressure. The total pressure was adjusted to 1.6 MPa-G by charging 0.45 MPa and supplying ethylene. Next, MMAO was press-fitted with 0.3 mmol nitrogen, and 0.0005 mmol of the compound (A-1) obtained in Example 1A and 0.0002 mmol of triphenylcarbenium tetrakis (pentafluorophenyl) borate were added in Schlenk for 15 minutes. The mixed solution was press-fitted with nitrogen, and the stirring speed was set to 250 rpm to initiate polymerization. Then, by continuously supplying only ethylene, the total pressure was maintained at 1.6 MPa-G, and polymerization was carried out at 95 ° C. for 15 minutes. After terminating the polymerization by adding a small amount of methanol into the system, unreacted ethylene was purged. The polymer was precipitated by putting the obtained polymer solution into a large excess of methanol / acetone mixed solution. The polymer was collected by filtration and dried under reduced pressure at 120 ° C. overnight.

As a result, 2.78 g of an ethylene / propylene / ENB copolymer having an ethylene content of 62.7 mol% and an ENB content of 0.9 mol% (3.1 wt%) was obtained. The polymerization activity was 22.2 kg / mmol-Ti / h. The results are shown in Table 8.

[Example 2-5]
<Manufacturing of ethylene / propylene / ENB copolymer>
The same operation as in Example 1-5 was carried out except that the compound (A-3) obtained in Example 2A was used instead of the compound (A-1).

As a result, 9.61 g of an ethylene / propylene / ENB copolymer having an ethylene content of 80.1 mol% and an ENB content of 7.3 mol% (21.0 wt%) was obtained. The polymerization activity was 76.9 kg / mmol-Ti / h. The results are shown in Table 8.

[Example 3-5]
<Manufacturing of ethylene / propylene / ethylidene norbornene copolymer>
The same operation as in Example 1-5 was carried out except that the compound (A-4) obtained in Example 3A was used instead of the compound (A-1).

As a result, 6.94 g of an ethylene / propylene / ENB copolymer having an ethylene content of 72.9 mol% and an ENB content of 2.7 mol% (9.7 wt%) was obtained. The polymerization activity was 55.5 kg / mmol-Ti / h. The results are shown in Table 8.

[Comparative Example 1-5]
<Manufacturing of ethylene / propylene / ethylidene norbornene copolymer>
The same operation as in Example 1-5 was carried out except that the compound (A-2) obtained in Comparative Example 1A was used instead of the compound (A-1).

As a result, 1.61 g of an ethylene / propylene / ENB copolymer having an ethylene content of 59.1 mol% and an ENB content of 1.4 mol% (4.8 wt%) was obtained. The polymerization activity was 12.9 kg / mmol-Ti / h. The results are shown in Table 8.

Examples 1-5, 2-5 and 3-5 using the transition metal compound [A] of the present invention are Comparative Examples 1-5 even when the polymerization is carried out under relatively high polymerization temperature conditions preferable for commercial production. The catalytic activity was clearly higher than that of the above, and the ENB content of the obtained copolymer and the conversion rate of the added ENB were substantially equal to or higher than those of the comparative example. If a transition metal compound that easily reacts with ENB is selected, the process can be made with less load in the monomer recovery step.

By using a novel transition metal compound according to the present invention and a catalyst for olefin polymerization containing the transition metal compound, a high molecular weight polyolefin can be obtained in a high yield, and when copolymerizing two or more kinds of olefins. In the above, a polyolefin having a high molecular weight and a high copolymer content can be obtained in a high yield. The polyolefin has excellent commercially suitable performance such as impact resistance, flexibility, high elasticity, light weight, transparency, high heat resistance, weather resistance, chemical resistance, etc. at a high level. Has extremely high industrial value.

Claims (10)

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

(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 anionic 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, and when n is 2 or more, a plurality of groups represented by X are the same. But they may be different, they may combine with each other to form a ring,
R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² and R ¹³ are independently hydrogen atoms and 1 carbon atoms, respectively. ~ 40 hydrocarbon groups, halogen atoms, halogen-containing groups, silicon-containing groups, oxygen-containing groups, nitrogen-containing groups or sulfur-containing groups.
However, at least one of R ⁵ and R ⁶ is not a hydrogen atom,
Adjacent substituents of R ^{1 to} R ¹³ may be bonded to each other to form a ring which may have a substituent. ) In the general formula [1], R ¹ , R ² , R ³ , R ⁴ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² and R ¹³ are each independently hydrogen. Atomic, hydrocarbon group with 1 to 40 carbon atoms, halogen atom, halogen-containing group, silicon-containing group, oxygen-containing group, nitrogen-containing group or sulfur-containing group, R ⁵ is a hydrogen atom, hydrocarbon with 1 to 40 carbon atoms The transition metal compound [A] according to claim 1, which is a hydrogen group, a halogen-containing group, a silicon-containing group, an oxygen-containing group, a nitrogen-containing group or a sulfur-containing group. In the general formula [1], R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² and R ¹³ are independent of each other. The transition metal compound [A] according to claim 1, which is a hydrogen atom, a hydrocarbon group having 1 to 40 carbon atoms, a halogen-containing group, a silicon-containing group, an oxygen-containing group, a nitrogen-containing group, or a sulfur-containing group. In the general formula [1],
X is independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 10 carbon atoms, a silicon-containing hydrocarbon group, or an oxygen-containing hydrocarbon group.
R ⁴ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ and R ¹² are hydrogen atoms,
R ¹ , R ² , R ³ , R ¹¹ and R ¹³ independently have a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group having 1 to 20 carbon atoms, and oxygen having 1 to 20 carbon atoms. The transition metal compound [A] according to any one of claims 1 to 3, which is a containing group or a nitrogen-containing group having 1 to 20 carbon atoms. In the general formula [1],
R ⁵ is a hydrocarbon group having 1 to 10 carbon atoms or a halogen-containing group having 1 to 10 carbon atoms.
The transition metal compound [A] according to claim 4, wherein R ¹¹ and R ¹³ are each independently a hydrocarbon group having 1 to 10 carbon atoms. In the general formula [1],
M is a titanium atom,
n is 2 or 3
X is a neutral ligand coordinated with a lone pair of electrons on a halogen or oxygen atom.
The transition metal compound [A] according to claim 5, wherein R ⁵ is an aromatic hydrocarbon group having 10 or less carbon atoms. A catalyst for olefin polymerization containing the transition metal compound [A] according to any one of claims 1 to 6. Furthermore, [B] [B-1] organometallic compounds,
[B-2] Organoaluminium oxy compounds and
[B-3] The catalyst for olefin polymerization according to claim 7, which comprises at least one compound selected from the group consisting of compounds that react with the transition metal compound [A] to form an ion pair. A method for producing an olefin polymer, which comprises a step of polymerizing an olefin in the presence of the catalyst for olefin polymerization according to claim 7 or 8. The olefin weight according to claim 9, wherein the step of polymerizing the olefin is a step of homopolymerizing ethylene, a step of homopolymerizing propylene, or a step of copolymerizing ethylene with an α-olefin having 3 or more and 20 or less carbon atoms. Manufacturing method of coalescence.