JP6886313B2 - Method for Producing Olefin Polymerization Catalyst and Ethylene Copolymer - Google Patents

Description

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

Olefin-based polymers such as polyethylene and polypropylene are environmentally friendly and clean materials composed of carbon and hydrogen, and are excellent in process moldability and physical properties. Due to this characteristic, it has been used in a wide range of fields such as automobiles, electrical equipment parts, food packaging, beverages / cosmetics / medical containers, civil engineering, and agricultural materials. In recent years, energy saving and reduction of environmental load have been emphasized, and there is an increasing demand for further weight reduction for many articles. On the other hand, if the appearance of the molded product obtained by inflation molding or hollow molding is defective, the product value is lowered. Therefore, not only the high strength that can be reduced in weight but also the appearance of the product is an important factor.

Olefin-based polymers are mainly produced using Ziegler-type, metallocene-type, or post-metallocene-type polymerization catalysts. Among these, the metallocene-type polymerization catalyst has higher activity than the Ziegler-type polymerization catalyst, and the obtained olefin-based polymer has features such as a narrow molecular weight distribution, and therefore can be obtained from the metallocene-type polymerization catalyst. Polymers are known to exhibit excellent mechanical properties such as high strength and high rigidity (Patent Documents 1 to 3).

International Publication No. 2008/087945 Japanese Unexamined Patent Publication No. 2005-206777 Japanese Unexamined Patent Publication No. 2005-2333

However, among the metallocene-type polymerization catalysts, the olefin-based polymer produced by using the polymerization catalyst of the cross-linking complex has very excellent mechanical strength, but when the olefin-based polymer is molded into a molded product such as a film or a bottle, Fish eyes are generated, and poor appearance is likely to occur.

An object of the present invention is to provide a catalyst for olefin polymerization capable of producing an olefin polymer capable of forming a molded product having a good appearance with few fish eyes.

The present invention is the following [1] to [ 6 ].

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

Component (A): At least one compound represented by the following formula (I), which is a compound other than the following component (B);

（式（Ｉ）中、Ｘは一価の基であり、それぞれ独立に、水素原子、ハロゲン原子、炭化水素基、ハロゲン含有基、ケイ素含有基、酸素含有基、イオウ含有基、窒素含有基、リン含有基、ホウ素含有基またはアルミニウム含有基であり、互いに同一でも異なっていてもよい。Ｍは、チタン原子、ジルコニウム原子またはハフニウム原子である。Ｃｐ ^１ は、ＭおよびＣｐ ^２ と共にサンドイッチ構造を形成することができるシクロペンタジエニル基または置換シクロペンタジエニル基を示し、Ｃｐ ^２ は、ＭおよびＣｐ ^１ と共にサンドイッチ構造を形成することができる置換シクロペンタジエニル基を示し、該置換シクロペンタジエニル基は、インデニル基、フルオレニル基およびアズレニル基から選択される基であり、これらが有する一つ以上の水素原子が炭素数１〜２０の炭化水素基で置換された基を有するインデニル基、フルオレニル基およびアズレニル基を含む、ただし、これらの場合において、シクロペンタジエニル基に縮合する不飽和環の二重結合の一部または全部が水添されたものは含まない。Ｙは炭素数１〜３０の２価の炭化水素基、炭素数１〜２０の２価のハロゲン化炭化水素基、２価のケイ素含有基、２価のゲルマニウム含有基、２価のスズ含有基、−Ｏ−、−ＣＯ−、−Ｓ−、−ＳＯ−、−ＳＯ_２−、−Ｇｅ−、−Ｓｎ−、−ＮＲ^ａ−、−Ｐ（Ｒ^ａ）−、−Ｐ（Ｏ）（Ｒ^ａ）−、−ＢＲ^ａ−または−ＡｌＲ^ａ−を示す。Ｒ^ａは炭素数１〜２０の炭化水素基、炭素数１〜２０のハロゲン化炭化水素基、水素原子、ハロゲン原子または窒素原子に炭素数１〜２０の炭化水素基が１個または２個結合した窒素化合物残基（−ＮＲＨまたは−ＮＲ_２；Ｒは炭素数１〜２０の炭化水素基）を示す。）。

In the formula (I), X is a monovalent group, and each of them independently has a hydrogen atom, a halogen atom, a hydrocarbon group, a halogen-containing group, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, and a nitrogen-containing group. phosphorus-containing group, a boron-containing group or an aluminum-containing group, good .M be the same or different from each other, .cp ¹ is a titanium atom, a zirconium atom or a hafnium atom, form a sandwich structure together with M and Cp ² Shows a cyclopentadienyl group or a substituted cyclopentadienyl group that can be, Cp ² represents a substituted cyclopentadienyl group that can form a sandwich structure with M and Cp ^{1, and the substituted cyclopentadi.} The enyl group is a group selected from an indenyl group, a fluorenyl group and an azurenyl group, and the fluorenyl group having one or more hydrogen atoms substituted with a hydrocarbon group having 1 to 20 carbon atoms is a fluorenyl group. It contains groups and azulenyl groups, but in these cases it does not include those in which some or all of the double bonds of the unsaturated ring fused to the cyclopentadienyl group are hydrogenated. Y has 1 to 1 carbon atoms. 30 divalent hydrocarbon groups, divalent halogenated hydrocarbon groups with 1 to 20 carbon atoms, divalent silicon-containing groups, divalent germanium-containing groups, divalent tin-containing groups, -O-,- CO-, _{-S-, -SO-, -SO 2-} , -Ge-, -Sn-, -NR ^a- , -P ( ^Ra )-, -P (O) (R ^a )-, -BR ^{Indicates a} − or −AlR ^a −. ^Ra has a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, a hydrogen atom, a halogen atom or a nitrogen atom having 1 to 20 carbon atoms. A nitrogen compound residue in which one or two hydrocarbon groups are bonded (-NRH or -NR ₂ ; R is a hydrocarbon group having 1 to 20 carbon atoms).

