JP7011919B2 - Catalysts for transition metal compounds and olefin polymerization - Google Patents

Description

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

A linear polymer having a polymerizable functional group at one end is expected to be used in a wide range of fields by taking advantage of its structural characteristics. For example, a macromonomer having a vinyl group at the terminal is used for producing a long-chain branched polymer by polymerizing at the same time as a monomer such as ethylene. Further, if the polymer using ethylene or propylene as a monomer has many double bonds at the ends, it can be developed into a polar resin composite material by functionalizing a vinyl group (see Patent Document 1).

However, conventionally, in order to produce a low molecular weight polymer, for example, a reactive hydrogen is charged to reduce the molecular weight, or a polymer produced by heat or an additive is decomposed. However, when hydrogen is inserted, the molecular weight of the produced polymer can be reduced, but the polymerization activity and the terminal double bond rate are lowered. Further, when the decomposition treatment is performed, the post-treatment cost increases, which makes it industrially difficult. Therefore, there has been a demand for a method for efficiently producing an α-olefin polymer having a high terminal double bond ratio and a low molecular weight.

By the way, low-density polyethylene (LDPE) produced by high-pressure radical polymerization has a complicated long-chain branched structure, so that it has a large melt tension, and as a result, it has good molding processability such as a small neck-in. It is used for various purposes. However, it cannot be said that the mechanical strength such as tensile strength, tear strength and impact resistance of the molded product obtained from low-density polyethylene is sufficient, and low-density polyethylene is inferior in high-speed film formation processability in T-die molding. There are still problems such as.

On the other hand, ethylene-based polymers obtained with Ziegler-catalyzed or metallocene-catalyzed materials, in contrast to LDPE, have high tensile strength, tear strength or impact resistance due to their molecular structure, and therefore require mechanical strength. However, there is a problem that the melt tension is small and the molding processability is inferior.

In order to solve these problems, [1] a method of blending LDPE with an ethylene-based polymer obtained by using a Ziegler catalyst or a metallocene catalyst (see Patent Document 2), and [2] expanding the molecular weight distribution by multistage polymerization. Method (see Patent Document 3), [3] Method for producing a long-chain branched ethylene-based polymer using a chromium catalyst, [4] Long-chain branched ethylene-based polymer using a specific metallocene catalyst. (See Patent Documents 4), [5] A method for producing a long-chain branched ethylene-based polymer by copolymerizing ethylene and diene using a specific metallocene catalyst (see Patent Documents 5 and 6). ) Etc. have been proposed.

However, the method of [1] inevitably increases the cost in preparing the blended product. The ethylene-based polymer obtained by the methods [2], [3], and [4] has a small number of long-chain branches, and does not have sufficient melt tension and molding processability. In the method of [5], if a large amount of diene is introduced, there is a concern that the mechanical properties inherent in the polymer may be deteriorated or gel may be generated.

In recent years, for the purpose of generating more long-chain branches and improving the melt tension, [6] a method of copolymerizing a macromonomer using a specific metallocene catalyst to produce a long-chain branched ethylene polymer (for example). , Patent Documents 7-9) have been reported. However, the macromonomer used here has a low proportion of the polymer having a vinyl group at the terminal and has a high molecular weight, so that it is hardly incorporated during polymerization and has sufficient long-chain branching to satisfy the molding processability. Not only is it impossible to obtain a polymer with a large number, but also a large amount of unreacted macromonomer remains (see Patent Document 10), which causes problems such as a decrease in the mechanical strength of the polymer and a complicated production process.

Therefore, if a polymer having a vinyl group at the terminal and having a relatively small molecular weight can be efficiently produced, the polymer having a large number of long-chain branches can be synthesized by using it as a macromonomer in the above-mentioned macromonomer copolymerization. It also enables a wide range of applications such as polar resin composite materials by functionalizing unsaturated bonds.

As a method for meeting this demand, [7] a method for producing a polymer having a vinyl group at the terminal and having a relatively small molecular weight by using a specific metallocene catalyst is disclosed (Patent Document 11). The development of a catalyst having higher polymerization activity has been desired.

WO2005 / 073282 Pamphlet WO99 / 046325 Pamphlet Japanese Unexamined Patent Publication No. 2-53811 Japanese Unexamined Patent Publication No. 4-213306 Special Table 1-50163 Gazette Special Table No. 4-506372 Gazette Japanese Unexamined Patent Publication No. 8-502303 Japanese Unexamined Patent Publication No. 2004-281676 Japanese Patent Publication No. 2001-511214 WO2006 / 080578 Pamphlet Japanese Unexamined Patent Publication No. 2009-143901

The present invention has been made to solve the above problems, that is, an olefin polymer having a high ratio of having a vinyl group at the terminal and a relatively low molecular weight as compared with the case of using a known metallocene compound. To provide a crosslinked metallocene compound for olefin polymerization capable of producing (macromonomer), to provide a catalyst for olefin polymerization containing the crosslinked metallocene compound, and to provide a catalyst for olefin polymerization containing the crosslinked metallocene compound. It is an object of the present invention to provide a method for efficiently producing an olefin polymer.

As a result of diligent research in view of such a situation, the present inventors have developed a new transition metal compound and developed it as a catalyst for olefin polymerization, thereby having a vinyl group at the terminal. In addition, they have found a method for efficiently producing an olefin polymer having a relatively small molecular weight, and have 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、Ｍの価数を満たす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、該アニオン配位子が、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、
Ｑは、周期表第１４族原子であり、
Ｒ¹～Ｒ¹²は、それぞれ独立に、水素原子、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、それぞれ同一でも異なっていてもよく、
ただし、Ｒ⁸およびＲ⁹のいずれか一方は、直鎖状部分の炭素数が３～１０の飽和炭化水素基または直鎖状部分の炭素数が３～１０の末端不飽和炭化水素基であり、
Ｒ⁷とＲ⁸は、互いに結合して置換基を有していてもよい飽和環を形成してもよく、
Ｒ⁹とＲ¹⁰は、互いに結合して置換基を有していてもよい飽和環を形成してもよく、
Ｒ¹¹とＲ¹²は、互いに結合してＱを含む環を形成してもよく、該環は置換基を有していてもよい。）

(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 satisfying the valence of M.
X is a neutral ligand capable of coordinating with a hydrogen atom, a halogen atom, a hydrocarbon group, an anionic ligand or an isolated electron pair, and the anion ligand is a halogen-containing group, a silicon-containing group, or oxygen. It is a containing group, a sulfur-containing group, a nitrogen-containing group, a phosphorus-containing group, a boron-containing group, an aluminum-containing group or a conjugated diene-based derivative group. But they may be different, they may combine with each other to form a ring,
Q is a group 14 atom of the periodic table,
R ¹ to R ¹² are independently hydrogen atoms, hydrocarbon groups having 1 to 40 carbon atoms, halogen-containing groups, silicon-containing groups, oxygen-containing groups, nitrogen-containing groups or sulfur-containing groups, and they are the same or different. May be
However, either R ⁸ or R ⁹ is a saturated hydrocarbon group having 3 to 10 carbon atoms in the linear portion or a terminal unsaturated hydrocarbon group having 3 to 10 carbon atoms in the linear portion. ,
R ⁷ and R ⁸ may be bonded to each other to form a saturated ring which may have a substituent.
R ⁹ and R ¹⁰ may be bonded to each other to form a saturated ring which may have a substituent.
R ¹¹ and R ¹² may be bonded to each other to form a ring containing Q, and the ring may have a substituent. )

[2]
In the general formula [1],
M is a zirconium atom or a hafnium atom,
X is independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group or an oxygen-containing group, respectively.
The transition metal compound [A] according to the above [1], wherein Q is a carbon atom or a silicon atom.

[3]
In the general formula [1],
Q is a silicon atom,
R ¹ to R ¹² are independently hydrogen atoms, hydrocarbon groups having 1 to 20 carbon atoms, oxygen-containing groups having 1 to 20 carbon atoms, or nitrogen-containing groups having 1 to 20 carbon atoms, and they are the same or different. The transition metal compound [A] according to the above [1], wherein the transition metal compound [A] may be used.

[4]
In the general formula [1],
R ¹ and R ⁶ are hydrogen atoms,
R ² to R ⁵ , R ¹¹ and R ¹² are each independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and may be the same or different from each other.
One of R ⁷ and R ¹⁰ is a hydrogen atom,
The transition metal compound [A] according to the above [3], wherein either R ⁸ or R ⁹ is a hydrogen atom.

[5]
In the general formula [1],
The transition metal compound [A] according to the above [4], wherein R ² to R ⁵ , R ⁷ and R ¹⁰ are hydrogen atoms.

[6]
A catalyst for olefin polymerization, which comprises the transition metal compound [A] according to any one of [1] to [5].

[7]
Further, (B-1) organometallic compound,
It contains at least one compound [B] selected from the group consisting of (B-2) an organoaluminum oxy compound and (B-3) a compound that reacts with a transition metal compound [A] to form an ion pair. The catalyst for olefin polymerization according to the above [6].

[8]
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 the above [6] or [7].

[9]
The olefin polymer according to the above [8], wherein the step of polymerizing the olefin is a step of homopolymerizing ethylene or copolymerizing ethylene with an α-olefin having 3 or more and 20 or less carbon atoms. Production method.

According to the olefin polymerization catalyst and the method for producing an olefin polymer according to the present invention, an olefin polymer having a high ratio of having a vinyl group at the terminal and a relatively low molecular weight as compared with the case of using a known metallocene compound ( Macromonomer) can be produced.