Component (B): At least one compound selected from the compounds represented by the following formulas (II), (III), (IV) and (V);

（式（ＩＩ）、（ＩＩＩ）および（ＩＶ）中、Ｒ^２、Ｒ^３ 、Ｒ ^５、Ｒ^６およびＲ^７は一価の基であり、それぞれ独立に、水素原子、炭化水素基、ハロゲン含有基、酸素含有基、窒素含有基、ホウ素含有基、イオウ含有基、リン含有基、ケイ素含有基、ゲルマニウム含有基またはスズ含有基であり、互いに同一でも異なっていてもよく、隣接した置換基は互いに結合して環を形成してもよい。Ｒ ^４ は、水素原子である。Ｑ^２は二価の基であり、炭素数１〜２０の炭化水素基、ハロゲン含有基、ケイ素含有基、ゲルマニウム含有基またはスズ含有基であり、Ｒ^３およびＱ^２は互いに結合して環を形成してもよい。Ｑ^３は二価の基であり、炭素数１〜２０の炭化水素基、ハロゲン含有基、ケイ素含有基、ゲルマニウム含有基またはスズ含有基であり、Ｒ^３およびＱ^３は互いに結合して環を形成してもよい、ただし、Ｑ ^３ は−Ｌ−Ｄ ^３ を含まない。Ｑ^４は、炭素原子、ケイ素原子、ゲルマニウム原子またはスズ原子であり、Ｒ^３およびＲ^７は互いに結合して環を形成してもよい。Ｘは一価の基であり、それぞれ独立に、水素原子、ハロゲン原子、炭化水素基、ハロゲン含有基、ケイ素含有基、酸素含有基、イオウ含有基、窒素含有基、リン含有基、ホウ素含有基またはアルミニウム含有基であり、互いに同一でも異なっていてもよい。Ｍは、チタン原子、ジルコニウム原子またはハフニウム原子である。Ｌは、炭素数１〜１０の直鎖の炭素鎖を有する二価の炭化水素基である。Ｄ^１、Ｄ^２およびＤ^３は、それぞれ下記式（Ｄ−ａ）、（Ｄ−ｂ）、（Ｄ−ｃ）、（Ｄ−ｄ）、（Ｄ−ｅ）、（Ｄ−ｆ）、（Ｄ−ｇ）、（Ｄ−ｈ）または（Ｄ−ｉ）で示される基である。）

(Formula (II), in (III) and ^{(IV), R 2, R} 3, R 5, R 6 and ^{R 7} is a monovalent group, each independently, a hydrogen atom, a hydrocarbon group, a halogen-containing Groups, oxygen-containing groups, nitrogen-containing groups, boron-containing groups, sulfur-containing groups, phosphorus-containing groups, silicon-containing groups, germanium-containing groups or tin-containing groups, which may be the same or different from each other and adjacent substituents. They may be bonded to each other to form a ring. R ⁴ is a hydrogen atom. Q ² is a divalent group, which is a hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing group, a silicon-containing group, and germanium. It is a containing group or a tin-containing group, and R ³ and Q ² may be bonded to each other to form a ring. Q ³ is a divalent group, which is a hydrocarbon group having 1 to 20 carbon atoms and a halogen-containing group. , a silicon-containing group, a germanium-containing group or a tin-containing group, ^{R 3} and ^{Q 3} may be bonded to each other to form a ring, provided that, .Q ^{4 Q 3} are free of ^{-L-D 3} is , Carbon atom, silicon atom, germanium atom or tin atom, R ³ and R ⁷ may be bonded to each other to form a ring. X is a monovalent group, which are independently hydrogen atom and halogen. Atomic, hydrocarbon groups, halogen-containing groups, silicon-containing groups, oxygen-containing groups, sulfur-containing groups, nitrogen-containing groups, phosphorus-containing groups, boron-containing groups or aluminum-containing groups, which may be the same or different from each other. Is a titanium atom, a zirconium atom or a hafnium atom. L is a divalent hydrocarbon group having a linear carbon chain having 1 to 10 carbon atoms. D ¹ , D ² and D ³ are as follows, respectively. Formulas (D-a), (D-b), (D-c), (D-d), (D-e), (D-f), (D-g), (D-h) or ( It is a group represented by Di).)

（式（Ｄ−ｂ）、（Ｄ−ｃ）、（Ｄ−ｄ）、（Ｄ−ｅ）、（Ｄ−ｆ）および（Ｄ−ｇ）中、Ｒ^８、Ｒ^９、Ｒ^１０、Ｒ^１１およびＲ^１３は一価の基であり、それぞれ独立に、水素原子、ハロゲン原子、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、ホウ素含有基、イオウ含有基、リン含有基、ケイ素含有基、ゲルマニウム含有基またはスズ含有基であり、互いに同一でも異なっていてもよく、隣接した置換基は互いに結合して環を形成してもよい。Ｒ^１２は一価の基であり、酸素含有基、窒素含有基、イオウ含有基またはリン含有基であり、隣接するＲ^１１と互いに結合して環を形成してもよい。Ｃｈは酸素原子または硫黄原子である。Ｐｎは窒素原子またはリン原子である。）

(In formulas (Db), (Dc), (Dd), (D-e), (Df) and (Dg), R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ And R ¹³ are monovalent groups, which are independently hydrogen atom, halogen atom, hydrocarbon group, halogen-containing group, silicon-containing group, oxygen-containing group, nitrogen-containing group, boron-containing group, sulfur-containing group, and phosphorus. It is a containing group, a silicon-containing group, a germanium-containing group or a tin-containing group, which may be the same or different from each other, and adjacent substituents may be bonded to each other to form a ring. R ¹² is a monovalent group. , and the oxygen-containing group, a nitrogen-containing group, a sulfur-containing group or a phosphorus-containing group, may be bonded to each other to form a ring with the adjacent R ¹¹ .ch is an oxygen atom or a sulfur atom .Pn is It is a nitrogen atom or a phosphorus atom.)

（式（Ｖ）中、Ｘは一価の基であり、それぞれ独立に、水素原子、ハロゲン原子、炭化水素基、ハロゲン含有基、ケイ素含有基、酸素含有基、イオウ含有基、窒素含有基、リン含有基、ホウ素含有基またはアルミニウム含有基であり、互いに同一でも異なっていてもよい。Ｍは、チタン原子、ジルコニウム原子またはハフニウム原子である。Ｃｐ^１およびＣｐ^２はＭと共にサンドイッチ構造を形成することができるシクロペンタジエニル基または置換シクロペンタジエニル基を示し、互いに同一でも異なっていてもよい。）。

(In the formula (V), X is a monovalent group, and each of them independently has a hydrogen atom, a halogen atom, a hydrocarbon group, a halogen-containing group, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, and a nitrogen-containing group. It is a phosphorus-containing group, a boron-containing group or an aluminum-containing group and may be the same or different from each other. M is a titanium atom, a zirconium atom or a hafnium atom. ^{Cp 1} and Cp ² form a sandwich structure with M. Indicates a cyclopentadienyl group or a substituted cyclopentadienyl group which can be the same or different from each other).

Ingredient (C):
(C-1) An organometallic compound represented by the following formula (VI), (VII) or (VIII),
(C-2) Organoaluminium oxy compound,
(C-3) A compound that reacts with the component (A) and the component (B) to form an ion pair, and (c-4) the above (c-1), the above (c-2) and the above (c). At least one component selected from the group consisting of solid components obtained by insolubilizing a component containing at least one selected from the group consisting of -3);
^{_{R a m Al (OR b)}} n H p X q ··· (VI)
(In formula (VI), ^Ra and R ^b each independently represent a hydrocarbon group having 1 to 15 carbon atoms and may be the same or different from each other. X represents a halogen atom and m is 0. <m ≦ 3, n satisfies 0 ≦ n <3, p satisfies 0 ≦ p <3, q satisfies 0 ≦ q <3, and m + n + p + q = 3).
_{^{M a AlR a 4 ··· (VII}} )
(Formula (VII) in, ^{M a} is .R ^a lithium atom, sodium atom or a potassium atom represents a hydrogen atom or a hydrocarbon group having a carbon number 1 to 15.)
R ^a _r M ^b R ^b _s X _t ... (VIII)
(In formula (VIII), ^Ra and R ^b each independently represent a hydrocarbon group having 1 to 15 carbon ^{atoms and may be the same or different from each other. M b} may be a magnesium atom, a zinc atom or a zinc atom. It is a cadmium atom. X represents a halogen atom. R satisfies 0 <r ≦ 2, s satisfies 0 ≦ s ≦ 1, t satisfies 0 ≦ t ≦ 1, and r + s + t = 2).

[2] For olefin polymerization according to [1], wherein L is a divalent hydrocarbon group having a linear carbon chain having 1 to 3 carbon atoms in the above formula (II), (III) or (IV). catalyst.

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

_{[4] When ethylene and 1-hexene are copolymerized with the extreme viscosity [η] 1 of the} polymer obtained when ethylene is homopolymerized using a catalyst containing the component (A) and ethylene and 1-hexene using the catalyst. The catalyst for olefin polymerization according to any one of [1] to [3], wherein the relationship of the following formula (1) is established between the extreme viscosity [η] _{2 of the polymer obtained in}

[Η] ₂ / [η] ₁ > 1.1 (1).

_{[5] When ethylene and 1-hexene are copolymerized with the extreme viscosity [η] 1 of the} polymer obtained when ethylene is homopolymerized using a catalyst containing the component (B) and ethylene and 1-hexene using the catalyst. The catalyst for olefin polymerization according to any one of [1] to [4], wherein the relationship of the following formula (2) is established with the ultimate viscosity [η] _{2 of the polymer obtained in 1.}

[Η] ₂ / [η] ₁ ≤ 1.1 (2).

[ 6 ] A method for producing an ethylene-based copolymer, which comprises a step of copolymerizing ethylene with an olefin having 3 to 20 carbon atoms in the presence of the olefin polymerization catalyst according to any one of [1] to [ 5]. There,
A method for producing an ethylene-based copolymer, wherein the density of the ethylene-based copolymer is 910 kg / m ³ or more and 980 kg / m ^{3 or less.}

According to the present invention, it is possible to provide a catalyst for olefin polymerization capable of producing an olefin polymer capable of forming a molded product having a good appearance with few fish eyes.

[Catalyst for olefin polymerization]
The catalyst for olefin polymerization according to the present invention contains the component (A), the component (B), and the component (C). As described above, among the metallocene compounds, the olefin-based polymer produced by using the polymerization catalyst of the cross-linking complex has excellent mechanical strength, but fish eyes occur when it is molded into a molded product such as a film or a bottle. , Appearance defects are likely to occur. Therefore, the present inventors have performed polymerization by coexisting a specific complex with a crosslinked complex to maintain high mechanical strength and suppress the generation of fish eyes, which is an olefin having an excellent appearance during molding. We have found a catalyst for olefin polymerization that can efficiently produce a polymer, and have completed the present invention. Hereinafter, the details of the present invention will be described.

(Ingredient (A))
The component (A) is at least one compound represented by the formula (I) and is a compound other than the component (B). The component (A) is a component capable of producing an olefin polymer having excellent mechanical strength.

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

Specific examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a chlorine atom or a bromine atom is preferable.