[Transition metal compound [A]]
The transition metal compound [A] according to the present invention is represented by the following general formula [1].

《Ｍ、ｎ、Ｘ》
一般式［１］において、Ｍは、周期表第４族遷移金属原子であり、好ましくはジルコニウム原子またはハフニウム原子であり、さらに好ましくはジルコニウム原子である。

<< M, n, X >>
In the general formula [1], M is a Group 4 transition metal atom of the periodic table, preferably a zirconium atom or a hafnium atom, and more preferably a zirconium atom.

n is an integer of 1 to 4 satisfying the valence of the transition metal atom M, and is preferably 1 or 2.
X is a neutral ligand capable of coordinating with a hydrogen atom, a halogen atom, a hydrocarbon group, an anionic ligand or an isolated electron pair, and the anion ligand is a halogen-containing group, a silicon-containing group, or oxygen. It is a containing group, a sulfur-containing group, a nitrogen-containing group, a phosphorus-containing group, a boron-containing group, an aluminum-containing group, or a conjugated diene-based derivative group.

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

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

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

Examples of the halogen-containing group include a fluoromethyl group, a trifluoromethyl group, a trichloromethyl group, a pentafluoroethyl group, a 2,2,2-trifluoroethyl group, a fluorophenyl group, a difluorophenyl group and a trifluorophenyl group. , Tetrafluorophenyl group, pentafluorophenyl group, trifluoromethylphenyl group, bistrifluoromethylphenyl group, hexachloroantimonate anion.

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

Among the silicon-containing groups, a trimethylsilylmethyl group is preferable.
Examples of the oxygen-containing group include a 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 and the like.

Among the oxygen-containing groups, a methoxy group, an ethoxy group, an iso-propoxy group and a tert-butoxy group are preferable.
Examples of the sulfur-containing group include a mesyl group (methanesulphonyl group), a phenylsulfonyl group, a tosyl group (p-toluenesulfonyl group), a trifuryl group (trifluoromethanesulfonyl group), a nonafryl group (nonafluorobutanesulfonyl group), and the like. Examples thereof include a mesylate group (methanesulfonate group), a tosylate group (p-toluenesulfonate group), a trifurate group (trifluoromethanesulfonate group), and a nonafrate group (nonafluorobutanesulfonate group).

Among the sulfur-containing groups, triflate (trifluoromethanesulfonate) is preferable.
Examples of the nitrogen-containing group include an amino group, a cyano group, a methylamino group, a dimethylamino group, an ethylamino group, a diethylamino group, an allylamino group, a diallylamino group, a benzylamino group, a dibenzylamino group, a pyrrolidinyl group and a piperidinyl. Examples thereof include a group, a morpholyl group, a pyrrolyl group, a bistrifurylimide group and the like.

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

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

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

で表される四員環、あるいは

Four-membered ring represented by, or

で表される四員環
（Ｍは、前記一般式（１）中のＭを表す。）
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。

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

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

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

<< Q >>
In the general formula [1], Q is a Group 14 atom of the periodic table, for example, a carbon atom, a silicon atom, a germanium atom or a tin atom, preferably a carbon atom or a silicon atom, and more preferably a silicon atom. Is.

《R ¹ to R ¹² 》
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 and R ¹² are each independently hydrogen. It is an 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. R ¹ to R ¹² are preferably a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group having 1 to 20 carbon atoms, or a nitrogen-containing group having 1 to 20 carbon atoms. R ¹ to R ¹² may be the same or different from each other.

Examples of the hydrocarbon group having 1 to 40 carbon atoms as R ¹ to R ¹² include a hydrocarbon group 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 , Tart-pentyl group (1,1-dimethylpropyl group), sheamil group, pentan-3-yl group, 2-methylpentyl group, 3-methylpentyl group, iso-hexyl group, 1,1-dimethylbutyl group (1,1-dimethylbutyl group) 2-Methylpentan-2-yl group), 3-methylpentane-2-yl group, 4-methylpentane-2-yl group, 2,2-dimethylbutyl group, 2,3-dimethylbutyl group, 3,3 -Dimethylbutyl group, texyl group, 3-methylpentane-3-yl group, 3,3-dimethylbut-2-yl group, hexane-3-yl group, 2-methylpentane-3-yl group, 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 an yl group, a 2,3,3-trimethylbutan-2-yl group, and a 2,4,4-trimethylpentan-2-yl group. ;
Vinyl group, allyl group, propenyl group, iso-propenyl group, allenyl group, buta-3-en-1-yl group, crotyl group, buta-3-en-2-yl group, metalryl group, pig-1,3 -Dienyl group, penta-4-en-1-yl group, penta-3-en-1-yl group, penta-2-en-1-yl group, iso-pentenyl group, 2-methylbut-3-en- 1-yl group, penta-4-en-2-yl group, prenyl group, 2-methyl-but-2-en-1-yl group, penta-3-en-2-yl group, 2-methyl-buta -3-en-2-yl group, penta-1-en-3-yl group, penta-2,4-dien-1-yl group, penta-1,3-dien-1-yl group, penta-1 , 4-diene-3-yl group, iso-prenyl group (2-methyl-buta-1,3-dien-1-yl group), penta-2,4-dien-2-yl group, hexa-5- En-1-yl group, hexa-4-en-1-yl group, hexa-3-en-1-yl group, hexa-2-en-1-yl group, 4-methyl-penta-4-en- 1-yl group, 3-methyl-pent-4-en-1-yl group, 2-methyl-penta-4-en-1-yl group, hexa-5-en-2-yl group, 4-methyl- Penta-3-en-1-yl group, 3-methyl-pent-3-en-1-yl group, 2,3-dimethyl-but-2-en-1-yl group, 2-methylpent-4-ene -2-Il group, 3-ethylpenta-1-ene-3-yl group, hexa-3,5-diene-1-yl group, hexa-2,4-dien-1-yl group, 4-methylpenta-1 , 3-Dien-1-yl group, 2,3-dimethyl-buta-1,3-dien-1-yl group, hexa-1,3,5-triene-1-yl group, 2- (cyclopentadi) A linear or branched alkenyl group or unsaturated double bond-containing group having 2 to 40 carbon atoms such as an enyl) propan-2-yl group and a 2- (cyclopentadienyl) ethyl group;
Ethynyl group, propa-2-in-1-yl group, propargyl group, buta-1-in-1-yl group, bututa-2-in-1-yl group, bututa-3-in-1-yl group, Penta-1-in-1-yl group, penta-2-in-1-yl group, penta-3-in-1-yl group, penta-4-in-1-yl group, 3-methyl-buta- 1-in-1-yl group, penta-3-in-2-yl group, 2-methyl-but-3-in-1-yl group, penta-4-in-2-yl group, hexa-1- In-1-yl group, 3,3-dimethyl-buta-1-in-1-yl group, 2-methyl-penta-3-in-2-yl group, 2,2-dimethyl-but-3-in A linear or branched alkynyl group or unsaturated triple having 2 to 40 carbon atoms such as a -1-yl group, a hexa-4-in-1-yl group, and a hexa-5-in-1-yl group. Bond-containing group;
Benzyl group, 2-methylbenzyl group, 4-methylbenzyl group, 2,4,6-trimethylbenzyl group, 3,5-dimethylbenzyl group, Kuminyl group, 2,4,6-tri-iso-propylbenzyl group, 4-tert-butylbenzyl group, 3,5-di-tert-butylbenzyl group, 1-phenylethyl group, benzhydryl group, cumyl group (2-phenylpropane-2-yl group), 2- (4-methylphenyl) ) Propan-2-yl group, 2- (3,5-dimethylphenyl) propan-2-yl group, 2- (4-tert-butylphenyl) propan-2-yl group, 2- (3,5-di) -Tert-Butylphenyl) Propan-2-yl group, 3-phenylpentane-3-yl group, 4-phenylhepta-1,6-dien-4-yl group, 1,2,3-triphenylpropane-2 -Il group, 1,1-diphenylethyl group, 1,1-diphenylpropyl group, 1,1-diphenyl-but-3-en-1-yl group, 1,1,2-triphenylethyl group, trityl group (Triphenylmethyl group), tri- (4-methylphenyl) methyl group, 2-phenylethyl group, styryl group (2-phenylvinyl group), 2- (2-methylphenyl) ethyl group, 2- (4-) Methylphenyl) ethyl group, 2- (2,4,6-trimethylphenyl) ethyl group, 2- (3,5-dimethylphenyl) ethyl group, 2- (2,4,6-tri-iso-propylphenyl) Ethyl group, 2- (4-tert-butylphenyl) ethyl group, 2- (3,5-di-tert-butylphenyl) ethyl group, 2-methyl-1-phenylpropane-2-yl group, 3-phenylpropi Lu group, cinnamyl group (3-phenylallyl group), neophil group (2-methyl-2-phenylpropyl group), 3-methyl-3-phenylbutyl group, 2-methyl-4-phenylbutane-2-yl group , Cyclopentadienyldiphenylmethyl group, 2- (1-indenyl) propan-2-yl group, (1-indenyl) diphenylmethyl group, 2- (1-indenyl) ethyl group, 2- (tetrahydro-1-indacenyl) ) Propan-2-yl group, (tetrahydro-1-indacenyl) diphenylmethyl group, 2- (tetrahydro-1-indacenyl) ethyl group, 2- (1-benzoindenyl) propan-2-yl group, (1- Benzoindenyl) diphenylmethyl group, 2- (1-benzoindenyl) ethyl group, 2- (9-fluorenyl) propane -2-yl group, (9-fluorenyl) diphenylmethyl group, 2- (9-fluorenyl) ethyl group, 2- (1-azurenyl) propan-2-yl group, (1-azulenyl) diphenylmethyl group, 2- An aromatic-containing linear or branched alkyl group having 7 to 40 carbon atoms such as (1-azulenyl) ethyl group and an unsaturated double bond-containing group;
Cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclopentenyl group, cyclopentadienyl group, dimethylcyclopentadienyl group, n-butylcyclopentadienyl group, n-butyl-methylcyclopentadienyl group, tetramethylcyclo Pentazienyl group, 1-methylcyclopentyl group, 1-allylcyclopentyl group, 1-benzylcyclopentyl group, cyclohexyl group, cyclohexenyl group, cyclohexadienyl group, 1-methylcyclohexyl group, 1-allylcyclohexyl group, 1-benzyl Cyclohexyl group, cycloheptyl group, cycloheptenyl group, cycloheptatrienyl group, 1-methylcycloheptyl group, 1-allylcycloheptyl group, 1-benzylcycloheptyl group, cyclooctyl group, cyclooctenyl group, cyclooctadienyl group, Cyclooctatrienyl group, 1-methylcyclooctyl group, 1-allylcyclooctyl group, 1-benzylcyclooctyl group, 4-cyclohexyl-tert-butyl group, norbornyl group, norbornenyl group, norbornadienyl group, 2- Methylbicyclo [2.2.1] heptane-2-yl group, 7-methylbicyclo [2.2.1] heptane-7-yl group, bicyclo [2.2.2] octane-1-yl group, bicyclo [2.2.2] Octane-2-yl group, 1-adamantyl group, 2-adamantyl group, 1- (2-methyladamantyl), 1- (3-methyladamantyl), 1- (4-methyladamantyl) , 1- (2-phenyladamantyl), 1- (3-phenyladamantyl), 1- (4-phenyladamantyl), 1- (3,5-dimethyladamantyl), 1- (3,5,7-trimethyladamantyl) ), 1- (3,5,7-triphenyladamantyl), pentarenyl group, indenyl group, fluorenyl group, indasenyl group, tetrahydroindasenyl group, benzoindenyl group, azulenyl group, etc. have 3 to 40 carbon atoms. Cyclic saturated and unsaturated hydrocarbon groups;
Phenyl group, trill group, xylyl group, mesityl group, cumenyl group, juryl group, 2,6-di-iso-propylphenyl group, 2,4,6-tri-iso-propylphenyl group, 4-tert-butylphenyl Group, 3,5-di-tert-butylphenyl group, allylphenyl group, (but-3-en-1-yl) phenyl group, (but-2-en-1-yl) phenyl group, metallicylphenyl group , Plenylphenyl group, 4-adamantylphenyl group, 3,5-di-adamantylphenyl group, naphthyl group, biphenyl group, terphenyl group, binaphthyl group, acenaphthalenyl group, phenanthryl group, anthracenyl group, pyrenyl group, ferrosenyl group, etc. Examples thereof include aromatic substituents having 6 to 40 carbon atoms.