Examples of the monovalent hydrocarbon group include methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, isopropyl, s-butyl, t-butyl, and the like. Isobutyl, pentan-2-yl, 2-methylbutyl, isopentyl, neopentyl, siamil, isohexyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, texyl, 4,4-dimethylpentyl, etc. Linear or branched alkyl groups of; vinyl, allyl, propenyl, isopropenyl, arenyl, butyl-3-en-1-yl, crotyl, butyl-3-en-2-yl, metallic, erythrenyl, penta- 4-En-1-yl, Penta-3-en-1-yl, Penta-2-en-1-yl, Isopentenyl, 2-Methylbuta-3-en-1-yl, Penta-4-en-2 -Linear or branched alkenyl groups such as yl, prenyl or unsaturated double bond-containing groups; linear or branched alkynyl groups such as ethynyl, propa-2-in-1-yl, propargyl Saturated triple bond-containing group; benzyl, 2-methylbenzyl, 4-methylbenzyl, 2,4,6-trimethylbenzyl, 3,5-dimethylbenzyl, cuminyl, 2,4,6-triisopropylbenzyl, 4-t- Aromatic-containing linear or branched alkyl groups such as butylbenzyl, 3,5-di-t-butylbenzyl, phenylethyl, benzhydryl or unsaturated double bond-containing groups; cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, Cyclic saturated hydrocarbon groups such as cycloheptyl, cycloheptatrienyl, norbornyl, norbornenyl, 1-adamantyl, 2-adamantyl; phenyl, trill, xylyl, mesityl, cumenyl, juryl, 2,6-diisopropylphenyl, 2,4 Aryl groups such as 6-triisopropylphenyl, 4-t-butylphenyl, 3,5-di-t-butylphenyl, naphthyl, biphenyl, t-phenyl, binaphthyl, acenaphthalenyl, phenanthryl, anthracenyl, pyrenyl, ferrosenyl; 1, Conjugated diene divalent derivative groups capable of forming a metallocyclopentene group, such as 3-butadienyl, isoprenyl, piperylenyl, 2,4-hexadienyl, 1,4-diphenyl-1,3-pentadienyl, cyclopentadienyl, etc. Can be done.

Among the hydrocarbon groups, methyl, isobutyl, neopentyl, siamil, benzyl, phenyl, trill, xylyl, mesityl, cumenyl, 1,3-butadienyl, isoprenyl, piperylenyl, 2,4-hexadienyl, 1,4-diphenyl are preferable. It is -1,3-pentadienyl.

Examples of the monovalent halogen-containing group include fluoromethyl, trifluoromethyl, trichloromethyl, pentafluoroethyl, 2,2,2-trifluoroethyl, fluorophenyl, difluorophenyl, trifluorophenyl, tetrafluorophenyl, and the like. Examples thereof include pentafluorophenyl, trifluoromethylphenyl, bistrifluoromethylphenyl, hexachloroantimonate anion and the like. Pentafluorophenyl is preferred.

Examples of the monovalent silicon-containing group include trimethylsilyl, triethylsilyl, triisopropylsilyl, diphenylmethylsilyl, t-butyldimethylsilyl, t-butyldiphenylsilyl, triphenylsilyl, tris (trimethylsilyl) silyl, trimethylsilylmethyl and the like. Can be mentioned. Preferably, it is trimethylsilylmethyl.

Examples of the monovalent oxygen-containing group include methoxy, ethoxy, n-propoxy, isopropoxy, allyloxy, n-butoxy, s-butoxy, isobutoxy, t-butoxy, benzyloxy, methoxymethoxy, phenoxy, 2,6. -Dimethylphenoxy, 2,6-diisopropylphenoxy, 2,6-di-t-butylphenoxy, 2,4,6-trimethylphenoxy, 2,4,6-triisopropylphenoxy, acetoxy, pivaloyloxy, benzoyloxy, trifluoro Examples thereof include acetoxy, perchlorate anion, and periodate anion. Preferred are methoxy, ethoxy, isopropoxy and t-butoxy.

Examples of the monovalent sulfur-containing group include mesylate, phenylsulfonyl, tosyl, trifuryl, nonafryl, mesylate, tosylate, triflate, and nonaflate. Preferred is triflate.

Examples of the monovalent nitrogen-containing group include amino, cyano, methylamino, dimethylamino, ethylamino, diethylamino, allylamino, diallylamino, benzylamino, dibenzylamino, pyrrolidinyl, piperidinyl, morpholyl, pyrrolyl and bistrifurylimide. And so on. Preferred are dimethylamino, diethylamino, pyrrolidinyl, pyrrolyl and bistrifurylimide.

Examples of the monovalent phosphorus-containing group include hexafluorophosphate anion and the like.

Examples of the monovalent boron-containing group include tetrafluoroborate anion, tetrakis (pentafluorophenyl) borate anion, (methyl) (tris (pentafluorophenyl)) borate anion, and (benzyl) (tris (penta). Fluorophenyl)) borate anion, tetrakis ((3,5-bistrifluoromethyl) phenyl) borate anion, BR ₄ (R is hydrogen, alkyl group, aryl group or halogen atom which may have a substituent, etc. Show).

As the monovalent aluminum-containing group, for example, a (M-halogen atom-aluminum atom-hydrocarbon group) four-membered ring or (M-hydrocarbon group-aluminum atom-hydrocarbon group) four-membered ring can be formed. AlR ₄ (R represents a hydrogen, an alkyl group, an aryl group which may have a substituent, a halogen atom, etc.) can be mentioned. In addition, M is M in the said formula (I).

In the formula (I), M is a titanium atom, a zirconium atom or a hafnium atom. Cp ¹ and Cp ² represent a cyclopentadienyl group or a substituted cyclopentadienyl group that can form a sandwich structure with M and may be the same or different from each other. The substituted cyclopentadienyl group is a group in which at least one hydrogen atom of the cyclopentadienyl group is substituted with a substituent.