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

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

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

Among the aromatic-containing linear or branched alkyl groups and unsaturated double bond-containing groups having 7 to 40 carbon atoms, benzyl group, 2-methylbenzyl group, 4-methylbenzyl group, 2,4 , 6-trimethylbenzyl group, 3,5-dimethylbenzyl group, Kuminyl group, 2,4,6-tri-iso-propylbenzyl group, 4-tert-butylbenzyl group, 3,5-di-tert-butylbenzyl Group, Benzyl Group, Kumil Group, 1,1-Diphenylethyl Group, Trityl Group, 2-Phenylethyl Group, 2- (4-Methylphenyl) Ethyl Group, 2- (2,4,6-trimethylphenyl) Ethyl Group , 2- (3,5-dimethylphenyl) ethyl group, 2- (2,4,6-tri-iso-propylphenyl) ethyl group, 2- (4-tert-butylphenyl) ethyl group, 2- (3) , 5-Di-tert-butylphenyl) ethyl group, styryl group, 2-methyl-1-phenylpropane-2-yl group, 3-phenylpropyl group, cinnamyl group, neophil group, cyclopentadienyldiphenylmethyl group, 2- (1-Indenyl) propane-2-yl group, (1-indenyl) diphenylmethyl group, 2- (1-indenyl) ethyl group, 2- (9-fluorenyl) propan-2-yl group, (9- Fluorenyl) diphenylmethyl group, 2- (9-fluorenyl) ethyl group and the like are preferable, and benzyl group, benzhydryl group, cumyl group, 1,1-diphenylethyl group, trityl group, 2-phenylethyl group and 3-phenylpropyl group are preferable. , Synamyl groups are more preferred.

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

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

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

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

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

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

As the oxygen-containing group, an oxygen-containing group having 1 to 20 carbon atoms is preferable, and for example, 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, and the like. iso-butoxy group, tert-butoxy group, metallicyloxy group, prenyloxy group, benzyloxy group, methoxymethoxy group, methoxyethoxy group, phenoxy group, naphthoxy group, toluyloxy group, iso-propylphenoxy group, allylphenoxy group, tert -Butylphenoxy group, methoxyphenoxy group, iso-propoxyphenoxy group, allyloxyphenoxy group, biphenyloxy group, binaphthyloxy group, methoxymethyl group, allyloxymethyl group, benzyloxymethyl group, phenoxymethyl group, methoxyethyl group, Allyloxyethyl group, benzyloxyethyl group, phenoxyethyl group, methoxypropyl group, allyloxypropyl group, benzyloxypropyl group, phenoxypropyl group, methoxyvinyl group, allyloxyvinyl group, benzyloxyvinyl group, 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-propoxy Phenyl group, allyloxyphenyl group, phenoxyphenyl group, methylenedioxyphenyl group, 3,5-dimethyl-4-methoxyphenyl group, 3,5-di-tert-butyl-4-methoxyphenyl group, frill group, methyl Examples thereof include a frill group, a tetrahydrofuryl group, a pyranyl group, a tetrahydropyranyl group, a flofuryl group, a benzofuryl group and a dibenzofuryl group.

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

The nitrogen-containing group is preferably a nitrogen-containing group having 1 to 20 carbon atoms, and for example, an amino group, a dimethylamino group, a diethylamino group, an allylamino group, a diallylamino group, a didecylamino group, a benzylamino group, or a dibenzylamino group. Pyrrolidinyl group, piperidinyl group, molyphoryl group, azepinyl group, dimethylaminomethyl group, dibenzylaminomethyl group, pyrrolidinylmethyl group, dimethylaminoethyl group, benzylaminomethyl group, benzylaminoethyl group, pyrrolidinylethyl group, Dimethylaminovinyl group, benzylaminovinyl group, pyrrolidinylvinyl group, dimethylaminopropyl group, benzylaminopropyl group, pyrrolidinylpropyl group, dimethylaminoallyl group, benzylaminoallyl group, pyrrolidinylallyl group, aminophenyl Group, dimethylaminophenyl group, 3,5-dimethyl-4-dimethylaminophenyl group, 3,5-di-iso-propyl-4-dimethylaminophenyl group, durolidinyl group, tetramethyldurolidinyl group, pyrrolidinyl Phenyl group, pyrrolylphenyl group, pyridylphenyl group, quinolylphenyl group, isoquinolylphenyl group, indolinylphenyl group, indolylphenyl group, carbazolylphenyl group, di-tert-butylcarbazolylphenyl group, Pyrrolyl group, Methylpyrrolyl group, Phenylpyrrolyl group, Pyridyl group, Kinolyl group, Tetrahydroquinolyl group, iso-quinolyl group, Tetrahydro-iso-quinolyl group, Indolyl group, Indolinyl group, Carbazolyl group, Di-tert-butylcarbazoli Examples thereof include a ru group, an imidazolyl group, a dimethylimidazolidinyl group, a benzoimidazolyl group, an oxazolyl group, an oxazolidinyl group, and a benzoxazolyl group.

Among the nitrogen-containing groups, amino group, dimethylamino group, diethylamino group, allylamino group, benzylamino group, dibenzylamino group, pyrrolidinyl group, piperidinyl group, morpholyl group, dimethylaminomethyl group, benzylaminomethyl group and pyrrolidini Lumethyl group, dimethylaminoethyl group, pyrrolidinylethyl group, dimethylaminopropyl group, pyrrolidinylpropyl group, dimethylaminoallyl group, pyrrolidinylallyl group, aminophenyl group, dimethylaminophenyl group, 3,5- Dimethyl-4-dimethylaminophenyl group, 3,5-di-iso-propyl-4-dimethylaminophenyl group, durolidinyl group, tetramethylduroridinyl group, pyrrolidinylphenyl group, pyrrolylphenyl group, carbazolyl Phenyl group, di-tert-butylcarbazolylphenyl group, pyrrolyl group, pyridyl group, quinolyl group, tetrahydroquinolyl group, iso-quinolyl group, tetrahydro-iso-quinolyl group, indolyl group, indolinyl group, carbazolyl group, di -Tert-Butylcarbazolyl group, imidazolyl group, dimethylimidazolidinyl group, benzoimidazolyl group, oxazolyl group, oxazolidinyl group, benzoxazolyl group and the like are preferable, and amino group, dimethylamino group, diethylamino group and pyrrolidinyl are preferable. Group, dimethylaminophenyl group, 3,5-dimethyl-4-dimethylaminophenyl group, 3,5-di-iso-propyl-4-dimethylaminophenyl group, durolidinyl group, tetramethyldurolidinyl group, pyrrolidinyl A phenyl group, a pyrrolyl group, a pyridyl group, a carbazolyl group, and an imidazolyl group are more preferable.

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

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

Of R ⁸ and R ⁹ , only R ⁸ and only R ⁹ or both R ⁸ and R ⁹ have a saturated hydrocarbon group having 3 to 10 carbon atoms in the linear portion or a carbon number in the linear portion. Are 3 to 10 terminal unsaturated hydrocarbon groups.

Saturated hydrocarbon groups having 3 to 10 carbon atoms in the linear moiety include, for example, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, and n-octyl group. , N-nonyl group, n-decyl group, sec-butyl group, tert-pentyl group, 2-methylpentane-2-yl group , 1- (n-propyl) cyclopentyl group , 1- (n-propyl) cyclohexyl group These include n-propyl group, n-butyl group, n-pentyl group, and n-hexyl group.

Examples of the terminal unsaturated hydrocarbon group having 3 to 10 carbon atoms in the linear moiety include an allyl group, a buta-3-en-1-yl group, a methallyl group , and a penta -4-en-1-yl. Group, prenyl group, hexa-5-en-1-yl group, hepta-6-en-1-yl group, octa-7-en-1-yl group, nona-8-en-1-yl group, deca -9-en-1-yl group, 2-methylbut-3-en-2-yl group, 2-methylpenta-4-en-2-yl group , 1 -allylcyclopentyl group , 1 -allylcyclohexyl group and the like. The allyl group, the buta-3-en-1-yl group, the penta-4-en-1-yl group, and the hexa-5-en-1-yl group are preferable.

R ⁷ and R ⁸ may be bonded to each other to form a saturated ring which may have a substituent. R ⁹ and R ¹⁰ may also be bonded to each other to form a saturated ring which may have a substituent. As these formed rings, a 5- to 8-membered ring composed of a saturated hydrocarbon (excluding the hydrocarbon of the indenyl ring portion) which is fused to the indenyl ring portion and may have a substituent may be used. preferable. The ring is more preferably a 5- or 6-membered ring, although the ring is not particularly limited as long as the effect of the present invention is exhibited. Examples thereof include a denyl ring, a substituted tetrahydroindacene ring and a substituted cyclopentatetrahydronaphthalene, and a substituted benzoindenyl ring and a substituted tetrahydroindacene ring are preferable.

R ¹¹ and R ¹² may be bonded to each other to form a ring containing Q, and the ring may have a substituent. The ring formed in this case preferably forms a saturated or unsaturated ring of a 3- to 8-membered ring which may have a substituent. The ring is not particularly limited as long as the effect of the present invention is exhibited, but is preferably ^a 4- to 6-membered ring. Examples thereof include a cyclobutane (siletan) ring, a substituted silacyclopentane (sirolan) ring, a substituted silacyclohexane (silinan), and a substituted silafluorene ring, and a substituted cyclopentane ring, a substituted silacyclobutane ring, and a substituted silacyclopentane ring are preferable. ..

<< Preferred Embodiment of Transition Metal Compound [A] >>
As a preferred embodiment of the transition metal compound [A], in the general formula [1], M is a zirconium atom or a hafnium atom, and X is independently a hydrogen atom, a halogen atom, and 1 to 20 carbon atoms. Can be mentioned as a transition metal compound in which Q is a carbon atom or a silicon atom, which is a hydrocarbon group, a silicon-containing group or an oxygen-containing group.

As a more preferable embodiment, in the above general formula [1], Q is a silicon atom, and R ¹ to R ¹² are independently hydrogen atoms, hydrocarbon groups having 1 to 20 carbon atoms, and 1 to 1 carbon atoms. Examples thereof include transition metal compounds having 20 oxygen-containing groups or 1 to 20 carbon atoms, each of which may be the same or different.

In a more preferable embodiment, in the above general formula [1], R ¹ and R ⁶ are hydrogen atoms, and R ² to R ⁵ , R ¹¹ and R ¹² are independently hydrogen atoms or carbon atoms 1 to 1, respectively. 10 hydrocarbon groups, each of which may be the same or different, with one of R ⁷ and R ¹⁰ being a hydrogen atom and one of R ⁸ and R ⁹ being a hydrogen atom. Compounds can be mentioned.

In a more preferable embodiment, in the above general formula [1], R ¹ to R ⁷ and R ¹⁰ are hydrogen atoms, and R ¹¹ and R ¹² are independently hydrogen atoms or carbon atoms having 1 to 10 carbon atoms, respectively. It is a hydrogen group and may be the same or different from each other, and a transition metal compound in which either R ⁸ or R ⁹ is a hydrogen atom can be mentioned.

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

For the sake of convenience, the ligand structure of the transition metal compound [A] excluding the MXn (metal moiety) is set to 2-indenyl ring moiety, cyclopentadienyl ring moiety, 2-indenyl ring moiety R ¹ , R ⁶ substituent and cyclopentadi. Enyl ring moiety R ⁷ , R ⁹ , R ¹⁰ substituent, 2-indenyl ring moiety R ² and R ⁵ substituent, 2-indenyl ring moiety R ³ and R ⁴ substituent, cyclopentadienyl ring moiety R ⁸ substituent , The structure of the cross-linked part is divided into 7 parts. The abbreviation for 2-indenyl ring moiety is α, the abbreviation for cyclopentadienyl ring moiety is β, 2-indenyl ring moiety R ¹ , R ⁶ substituent and cyclopentadienyl ring moiety R ⁷ , R ⁹ , R ¹⁰ substituents. The abbreviation for γ is γ, the abbreviation for 2-indenyl ring moiety R ² and R ⁵ substituent is δ, the abbreviation for 2-indenyl ring moiety R ³ and R ⁴ substituent substituent is ε, cyclopentadienyl ring moiety R ⁸ substitution. The abbreviation of the group is ζ, the abbreviation of the structure of the crosslinked portion is η, and the abbreviation of each substituent is shown in [Table 1] to [Table 7].

なお、前記［表１］および［表２］中の波線は架橋部分との結合部位を示す。

The wavy lines in [Table 1] and [Table 2] indicate the binding site with the cross-linked portion.

前記［表３］中のＲ¹、Ｒ⁶、Ｒ⁷、Ｒ⁹およびＲ¹⁰置換基は、その組み合わせにおいて互いに同一でも異なっていてもよい。

The R ¹ , R ⁶ , R ⁷ , R ⁹ and R ¹⁰ substituents in [Table 3] may be the same or different from each other in the combination.

前記［表４］中のＲ²およびＲ⁵置換基は、その組み合わせにおいて互いに同一でも異なっていてもよい。

The R ² and R ⁵ substituents in the above [Table 4] may be the same or different from each other in the combination.

前記［表５］中のＲ³およびＲ⁴置換基は、その組み合わせにおいて互いに同一でも異なっていてもよい。

The R ³ and R ⁴ substituents in the above [Table 5] may be the same or different from each other in the combination.

Specific examples of the metal portion MXn include TiF ₂ , TiCl ₂ , TiBr ₂ , TiI ₂ , Ti (Me) ₂ , Ti (Bn) ₂ , Ti (Allly) 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 ( _CH2 -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 (Allly) ₂ , Zr ( _CH2 -tBu) ₂ , Zr (1,3-butadienyl), Zr (1,3-pentadienyl), Zr (2,4-hexadienyl), Zr (1,4-diphenyl-1,3-pentadienyl), Zr ( _CH2 -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 (Allly) ) ₂ , Hf ( _CH2 -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 2-indenyl ring moiety is α-1 in [Table 1], and the cyclopentadienyl ring moiety is β-1, 2-indenyl ring moiety R ¹ , R ⁶ in [Table 2]. Substituents and cyclopentadienyl ring moieties R ⁷ and R ⁹ substituents are all in [Table 3] γ-1, 2-indenyl ring moieties R ² and R ⁵ substituents are both in [Table 4]. δ-1, 2-indenyl ring moiety R ³ and R ⁴ substituents are all ε-1 in [Table 5], cyclopentadienyl ring moiety R ⁸ substituents are ζ-5 in [Table 6], When the cyclopentadienyl ring moiety R ⁹ substituent is composed of a combination of γ-17 in [Table 3] and the crosslinked moiety is η-20 in [Table 7], and the MXn of the metal moiety is ZrCl ₂ . The compound represented by the following formula [2] is exemplified.

The 2-indenyl ring moiety is α-2 in [Table 1], and the cyclopentadienyl ring moiety is β-1, 2-indenyl ring moiety ^R1 , R ⁶ substituent and cyclopenta in [Table 2]. The dienyl ring moiety R ⁷ , R ⁹ and R ¹⁰ substituents are all γ-1 in [Table 3], and the cyclopentadienyl ring moiety R ⁸ substituent is ζ-18 in [Table 6], the crosslinked moiety. Is composed of the combination of η-4 in [Table 7], and when the MXn of the metal portion is Zr (NMe ₂ ) ₂ , the compound represented by the following formula [3] is exemplified.