Examples of the substituent in the substituted cyclopentadienyl group include a hydrocarbon group (preferably a hydrocarbon group having 1 to 20 carbon atoms, hereinafter also referred to as “hydrocarbon group (f1)”), and a silicon-containing group (preferably carbon). The number 1 to 20 of the silicon-containing group, hereinafter also referred to as “silicon-containing group (f2)”) can be mentioned. In addition, examples of the substituent in the substituted cyclopentadienyl group include heteroatom-containing groups (excluding the silicon-containing group (f2)) such as a halogenated hydrocarbon group, an oxygen-containing group, and a nitrogen-containing group.

Examples of the hydrocarbon group (f1) include a linear or branched hydrocarbon group (alkyl group, alkenyl group, alkynyl group, etc.), a cyclic saturated hydrocarbon group (cycloalkyl group, etc.), and a cyclic unsaturated hydrocarbon. Examples include groups (aryl groups, etc.). The hydrocarbon group (f1) includes a group in which any two hydrogen atoms bonded to carbon atoms adjacent to each other are simultaneously substituted to form an alicyclic or aromatic ring.

Specific examples of the hydrocarbon group (f1) include methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group and n-octyl group. Linear aliphatic hydrocarbon groups such as n-nonyl group, n-decanyl group and allyl group; isopropyl group, isobutyl group, sec-butyl group, t-butyl group, amyl group, 3-methylpentyl Group, neopentyl group, 1,1-diethylpropyl group, 1,1-dimethylbutyl group, 1-methyl-1-propylbutyl group, 1,1-propylbutyl group, 1,1-dimethyl-2-methylpropyl group , 1-Methyl-1-isopropyl-2-methylpropyl group and other branched aliphatic hydrocarbon groups; cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, norbornyl group, adamantyl group and other cyclic saturated hydrocarbons. Group; Cyclic unsaturated hydrocarbon group such as phenyl group, naphthyl group, biphenyl group, phenanthryl group, anthracenyl group and their nuclear alkyl substituents; at least one hydrogen contained in the saturated hydrocarbon group such as benzyl group and cumyl group. Examples include groups in which the atom is substituted with an aryl group.

Examples of the silicon-containing group (f2) include a group in which a silicon atom is directly covalently bonded to the ring carbon of a cyclopentadienyl group, and specifically, an alkylsilyl group (trimethylsilyl or the like) or an arylsilyl group. (Triphenylsilyl group, etc.) can be mentioned.

Specific examples of the hetero atom-containing group (excluding the silicon-containing group (f2)) include a methoxy group, an ethoxy group, a phenoxy group, an N-methylamino group, a trifluoromethyl group, a tribromomethyl group, and a pentafluoroethyl group. Examples include a group and a pentafluorophenyl group.

Among the hydrocarbon groups (f1), linear or branched aliphatic hydrocarbon groups having 1 to 20 carbon atoms, specifically, methyl group, ethyl group, n-propyl group, n-butyl group, n -Hexyl group, isopropyl group, isobutyl group, sec-butyl group, t-butyl group and neopentyl group are preferable.

The substituted cyclopentadienyl group includes an indenyl group, a fluorenyl group, an azulenyl group and a group in which one or more hydrogen atoms contained therein are substituted with the hydrocarbon group, and in the case of an indenyl group, a fluorenyl group, an azulenyl group. May be hydrogenated in part or in whole of the double bond of the unsaturated ring fused to the cyclopentadienyl group.

In the formula (I), Y is a divalent hydrocarbon group having 1 to 30 carbon atoms, a divalent halogenated hydrocarbon group having 1 to 20 carbon atoms, a divalent silicon-containing group, and a divalent germanium-containing group. , Divalent tin-containing groups, -O-, -CO-, -S-, -SO-, -SO _2- , -Ge-, -Sn-, -NR ^a- , -P (R ^a )-, ^{-P (O) (R a)} -, - BR a - or -AlR ^a - shows the. ^Ra has one or two hydrocarbon groups having 1 to 20 carbon atoms bonded to a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, a hydrogen atom, a halogen atom or a nitrogen atom. The nitrogen compound residue (-NRH or -NR ₂ ; R is a hydrocarbon group having 1 to 20 carbon atoms).

The component (A) is a crosslinked metallocene compound represented by the following formula (A) other than the component (B) among the compounds represented by the formula (I) (hereinafter, “crosslinked metallocene compound (A)”). Also referred to as) is preferable.

架橋型メタロセン化合物（Ａ）は、構造上、次の特徴［ｍ１］および［ｍ２］を備える。
［ｍ１］二つの配位子のうち、一つは置換基を有していてもよいシクロペンタジエニル基であり、他の一つは置換基を有するフルオレニル基（以下「置換フルオレニル基」ともいう）である。
［ｍ２］二つの配位子が、アリール（ａｒｙｌ）基を有する炭素原子またはケイ素原子からなるアリール基含有共有結合架橋部（以下「架橋部」ともいう）によって結合されている。

The crosslinked metallocene compound (A) structurally has the following features [m1] and [m2].
[M1] Of the two ligands, one is a cyclopentadienyl group which may have a substituent, and the other one is a fluorenyl group having a substituent (hereinafter, also referred to as "substituted fluorenyl group"). ).
[M2] Two ligands are bonded by an aryl group-containing covalent bond cross-linking portion (hereinafter, also referred to as “cross-linking portion”) composed of a carbon atom or a silicon atom having an aryl group.

In the above formula (A), R ¹ , R ² , R ³ and R ⁴ independently represent a hydrogen atom, a hydrocarbon group, a silicon-containing group or a hetero atom-containing group other than a silicon-containing group, and represent a hydrogen atom and a hydrocarbon. A group or a silicon-containing group is preferable, and two adjacent groups may be bonded to each other to form a ring.