The 2-indenyl ring moiety is α-1 in [Table 1], and the cyclopentadienyl ring moiety is β-1, 2-indenyl ring moiety ^R1 , R ⁶ substituent and cyclopenta in [Table 2]. The dienyl ring moieties R ⁷ and R ⁹ substituents are all γ-1, 2 in [Table 3], and the 2-indenyl ring moieties R ² and R ⁵ substituents are both δ-2, 2 in [Table 4]. -The indenyl ring moiety R ³ and R ⁴ substituents are both ε-1 in [Table 5], and the cyclopentadienyl ring moiety R ⁸ substituents are ζ-2, cyclopentadienyl ring in [Table 6]. When the partial R ⁹ substituent is composed of a combination of γ-2 in [Table 3] and the crosslinked moiety is η-31 in [Table 7], and the MXn of the metal moiety is Hf (Me) ₂ , the following formula is used. The compound represented by [4] is exemplified.

The 2-indenyl ring moiety is α-1 in [Table 1], the cyclopentadienyl ring moiety is β-2 in [Table 2], the 2-indenyl ring moiety ^R1 , R ⁶ substituent and cyclopenta. The γ-1,2-indenyl ring moiety R ² and R ⁵ substituents in [Table ³ ] are all δ-1,2-indenyl rings in [Table 4]. The partial R ³ and R ⁴ substituents are both ε-1 in [Table 5], the cyclopentadienyl ring moiety R ⁸ substituent is ζ-1 in [Table 6], and the crosslinked moiety is in [Table 7]. When the MXn of the metal portion is Ti (1,3-pentadienyl), the compound represented by the following formula [5] is exemplified.

In the transition metal compound [A] of the present invention, the surface of the cyclopentadienyl ring portion that is bonded to the central metal across the crosslinked portion exists in two directions (front surface and back surface). Therefore, when there is no plane of symmetry in the 2-indenyl ring moiety and the cyclopentadienyl ring moiety, there are two types of structural isomers represented by the following general formulas [6a] or [6b] as an example.

同様に、架橋部分の置換基Ｒ¹¹とＲ¹²が同一でない場合にも、一例として下記一般式［７ａ］あるいは［７ｂ］で示される２種類の構造異性体が存在する。

Similarly, even when the substituents R ¹¹ and R ¹² of the crosslinked moiety are not the same, there are two types of structural isomers represented by the following general formulas [7a] or [7b] as an example.

Purification, fractionation, 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 known production methods, in addition to those mentioned as the production method of the transition metal compound [A], JP-A-10-109996, "Organometrics 1999, 18, 5347.", "Organometrics 2012, 31, 4340." , Japanese Patent Publication No. 2011-502192, and the like.

In the present invention, the transition metal compound [A] may be used alone, or two or more of the transition metal compounds [A] having different chemical structures may be used in combination. Further, one structural isomer having the same chemical structure may be used alone, a mixture of structural isomers having the same chemical structure may be used, or a combination thereof 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 examples of typical synthetic routes are shown below, but the production method is not particularly limited.

The substituted cyclopentadiene compound as a starting material can be produced by a known method, and the production method is not particularly limited. Known production methods include, for example, "Tetrahedron Lett. 1989, 30, 3513.", "J. Org. Chem. 1990, 55, 3395.", "Inorg. Chem. 991, 30, 853.", "Organochemicals 1997". , 16,2503. ”,“ J. Organicomet. Chem. 1999, 577, 211. ”,“ J. Organicomet. Chem. 1999, 590, 169. ”, Japanese Patent Publication No. 2002-535339,“ J. Organicomet. Chem. 2003,677,133. ”,“ J. Organicomet. Chem. 2005, 690, 952. ”,“ Org. Let. 2008, 10, 2545. ”, And the like.

The substituted indene compound as a starting material can be produced by a known method, and the production method is not particularly limited. As known production methods, for example, "Organometrics 1994, 13, 954.", "Eur. J. Org. Chem. 2005, 1058.", "Organometrics 2006, 25, 1217.", Japanese Patent Application Laid-Open No. 2006-509059. "Bioorg. Med. Chem. 2008,16,7399.", WO2009 / 080216A, "Organometrics 2011,30,5744." Chem. Eur. J. 2012, 18, 4174. ”, JP-A-2012-0123007, JP-A-2012-121882, JP-A-2014-196319, JP-A-2014-513735, JP-A-2015- Examples thereof include Japanese Patent Application Laid-Open No. 063495 and Japanese Patent Application Laid-Open No. 2016-501952.

Among the substituted indene compounds, the 2-position-unsubstituted compound can be brominated at the 2-position by a known method as shown in the following reaction formula [1], and the production method is not particularly limited. ..

なお、前記反応式［１］中、ＮＢＳはＮ－ブロモこはく酸イミドを示し、ＰＴＳＡはｐ－トルエンスルホン酸およびその一水和物を示している。インデン化合物には、５員環部分二重結合位置異性体が存在するが、それら異性体の混合物を用いてもよい。公知の製造方法として例えば、前記で示した特開２０１２－１２１８８２号公報、特開２０１５－０６３４９５号公報の他に、特開２０１４－１１１５６８号公報などが挙げられる。

In the reaction formula [1], NBS indicates N-bromosuccinic acid imide, and PTSA indicates p-toluenesulfonic acid and its monohydrate. The indene compound has a 5-membered ring partial double bond position isomer, and a mixture of these isomers may be used. As known production methods, for example, in addition to JP-A-2012-121882 and JP-A-2015-063495 shown above, JP-A-2014-11168 and the like can be mentioned.

The transition metal compound [A] and the precursor compound (ligand) can be produced by a known method using various substituted cyclopentadienyl compounds and various substituted indene compounds produced by the above-mentioned method or the like. When Q is a silicon atom, a germanium atom or a tin atom, it can be produced by, for example, a method as shown by the following reaction formula [2], and the production method is not particularly limited.

In the reaction formula [2], the organomagnesium reagent prepared from the 2-bromination-substituted inden compound and the organolithium reagent prepared from the substituted cyclopentadienyl compound in the synthesis of the precursor compound (ligand) are It is preferable to react with the chloride containing Q stepwise, and the order thereof may be arbitrary. After the reaction with the organometallic reagent in the first step, the by-product inorganic compound may be removed by inactive atmosphere, and the reaction product may be isolated by an operation such as distillation, crystallization or washing before use. May be good. During the reaction with the organometallic reagent in the second step, DMI (1,3-dimethyl-2-imidazolidinone), DMPU (N, N'-dimethylpropylene urea), HMPA (hexamethylphosphoric acid triamide), etc. are used. , 0.1 to 5.0 equivalents are preferably added to the organometallic reagent, more preferably DMI, and 1.0 equivalent. The substituted inden compound, the substituted cyclopentadienyl compound and the precursor compound (ligand) have 5-membered ring partial double bond position isomers, and a mixture of these isomers may be used.

As known methods for producing the transition metal compound (A) and the precursor compound (ligand), for example, in addition to those shown above, "Macromopolymers 1995, 28, 3771.", JP-A-11-315089, JP. JP-A-2001-302687, JP-A-2001-220404, "Polymer Papers 2002,59,243.", JP-A-2003-522194, "Macromolecules 2004,37,2342.", JP-A-2007. Examples thereof include Japanese Patent Application Laid-Open No. 320935 and Japanese Patent Application Laid-Open No. 2011-126913.

When Q is a carbon atom, it can be produced by the following method, and the production method is not particularly limited.

In the above [Formula 3], base is a basic substance capable of producing a cyclopentadienyl anion, and is an organometallic compound such as sodium hydride, n-butyllithium, a Grignard reagent, sodium hydroxide, or water. Examples thereof include inorganic bases such as potassium oxide and organic bases such as diethylamine and pyrrolidine, but the present invention is not particularly limited. A fulvene compound can be synthesized from a substituted cyclopentadienyl compound and a carbonyl compound in the presence of a basic substance by a known method, and a precursor compound (precursor compound) can be synthesized by a reaction with an organic magnesium reagent prepared from a 2-bromination substituted inden compound. It is possible to produce a ligand). The substituted inden compound, the substituted cyclopentadienyl compound and the precursor compound (ligand) have 5-membered ring partial double bond position isomers, and a mixture of these isomers may be used.

As known methods for producing the transition metal compound [A] and the precursor compound (ligand), for example, in addition to those shown above, "Macromometallics 2003, 36, 9325.", "Organometallics 2004, 23, 5332." , "Eur. J. Inorg. Chem. 2005, 1003.", "Eur. J. Inorg. Chem. 2009, 1759.", And the like.

[Catalyst for olefin polymerization]
The catalyst for olefin polymerization of the present invention contains the transition metal compound [A], and further
(B-1) Organometallic compound (B-2) Selected from the group consisting of an organoaluminum oxy compound (c-2) and (B-3) a compound that reacts with a transition metal compound [A] to form an ion pair. It is preferable to contain at least one compound [B].