For example, R ¹ , R ² , R ³ and R ⁴ are all hydrogen atoms, or ^one or more of R 1, R ² , R ³ and R ⁴ are hydrocarbon groups (preferably 1 to 1 carbon atoms). 20 hydrocarbon groups) or silicon-containing groups (preferably silicon-containing groups having 1 to 20 carbon atoms). In addition, heteroatom-containing groups such as halogenated hydrocarbon groups, oxygen-containing groups, and nitrogen-containing groups can also be mentioned.

When ^{two or more of R 1} , R ² , R ³ and R ⁴ are substituents other than hydrogen atoms, the substituents may be the same or different from each other, and R ¹ , R ² , R ³ and two groups adjacent to each other of R ⁴ may form an alicyclic or aromatic ring bonded to each other.

Examples of the hydrocarbon group in R ^{1 to} R ⁴ and a preferable group include the hydrocarbon group (f1) defined in the place of the substituted cyclopentadienyl group. Examples of the silicon-containing group in R ^{1 to} R ⁴ and a preferable group include the silicon-containing group (f2) defined in the place of the substituted cyclopentadienyl group. Examples of the heteroatom-containing group in R ^{1 to} R ⁴ include the groups exemplified in the above-mentioned substituted cyclopentadienyl group.

In the above formula (A), R ⁵ , R ⁸ , R ⁹ and R ¹² independently represent a hydrogen atom, a hydrocarbon group, a silicon-containing group or a hetero atom-containing group other than a silicon-containing group, and represent a hydrogen atom and a hydrocarbon. Groups or silicon-containing groups are preferred. R ⁶ and R ¹¹ are the same atom or the same group selected from hetero atom-containing groups other than hydrogen atom, hydrocarbon group, silicon-containing group and silicon-containing group, and the hydrogen atom, hydrocarbon group and silicon-containing group are preferable. R ⁷ and R ¹⁰ are the same atom or the same group selected from hetero atom-containing groups other than hydrogen atom, hydrocarbon group, silicon-containing group and silicon-containing group, and the hydrogen atom, hydrocarbon group and silicon-containing group are preferable. R ⁶ and R ⁷ may be coupled to each other to form a ring, and R ¹⁰ and R ¹¹ may be coupled to each other to form a ring. However, R ⁶ , R ⁷ , R ¹⁰ and R ¹¹ are not all hydrogen atoms.

From the perspective of polymerization activity, it is preferred that ^{R 6} and ^{R 11} is not each is hydrogen ^atom, R ^6, R ^7, more preferably ^{R 10} and ^{R 11} are not both a hydrogen atom, ^{R 6} and R ^{It is more preferable that 11} is the same group selected from the hydrocarbon group and the silicon-containing group, and R ⁷ and R ¹⁰ are the same group selected from the hydrocarbon group and the silicon-containing group. It is also preferable that R ⁶ and R ⁷ are bonded to each other to form an alicyclic or aromatic ring, and R ¹⁰ and R ¹¹ are bonded to each other to form an alicyclic or aromatic ring.

Examples of the hydrocarbon group in R ^{5 to} R ¹² and a preferable group include the hydrocarbon group (f1) defined in the place of the substituted cyclopentadienyl group. Examples of the silicon-containing group in R ^{5 to} R ¹² and a preferable group include the silicon-containing group (f2) defined in the place of the substituted cyclopentadienyl group. Examples of the heteroatom-containing group in R ^{5 to} R ¹² include the groups exemplified in the above-mentioned substituted cyclopentadienyl group. The substituted fluorenyl group when R ⁶ and R ⁷ (R ¹⁰ and R ¹¹ ) are bonded to each other to form an alicyclic or aromatic ring is derived from the compounds represented by the following formulas (B) to (F). Groups are a good example.

前記式（Ａ）中、Ｒ^１３およびＲ^１４はそれぞれ独立にアリール基を示し、Ｙ^１は炭素原子またはケイ素原子を示す。製造上の容易性から、Ｒ^１３およびＲ^１４は互いに同一であることが好ましい。アリール基としては、例えば、フェニル基、ナフチル基、アントラセニル基およびこれらが有する芳香族水素（ｓｐ２型水素）の一つ以上が置換基で置換された基が挙げられる。置換基としては、前記置換シクロペンタジエニル基の箇所にて定義した炭化水素基（ｆ１）およびケイ素含有基（ｆ２）や、ハロゲン原子およびハロゲン化炭化水素基が挙げられる。

In the formula (A), R ¹³ and R ¹⁴ each independently represent an aryl group, and Y ¹ represents a carbon atom or a silicon atom. From the viewpoint of ease of manufacture, ^{it is preferable that R 13} and R ¹⁴ are the same as each other. Examples of the aryl group include a phenyl group, a naphthyl group, an anthracenyl group, and a group in which one or more of the aromatic hydrogens (sp2-type hydrogens) contained therein are substituted with a substituent. Examples of the substituent include a hydrocarbon group (f1) and a silicon-containing group (f2) defined in the place of the substituted cyclopentadienyl group, and a halogen atom and a halogenated hydrocarbon group.

Specific examples of the aryl group include an unsubstituted aryl group having 6 to 14 carbon atoms, preferably 6 to 10 carbon atoms such as a phenyl group, a naphthyl group, an anthracenyl group, and a biphenyl group; a tolyl group, a dimethylphenyl group, an isopropylphenyl group, n. -Alkyl group substituted aryl groups such as butylphenyl group and t-butylphenyl group; Cycloalkyl group substituted aryl groups such as cyclohexylphenyl group; aryl halide groups such as chlorophenyl group, bromophenyl group, dichlorophenyl group and dibromophenyl group; Examples thereof include alkyl halide-substituted aryl groups such as (trifluoromethyl) phenyl group and bis (trifluoromethyl) phenyl group. The position of the substituent is preferably the meta position and / or the para position. Among these, a substituted phenyl group in which the substituent is located at the meta position and / or the para position is more preferable.