Further, the catalyst for olefin polymerization of the present invention can contain a solid carrier [S], if necessary.
Examples of the organometallic compound (B-1) include organometallic compounds represented by the following general formulas (B-1a), (B-1b) or (B-1c).
R^a _mAl (OR^{b b})_nH_pX_{q q} … (B-1a)
[In the general formula (B-1a), R^aAnd R^{b b}Indicates a hydrocarbon group having 1 to 15 carbon atoms, and each other
It may be the same or different, where X is a halogen atom, m is 0 <m ≦ 3, n is 0 ≦ n <3, p is 0 ≦ p <3, and q is 0 ≦ q <3. And m + n + p + q = 3. ]
M^aAlR^a _Four … (B-1b)
[In the general formula (B-1b), M^aIndicates Li, Na or K, R^aIndicates a hydrocarbon group having 1 to 15 carbon atoms. ]
R^a _rM^{b b}R^{b b} _s X_t … (B-1c)
[In the general formula (B-1c), R^aAnd R^{b b}Represents a hydrocarbon group having 1 to 15 carbon atoms and may be the same or different from each other.^{b b}Is selected from Mg, Zn and Cd, where X represents a halogen atom, r is 0 <r ≦ 2, s is 0 ≦ s ≦ 1, t is 0 ≦ t ≦ 1, and r + s + t = 2. .. ]

As the organometallic compound (B-1), the compounds disclosed in JP-A No. 11-315109 and EP0874005A can be used without limitation.
The organic metal compound (B-1) is preferably represented by the general formula (B-1a), and specifically, trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, trihexylaluminum, and tri. Trialkylaluminum such as octylaluminum, tri2-ethylhexylaluminum, dimethylaluminum chloride, diethylaluminum chloride, diisopropylaluminum chloride, diisobutylaluminum chloride, dialkylaluminum halide such as dimethylaluminum bromide, methylaluminum sesquichloride, ethylaluminum sesquichloride, isopropyl Alkylaluminum sesquihalides such as aluminum sesquichloride, butylaluminum sesquichloride, ethylaluminum sesquibramide, alkylaluminum dichlorides such as methylaluminum dichloride, ethylaluminum dichloride, isopropylaluminum dichloride, ethylaluminum dibromid, dimethylaluminum hydride, diethylaluminum hydride. , Dihydrophenyl aluminum hydride, diisopropyl aluminum hydride, di-n-butyl aluminum hydride, diisobutyl aluminum hydride, diisohexyl aluminum hydride, diphenyl aluminum hydride, dicyclohexyl aluminum hydride, di-sec-heptyl aluminum hydride, di-sec-nonyl aluminum Examples thereof include alkylaluminum hydrides such as hydrides, dimethylaluminum ethoxides, diethylaluminum ethoxides, diisopropylaluminum methoxides, diisobutylaluminum ethoxides and the like.

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

Examples of the compound (B-3) include Japanese Patent Laid-Open No. 1-501950, Japanese Patent Application Laid-Open No. 1-502036, Japanese Patent Application Laid-Open No. 3-179005, Japanese Patent Application Laid-Open No. 3-179006, JP-A-3-207703, and Japanese Patent Publication No. 3-207703. Lewis acids, ionic compounds, borane compounds and carborane compounds described in Kaihei 3-207704, US Pat. No. 5,321,106 and the like, as well as heteropoly compounds and isopoly compounds can be used without limitation.

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

The solid carrier [S] is an inorganic compound or an organic compound, and is a solid in the form of granules or fine particles.
Examples of the inorganic compound used as the solid carrier [S] include porous oxides, solid aluminoxane compounds, inorganic chlorides, clays, clay minerals and ion-exchange layered compounds.

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

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

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

Examples of the solid aluminoxane compound include aluminoxane having a structure represented by the following general formula (S-a), aluminoxane having a structure represented by the following general formula (Sb), and the following general formula (S-c). Examples thereof include aluminoxane having a repeating unit represented by a repeating unit and a repeating unit represented by the following general formula (Sd) as a structure.

In the above formulas (S-a) to (S-d), R ^e is independently a hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms, and specifically, a methyl group and 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, trill 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. Further, a part of R ^e may be substituted with a halogen atom such as chlorine or bromine, and the halogen content may be 40% by weight or less based on R ^e . In the above formulas (Sc) and (Sd), a straight line in which one is not connected to an atom indicates a bond with another atom (not shown).

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

Unlike the conventionally known carrier for olefin polymerization catalyst, the solid aluminoxane compound does not contain an inorganic solid component such as silica or alumina and an organic polymer component such as polyethylene or polystyrene, and is a solid containing an alkylaluminum compound as a main component. It is a compound. "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] and the aluminoxane component are brought into contact with each other to prepare a catalyst for olefin polymerization (eg, a catalyst for ethylene polymerization), and the prepared catalyst for olefin polymerization. Is to maintain a substantially solid state of the aluminoxane component when polymerizing an olefin (eg, ethylene) using (eg, suspension polymerization).

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, even if a part of the aluminoxane component is eluted in the polymerization environment, it does not deviate from the gist of the present invention. 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 0.05 to 0.6, and more preferably 0.1 to 0.5.

The dissolution ratio of the solid aluminoxane compound to 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%. ..

For the dissolution ratio, 2 g of the solid aluminoxane compound carrier was added to 50 ml of n-hexane maintained at 25 ° C., and the mixture was stirred for 2 hours, and then the solution portion was separated using a G-4 glass filter. It is 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 without limitation, and for example, the solid polyaluminoxane composition described in International Publication No. 2014/123212 can also be used. Known manufacturing methods include, for example, Japanese Patent Application Laid-Open No. 7-42301, Japanese Patent Application Laid-Open No. 6-220126, Japanese Patent Application Laid-Open No. 6-220128, Japanese Patent Application Laid-Open No. 11-140113, Japanese Patent Application Laid-Open No. 11-310607, and Japanese Patent Application Laid-Open No. Examples thereof include the production methods described in Kai 2000-38410, JP-A-2000-95810, International Publication No. 2010/55652, and the like.

The average particle size of the solid aluminoxane compound is generally in the range of 0.01 to 50,000 μm, preferably 0.1 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 particles. First, the particle size d of each particle is obtained by measuring the length of the particle image sandwiched between two parallel lines in the horizontal direction and the vertical direction by the following formula.
Particle size d = ((horizontal length) ² + (vertical length) ² ) ^0.5

Next, the weight average particle size of the solid aluminoxane compound is obtained by the following formula using the particle size d and the number of particles n obtained above.
Average particle size = Σnd ⁴ / Σnd ³
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.

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

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

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

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

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

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

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

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

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

<Usage and order of addition of each component>
The catalyst for olefin polymerization of the present invention is the transition metal compound [A] (hereinafter, also referred to as component (A)), the compound [B] (hereinafter, also referred to as component (B)), and the solid carrier [S]. When (hereinafter, also referred to as a component (S)) is contained, the ethylene polymerization catalyst is prepared by mixing the component (A), the component (S), and optionally the component (B) in an inert hydrocarbon and bringing them into contact with each other. , Can be prepared.

As a method of contacting each component, paying attention to the order of contact, for example,
(I) Method of contacting component (A) with component (S) (ii) Method of contacting component (B) with component (S) and then contacting component (A) (iii) Component with component (A) A method of contacting (B) and then contacting the component (S) (iv) A method of contacting the component (S) with the component (B) and then contacting the mixture of the component (A) and the component (B).
(V) A method of contacting the component (B) with the component (S), further contacting the component (B), and then contacting the mixture of the component (A) and the component (B) can be mentioned. 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) and (iii) 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 preferable. , Alkyldiethanolamine, polyoxyalkylenealkylamine, glycerin fatty acid ester, N-acylamino acid are more preferable. These may be used alone or in combination of two or more.

Examples of the solvent used for preparing the ethylene polymerization catalyst according to the present invention include inert hydrocarbon solvents, 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, chlorbenzene, and dichloromethane, or mixtures thereof. Can be mentioned.

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 abruptly performed, the component (S) is disintegrated 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 reaction is carried out at a rate at which the initial contact temperature can be maintained. Is preferable. The same applies to the case where the component (B) and the component (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 the total transition metal atom (M) in the component (B-1) is usually 0.01 to 100, It is used in an amount of 000, preferably 0.05 to 50,000.

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

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

The catalyst for olefin polymerization 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 catalyst for olefin polymerization to form a prepolymerized solid catalyst component.

The prepolymerized solid catalyst component can be prepared by prepolymerizing the olefin in the presence of the catalyst for olefin polymerization according to the present invention, usually in an inert hydrocarbon solvent, and is a batch type, a semi-continuous type, or a continuous type. It can be carried out by any of the above methods, and can also be carried out under reduced pressure, normal pressure or pressure. 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 may be separated from the suspension, then suspended in the inert hydrocarbon again, and the olefin may be introduced into the obtained suspension. Further, the olefin may be introduced after drying.

The prepolymerization temperature is −20 to 80 ° C., preferably 0 to 60 ° C., and the prepolymerization time is 0.5 to 100 hours, preferably about 1 to 50 hours.
As the form of the solid catalyst component used for the prepolymerization, those already described can be used without limitation. Further, 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 a 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-mentioned component (G) may coexist for the purpose of suppressing fouling or improving the 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 and the component (G) are brought into contact with each other, the component (G) is 0.1 to 20 parts by weight, preferably 0.3 to 10 parts by weight, based on 100 parts by weight of the olefin polymerization catalyst. More preferably, it is used in an amount of 0.4 to 5 parts by weight.
The mixed contact between the catalyst for olefin polymerization 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 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 the hydrocarbon as a dispersion medium from the obtained suspension of the prepolymerized catalyst by filtration or the like.

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 although there is no particular lower limit, it is practically 0.001% by weight. The drying time is usually 1 to 48 hours depending 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, it is not necessary to accompany the solvent used for suspension in the gas phase polymerization system, so that stable polymerization can be performed.

[Method for producing olefin polymer]
The method for producing an olefin polymer of the present invention is characterized by comprising a step of polymerizing an olefin in the presence of the catalyst for olefin polymerization. The step of polymerizing the olefin is preferably a step of homopolymerizing ethylene or copolymerizing ethylene with an olefin having 3 or more and 20 or less carbon atoms.

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

When polymerizing an olefin 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 ⁻ per liter of reaction volume. It is used in an amount of ⁸ to 1 × 10 ⁻² mol. Further, the component (B) is preferably used, and the compound represented by the general formula (B-1a) or the component (B-2) is more preferably used.

When polymerizing an olefin, the lower limit of the polymerization temperature is 0 ° C., preferably 40 ° C., particularly preferably 60 ° C. The higher the temperature, the more advantageous in terms of heat removal etc. in production on an industrial scale. The upper limit is usually 200 ° C., preferably 170 ° C., and the polymerization pressure is usually normal pressure to 100 kg / cm ² , preferably normal pressure to 50 kg / cm ² .

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

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

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

According to the method for producing an olefin polymer according to the present invention, an olefin polymer (macromonomer) having a high ratio of having a vinyl group at the terminal and a relatively low molecular weight is produced as compared with the case of using a known metallocene compound. can do.

[Olefin polymer]
The olefin polymer (macromonomer) produced by the method for producing an olefin polymer according to the present invention preferably simultaneously satisfies the following requirements (1) to (3).
(1) Mn is 5000 to 15000.
(2) The relationship of α × Mn ≧ 2800 is satisfied.
(3) The relationship of Mw / Mn ≤ 3.5 is satisfied.

α indicates the number of vinyl terminals per 1000 main chain methylene carbons of the olefin polymer, Mn indicates the number average molecular weight measured by GPC, and Mw indicates the weight average molecular weight measured by GPC.
The olefin polymer obtained by the method for producing an olefin polymer according to the present invention has an unsaturated bond site such as a vinyl group at the end of the polymer.

The number average molecular weight (Mn) of the olefin polymer is preferably 5,000 to 15,000, more preferably 5,000 to 12,500, and even more preferably 5,000 to 10,000.

It is well known to those skilled in the art that the number of vinyl terminals of an olefin polymer can be determined by analysis such as ¹ H-NMR, ¹³ C-NMR or FT-IR, and in the present invention, ¹ H-NMR is used. It was analyzed.

The terminal vinyl ratio is
Terminal vinyl ratio (%) = α / 14000 x Mn x 100
(However, α indicates the number of vinyl terminals per 1000 main chain methylene carbons of the polymer, Mn indicates the number average molecular weight, and Mw indicates the weight average molecular weight).
When the terminal vinyl ratio is 20%, α × Mn = 2800. When a macromonomer having a terminal vinyl ratio of less than 20% is used as a macromonomer for long-chain branching, most of them do not contribute to the polymerization and remain unreacted. Therefore, a polymer having a small number of long-chain branches is produced, which does not satisfy the moldability. The olefin polymer obtained in the present invention preferably has α × Mn of 2800 or more, more preferably 4000 or more, and further preferably 5000 or more.

The ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is preferably 3.5 or less, and more preferably 3.0 or less.
Since the olefin polymer satisfying this property has a high terminal unsaturated bond rate and a molecular weight generally smaller than that of known products, the uptake rate during copolymerization is increased, and the melt fluidity and molding processability are excellent.

Furthermore, since the olefin polymer obtained by the production method of the present invention has a high vinyl group number at the terminal, graft modification and the like are easy. That is, the olefin polymer obtained by the method of the present invention is subjected to an oxidation reaction, a graft reaction, an ensynthesis reaction and the like to carry out a functionalized olefin polymer and an olefin polymer polar resin composite material (for example, antistatic). It can also be applied to agents, cosmetic additives, mold release agents for toners, pigment dispersants, lubricants for vinyl chloride resins, paints, adhesives, etc.).

Hereinafter, the present invention will be described in more detail based on Examples, but the present invention is not limited to these Examples.
[Measurement of various physical properties]
The method for measuring the physical properties of the olefin polymer is shown below.

<Melt flow rate (MFR)>
The melt flow rate was measured under the conditions of 190 ° C. and a 2.16 kg load (kgf).
<Density (D)>
The strands obtained during the MFR measurement were heat-treated at 100 ° C. for 30 minutes, left at room temperature for 1 hour, and then measured by the density gradient tube method.

<Number average molecular weight (Mn), weight average molecular weight (Mw), molecular weight distribution (Mw / Mn)>
The molecular weight and the molecular weight distribution were measured as follows using a GPC-viscosity detector (GPC-VISCO) PL-GPC220 manufactured by Agilent.

Two Agilent PLgel Olexis are used for the analysis column, a differential refractometer and a 3-capillary viscometer are used for the detector, the column temperature is 145 ° C., o-dichlorobenzene is used as the mobile phase, and the flow velocity is 1.0 ml. The sample concentration was 0.1% by weight. As the standard polystyrene, one manufactured by Tosoh Co., Ltd. was used. In the molecular weight calculation, the measured viscosity was calculated from the viscometer and the refraction meter, 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.

<Quantitative analysis of terminal structure>
The number of vinyl terminals (α) per 1000 main chain methylene carbons of the olefin polymer was determined using ¹ H-NMR (JEOL ECA-500).

<Synthesis of transition metal compounds>
[Synthesis Example 1] Synthesis of dimethylsilylene (2-indenyl) (3-n-butylcyclopentadienyl) zirconium dichloride (hereinafter referred to as compound (A)) [Synthesis Example 1-1]
2.02 g (83.1 mmol) of magnesium pieces were charged into a 200 mL reactor that had been sufficiently dried and substituted with argon, and the mixture was vigorously stirred for 30 minutes while heating under reduced pressure. After cooling to room temperature, a piece of iodine and 25 mL of tetrahydrofuran were charged and stirred. A 20 mL diluted solution of 2-bromoinden 3.92 g (20.1 mmol) in tetrahydrofuran was slowly added, and the mixture was heated under reflux in an oil bath at 80 ° C. for 1 hour. This reaction solution was slowly added to 12.0 mL (100 mmol) of dimethylsilyldichloride in 10 mL of n-hexane under cooling at −78 ° C., and stirring was continued for 18 hours while returning to room temperature. After distilling off the solvent of the reaction solution and unreacted dimethylsilyldichloride, 20 mL of tetrahydrofuran and 1.90 mL (20.2 mmol) of 1,3-dimethyl-2-imidazolidinone were added to the residue. 9.79 g (tetrahydrofuran solution, 25 wt%, 20.0 mmol) of n-butylcyclopentadiene solution and 20 mL of tetrahydrofuran were placed in a 100 mL reactor that had been sufficiently dried and substituted with argon, and 12.5 mL of n-butyllithium solution (hexane solution) was charged. , 1.60M, 20.0 mmol) was added, and the mixture was stirred at room temperature for 2 hours. This solution was added dropwise to the reaction residue diluted solution cooled to −78 ° C., and stirring was continued for 17 hours while slowly returning to room temperature. A saturated aqueous solution of ammonium chloride was added, the soluble component was extracted with n-hexane, the obtained fraction was washed with saturated brine, and dried over anhydrous magnesium sulfate. After filtering magnesium sulfate, the filtrate is distilled off and the obtained residue is purified by silica gel column chromatography. The target product represented by the following formula (AL) (hereinafter referred to as compound (AL)). Was obtained as an isomer mixture of 4.65 g (yield 79%).
^{1 1} H NMR (270 MHz, CDCl ₃ ) δ 7.52-7.35 (2H, m, Ar-H), 7.32-7.08 (3H, m, Ar-H & C = CH-C), 7. 02-5.70 (3H, m, C = CH-C), 3.60-2.87 (3H, m, Ar-CH ₂ -C & Si-CH), 2.39 (2H, t, J = 7) .7Hz, -CH ₂ -C _{3H 7} ), 1.59-1.41 (2H, m, -CH _2- ), 1.41-1.20 (2H, m, -CH _2- ), 0 .87 (3H, t, J = 7.2Hz, -C _{3H 6} -CH ₃ ), 0.50-0.02 (6H, m, Si-CH ₃ ) ppm

[Synthesis Example 1-2]
In a 100 mL reactor sufficiently dried and substituted with argon, 0.30 g (1.01 mmol) of the compound (AL) obtained in [Synthesis Example 1-1], 10 mL of toluene and 0.2 mL of tetrahydrofuran were charged and stirred. .. After adding 1.25 mL of an n-butyllithium solution (hexane solution, 1.60 M, 2.00 mmol) to this solution at room temperature, stirring was continued for 3 hours in an oil bath at 40 ° C. After distilling off the solvent of the reaction solution, 20 mL of diethyl ether was added to the obtained solid. The solution was cooled to 0 ° C., 0.23 g (1.00 mmol) of zirconium tetrachloride was added, and stirring was continued at room temperature for 17 hours. After distilling off the solvent of the reaction solution, dichloromethane was added to the obtained solid to prepare a suspension, and the insoluble material was removed by a membrane syringe filter. After decompressing and concentrating the obtained solution, the suspension was prepared by adding n-hexane, the insoluble matter was filtered off with a glass filter, and the residue was dried under reduced pressure to be represented by the following formula (A). 0.22 g (yield 49%) of the yellow powdery compound dimethylsilylene (2-indenyl) (3-n-butylcyclopentadienyl) zirconium dichloride (hereinafter referred to as compound (A)) was obtained.
^{1 1} H NMR (270 MHz, CDCl ₃ ) δ 7.70-7.55 (2H, m, Ar-H), 7.38-7.26 (2H, m, Ar-H), 6.58 (1H, Ar-H) t, J = 2.5Hz, Cp-H), 6.15 (1H, dd, J = 2.5and0.9Hz, Ind-H), 6.07 (1H, dd, J = 2.5and0.9Hz, Ind-H), 5.98 (1H, t, J = 2.8Hz, Cp-H), 5.66 (1H, t, J = 2.4Hz, Cp-H), 2.62 (2H, t) , J = 7.7Hz, Cp-CH _2- ), 1.58-1.40 (2H, m, CH ₂ -CH _2- ), 1.40-1.20 (2H, m, CH ₂ -CH) _2- ), 0.87 (3H, t, J = 7.3Hz, CH ₂ -CH ₃ ), 0.80 (3H, s, Si-CH ₃ ), 0.77 (3H, s, Si-CH) ₃ ) ppm
FD-Mass Spectrometry (M ⁺ ): 454

[Synthesis Example 2] Dimethylsilylene (cyclopentadienyl) (3-n-butylcyclopentadienyl) zirconium dichloride (hereinafter referred to as compound (a-1)) is a method described in JP-A-2009-143901. Synthesized by.