In the formula (A), X represents an alkyl group which may contain a hetero atom, and X may be the same or different. Examples of the alkyl group include atoms or groups similar to X in the above formula (I).

The crosslinked metallocene compound (A) can be produced by a known method, and the production method is not particularly limited. Known methods include, for example, the methods described in International Publication No. 01/27174 and International Publication No. 04/029062.

When ethylene and 1-hexene are copolymerized using the catalyst and _{the extreme viscosity [η] 1 of the} polymer obtained when ethylene is homopolymerized using the catalyst containing the component (A) according to the present invention. It is preferable that the relationship of the following formula (1) is established with the ultimate viscosity [η] ₂ of the obtained polymer from the viewpoint of improving the strength of the obtained polymer.

[Η] ₂ / [η] ₁ > 1.1 (1)
[Η] ₂ / [η] ₁ is more preferably 1.3 or more, and even more preferably 1.5 or more. The upper limit of [η] ₂ / [η] ₁ is not particularly limited, but may be, for example, 3.0 or less. Here, the "catalyst containing the component (A)" refers to a catalyst that may contain the component (C) in addition to the component (A). As the conditions for homopolymerizing ethylene, the polymerization was carried out at 0.65 MPa · G under the hydrogen concentration conditions of triisobutylaluminum 0.50 mmol / L, 75 ° C. and ethylene / hydrogen (0.45 mol%), and the weight was increased. The yield of coalescence is in the range of 10-120 g. The conditions for copolymerizing ethylene and 1-hexene are 0.50 mmol / L of triisobutylaluminum and 3.0 ml of 1-hexene at 75 ° C. and ethylene / hydrogen (0.45 mol%). Polymerization was carried out at 0.65 MPa · G under hydrogen concentration conditions, and the yield of the polymer was in the range of 10 to 120 g. Specifically, the ultimate viscosities [η] ₁ and [η] ₂ are obtained by the method described later.

Further, in the present invention, the component (A) includes a compound other than the compound represented by the formula (I) and satisfying the formula (1).

(Component (B))
The component (B) is at least one compound selected from the compounds represented by the formulas (II), (III), (IV) and (V). The component (B) is a component capable of suppressing the generation of fish eyes and improving the appearance when the obtained polymer is molded into a molded product such as a film or a bottle. Component (B) is preferably a compound represented by the formula (III) or (IV), among the compounds represented by the formula (IV), Compound D 3 _-L is a straight-chain hydrocarbon group More preferred.

In the formulas (II), (III) and (IV), R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are monovalent groups and are independently hydrogen atoms and hydrocarbons, respectively. Groups, halogen-containing groups, oxygen-containing groups, nitrogen-containing groups, boron-containing groups, sulfur-containing groups, phosphorus-containing groups, silicon-containing groups, germanium-containing groups or tin-containing groups, which may be the same or different from each other and are adjacent to each other. The substituents may be bonded to each other to form a ring. In the present specification, "may be the same or different from each other" means that the substituents described by the same number in the metallocene compounds may be the same or different, and further, different metallocene compounds may be used. , Means that the substituents having the same number may be the same or different.