[Synthesis Example 3] Dimethylsilylenebis (cyclopentadienyl) zirconium dichloride (hereinafter referred to as compound (a-2)) was purchased from Wako Pure Chemical Industries, Ltd.

[Example 1]
<Preparation of solid catalyst component (X-1)>
Using a reactor with a stirrer with an internal volume of 270 L, as a solid carrier [S] under a nitrogen atmosphere, silica gel (manufactured by Fuji Silicia Chemical Co., Ltd., cumulative 50% particle size of volume distribution by laser photodiffraction scattering method: 70 μm, specific surface area) Surface area: 340 m ² / g, pore volume: 1.3 cm ³ / g, dried at 250 ° C. for 10 hours, hereinafter referred to as solid carrier [S-1]) 10 kg was suspended in 77 L of toluene. It was cooled to 0-5 ° C. 19.4 liters of a toluene solution of methylaluminoxane (3.5 mol / L in terms of Al atom) as a component (B) was added dropwise to this suspension over 30 minutes. At this time, the temperature inside the system was kept at 0 to 5 ° C. Then, these were contacted at 0 to 5 ° C. for 30 minutes, then the temperature in the system was raised to 95 ° C. over 1.5 hours, and then contacted at 95 ° C. for 4 hours. Then, the temperature was lowered to room temperature, the supernatant was removed by decantation, and the residue was washed twice with toluene to prepare a toluene slurry having a total volume of 115 liters. When a part of the obtained slurry was collected and analyzed, the solid content concentration was 122.6 g / L and the Al concentration was 0.612 mol / L.

Next, 30 mL of toluene and 1.63 mL (solid content weight 0.2 g) of the slurry obtained above were charged into a reactor with a stirrer having an internal volume of 200 mL sufficiently substituted with nitrogen under a nitrogen atmosphere. Next, 5.0 μmol of a toluene solution of compound (A) was added as Zr, and these were contacted at an in-system temperature of 20 to 25 ° C. for 1 hour, the supernatant was removed by decantation, and then twice using hexane. Washed. As a result, a slurry of the solid catalyst component (X-1) having a total volume of 40 mL was prepared.

<Manufacturing of olefin polymer>
After adding 500 ml of heptane to a SUS autoclave having an internal volume of 1 liter sufficiently substituted with nitrogen under a nitrogen atmosphere, ethylene was circulated and the inside of the reactor was saturated with ethylene. Next, 10 mL of 1-hexene, 0.375 mmol of triisobutylaluminum, and 10.0 mg of the solid catalyst component (X-1) in the form of a slurry were charged as a solid component, and then the mixture was charged with ethylene at 80 ° C. and 0. The temperature was raised to 0.8 MPaG, the pressure was increased, and the polymerization reaction was carried out for 90 minutes. The obtained polymer was filtered and then vacuum dried at 80 ° C. for 10 hours to obtain 163.9 g of an olefin polymer. The catalytic activity was 16400 g / g-solid catalytic component.
Table 8 shows the results of measuring the physical properties of the obtained olefin polymer.

[Comparative Example 1]
<Preparation of solid catalyst component (X-2)>
A slurry of the solid catalyst component (X-2) was prepared by the same method as in Example 1 except that the compound (a-1) was used instead of the compound (A).

<Manufacturing of olefin polymer>
After adding 500 ml of heptane to a SUS autoclave having an internal volume of 1 liter sufficiently substituted with nitrogen under a nitrogen atmosphere, ethylene was circulated and the inside of the reactor was saturated with ethylene. Next, 10 mL of 1-hexene, 0.375 mmol of triisobutylaluminum, and 10.0 mg of the solid catalyst component (X-2) in the form of a slurry were charged as a solid component, and then the mixture was charged with ethylene at 80 ° C. and 0. The temperature was raised to 0.8 MPaG, the pressure was increased, and the polymerization reaction was carried out for 90 minutes. The obtained polymer was filtered and then vacuum dried at 80 ° C. for 10 hours to obtain 64.8 g of an olefin polymer. The catalytic activity was 6500 g / g-solid catalytic component.
Table 8 shows the results of measuring the physical properties of the obtained olefin polymer.

[Comparative Example 2]
<Preparation of solid catalyst component (X-3)>
A slurry of the solid catalyst component (X-3) was prepared by the same method as in Example 1 except that the compound (a-2) was used instead of the compound (A).

<Manufacturing of olefin polymer>
After adding 500 ml of heptane to a SUS autoclave having an internal volume of 1 liter sufficiently substituted with nitrogen under a nitrogen atmosphere, ethylene was circulated and the inside of the reactor was saturated with ethylene. Next, 10 mL of 1-hexene, 0.375 mmol of triisobutylaluminum, and 200 mg of the solid catalyst component (X-3) in the form of a slurry were charged as a solid component, and then at 80 ° C. and 0.8 MPaG with ethylene. The temperature was raised and the pressure was increased, and the polymerization reaction was carried out for 90 minutes. The obtained polymer was filtered and then vacuum dried at 80 ° C. for 10 hours to obtain 38.9 g of an olefin polymer. The catalytic activity was 200 g / g-solid catalytic component.
Table 8 shows the results of measuring the physical properties of the obtained olefin polymer.

Examples using the transition metal compound [A] (crosslinked (2-indenyl) cyclopentadienyl type compound) of the present invention have a lower molecular weight and the same level of vinyl terminal numbers as those of Comparative Examples 1 and 2. When the olefin polymer was obtained, it showed clearly high catalytic activity. That is, it is clear that the transition metal compound [A] of the present invention can produce a macromonomer with high activity and a high terminal vinyl ratio.

Claims (9)

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 satisfying the valence of M.
X is a neutral ligand capable of coordinating with a hydrogen atom, a halogen atom, a hydrocarbon group, an anionic ligand or an isolated electron pair, and the anion ligand is a halogen-containing group, a silicon-containing group, or oxygen. It is a containing group, a sulfur-containing group, a nitrogen-containing group, a phosphorus-containing group, a boron-containing group, an aluminum-containing group or a conjugated diene-based derivative group. But they may be different, they may combine with each other to form a ring,
Q is a group 14 atom of the periodic table,
R ¹ to R ¹² are independently hydrogen atoms, hydrocarbon groups having 1 to 40 carbon atoms, halogen-containing groups, silicon-containing groups, oxygen-containing groups, nitrogen-containing groups or sulfur-containing groups, and they are the same or different. May be
However, either R ⁸ or R ⁹ is an n-propyl group, an n-butyl group, an allyl group or a pig-3-en-1-yl group .
R ⁷ and R ⁸ may be bonded to each other to form a saturated ring which may have a substituent.
R ⁹ and R ¹⁰ may be bonded to each other to form a saturated ring which may have a substituent.
R ¹¹ and R ¹² may be bonded to each other to form a ring containing Q, and the ring may have a substituent. ) In the general formula [1],
M is a zirconium atom or a hafnium atom,
X is independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group or an oxygen-containing group, respectively.
The transition metal compound [A] according to claim 1, wherein Q is a carbon atom or a silicon atom. In the general formula [1],
Q is a silicon atom,
R ¹ to R ⁷ and R ¹⁰ to R ¹² are independently composed of a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group having 1 to 20 carbon atoms, or a nitrogen-containing group having 1 to 20 carbon atoms. The transition metal compound [A] according to claim 1, wherein each of them may be the same or different. In the general formula [1],
R ¹ and R ⁶ are hydrogen atoms,
R ² to R ⁵ , R ¹¹ and R ¹² are each independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and may be the same or different from each other.
One of R ⁷ and R ¹⁰ is a hydrogen atom,
The transition metal compound [A] according to claim 3, wherein any one of R ⁸ and R ⁹ is a hydrogen atom. In the general formula [1],
The transition metal compound [A] according to claim 4, wherein R ² to R ⁵ , R ⁷ and R ¹⁰ are hydrogen atoms. A catalyst for olefin polymerization, which comprises the transition metal compound [A] according to any one of claims 1 to 5. Further, (B-1) organometallic compound,
It contains at least one compound [B] selected from the group consisting of (B-2) an organoaluminum oxy compound and (B-3) a compound that reacts with a transition metal compound [A] to form an ion pair. The catalyst for olefin polymerization according to claim 6. 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 6 or 7. The production of the olefin polymer according to claim 8, wherein the step of polymerizing the olefin is a step of homopolymerizing ethylene or copolymerizing ethylene with an α-olefin having 3 or more and 20 or less carbon atoms. Method.