Examples of the monovalent hydrocarbon group include methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decanyl, and n-. Undecanyl, n-dodecanyl, n-eicosanyl, isopropyl, s-butyl, t-butyl, isobutyl, pentan-2-yl, 2-methylbutyl, isopentyl, neopentyl, t-pentyl, sheamil, pentan-3-yl, 2- Methylpentyl, 3-methylpentyl, isohexyl, 1,1-dimethylbutyl, 3-methylpentane-2-yl, 4-methylpentane-2-yl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3 , 3-Dimethylbutyl, Texyl, 3-methylpentane-3-yl, 3,3-dimethylbut-2-yl, hexane-3-yl, 2-methylpentane-3-yl, heptane-4-yl, 2 , 4-Dimethylpentane-3-yl, 3-ethylpentane-3-yl, 4,4-dimethylpentyl, 4-methylheptan-4-yl, 4-propylheptan-4-yl, 2,3,3- Linear or branched alkyl groups with 1 to 20 carbon atoms such as trimethylbutan-2-yl, 2,3,4-trimethylpentane-3-yl;
Vinyl, allyl, propenyl, isopropenyl, allenyl, porcine-3-en-1-yl, crotyl, porcine-3-en-2-yl, metalyl, erythrenyl, penta-4-en-1-yl, penta-3 -En-1-yl, penta-2-en-1-yl, isopentenyl, 2-methylbut-3-en-1-yl, penta-4-en-2-yl, prenyl, 2-methyl-buta- 2-en-1-yl, penta-3-en-2-yl, 2-methyl-but-3-en-2-yl, penta-1-en-3-yl, penta-2,4-diene- 1-yl, penta-1,3-dien-1-yl, penta-1,4-dien-3-yl, isoprenyl, penta-2,4-dien-2-yl, hexa-5-en-1- Il, Hexa-4-en-1-yl, Hexa-3-en-1-yl, Hexa-2-en-1-yl, 4-Methyl-penta-4-en-1-yl, 3-Methyl- Penta-4-en-1-yl, 2-methyl-penta-4-en-1-yl, hexa-5-en-2-yl, 4-methyl-pent-3-en-1-yl, 3- Methyl-penta-3-en-1-yl, 2,3-dimethyl-but-2-en-1-yl, 2-methylpenta-4-en-2-yl, 3-ethylpenta-1-en-3-yl Il, Hexa-3,5-diene-1-yl, Hexa-2,4-dien-1-yl, 4-methylpenta-1,3-dien-1-yl, 2,3-dimethyl-buta-1, 2 carbon atoms such as 3-diene-1-yl, hexa-1,3,5-triene-1-yl, 2- (cyclopentadienyl) propan-2-yl, 2- (cyclopentadienyl) ethyl ~ 20 linear or branched alkenyl groups or unsaturated double bond containing groups;
Ethynyl, propa-2-in-1-yl, propargyl, porcine-1-in-1-yl, porcine-2-in-1-yl, porcine-3-in-1-yl, penta-1-in- 1-yl, penta-2-in-1-yl, penta-3-in-1-yl, penta-4-in-1-yl, 3-methyl-buta-1-in-1-yl, penta- 3-in-2-yl, 2-methyl-but-3-in-1-yl, penta-4-in-2-yl, hexa-1-in-1-yl, 3,3-dimethyl-buta- 1-in-1-yl, 2-methyl-penta-3-in-2-yl, 2,2-dimethyl-but-3-in-1-yl, hexa-4-in-1-yl, hexa- Linear or branched alkynyl groups or unsaturated triple bond-containing groups having 2 to 20 carbon atoms such as 5-in-1-yl;
Benzyl, 2-methylbenzyl, 4-methylbenzyl, 2,4,6-trimethylbenzyl, 3,5-dimethylbenzyl, cuminyl, 2,4,6-triisopropylbenzyl, 4-t-butylbenzyl, 3,5 -Di-t-butylbenzyl, phenylethyl, benzhydryl, cumyl, 2- (4-methylphenyl) propan-2-yl, 2- (3,5-dimethylphenyl) propan-2-yl, 2- (4-) t-butylphenyl) propan-2-yl, 2- (3,5-di-t-butylphenyl) propan-2-yl, 3-phenylpentane-3-yl, 4-phenylhepta-1,6-diene -4-yl, 1,2,3-triphenylpropan-2-yl, 1,1-diphenylethyl, 1,1-diphenylpropyl, 1,1-diphenyl-3-ene-1-yl, 1 , 1,2-Triphenylethyl, trityl, tri- (4-methylphenyl) methyl, 2-phenylethyl, styryl, 2- (2-methylphenyl) ethyl, 2- (4-methylphenyl) ethyl, 2- (2,4,6-trimethylphenyl) ethyl, 2- (3,5-dimethylphenyl) ethyl, 2- (2,4,6-triisopropylphenyl) ethyl, 2- (4-t-butylphenyl) ethyl , 2- (3,5-di-t-butylphenyl) ethyl, 2-methyl-1-phenylpropan-2-yl, 3-phenylpropyl, 2-cinnamyl, neofil, 3-methyl-3-phenylbutyl, 2-Methyl-4-phenylbutane-2-yl, cyclopentadienyldiphenylmethyl, 2- (1-indenyl) propan-2-yl, (1-indenyl) diphenylmethyl, 2- (1-indenyl) ethyl, 2- (Tetrahydro-1-indacenyl) propan-2-yl, (tetrahydro-1-indacenyl) diphenylmethyl, 2- (tetrahydro-1-indacenyl) ethyl, 2- (1-benzoindenyl) propan-2-yl , (1-Benzoindenyl) diphenylmethyl, 2- (1-benzoindenyl) ethyl, 2- (9-fluorenyl) propan-2-yl, (9-fluorenyl) diphenylmethyl, 2- (9-fluorenyl) Aromatic-containing linear or branched alkyl having 7 to 20 carbon atoms such as ethyl, 2- (1-azulenyl) propan-2-yl, (1-azulenyl) diphenylmethyl, 2- (1-azulenyl) ethyl Group or unsaturated double bond-containing group;
Cyclopropyl, cyclobutyl, cyclopentyl, cyclopentenyl, cyclopentadienyl, dimethylcyclopentadienyl, n-butylcyclopentadienyl, n-butyl-methylcyclopentadienyl, tetramethylcyclopentadienyl, methylcyclopentyl, allyl Cyclopentyl, benzylcyclopentyl, cyclohexyl, cyclohexenyl, cyclohexadienyl, methylcyclohexyl, allylcyclohexyl, benzylcyclohexyl, cycloheptyl, cycloheptenyl, cycloheptatrienyl, methylcycloheptyl, allylcycloheptyl, benzylcycloheptyl, cyclooctyl, cyclooctenyl, Cyclooctadienyl, cyclooctatrienyl, methylcyclooctyl, allylcyclooctyl, benzylcyclooctyl, 4-cyclohexyl-t-butyl, norbornyl, norbornenyl, norbornadienyl, 2-methylbicyclo [2.2.1] Heptan-2-yl, 7-methylbicyclo [2.2.1] heptane-7-yl, bicyclo [2.2.2] octane-1-yl, bicyclo [2.2.2] octane-2-yl , 1-adamantyl, 2-adamantyl, 1- (2-methyladamantyl), 1- (3-methyladamantyl), 1- (4-methyladamantyl), 1- (2-phenyladamantyl), 1- (3-) Phenyl adamantyl), 1- (4-phenyl adamantyl), 1- (3,5-dimethyl adamantyl), 1- (3,5,7-trimethyl adamantyl), 1- (3,5,7-triphenyl adamantyl) , Pentalenyl, indenyl, fluorenyl, indacenyl, tetrahydroindacenyl, benzoindenyl, azulenyl, etc., cyclically saturated or unsaturated hydrocarbon groups having 3 to 20 carbon atoms;
Phenyl, trill, xsilyl, mesityl, cumenyl, juryl, 2,6-diisopropylphenyl, 2,4,6-triisopropylphenyl, 4-t-butylphenyl, 3,5-di-t-butylphenyl, allylphenyl, (Buta-3-en-1-yl) Phenyl, (Buta-2-en-1-yl) Phenyl, Metallylphenyl, Plenylphenyl, 4-adamantylphenyl, 3,5-di-adamantylphenyl, naphthyl, biphenyl , T-Phenyl, binaphthyl, acenaphthalenyl, phenanthryl, anthracenyl, pyrenyl, ferrosenyl and other aryl groups having 6 to 20 carbon atoms; and the like.

Among the linear or branched alkyl groups having 1 to 20 carbon atoms, methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, etc. are preferable. Isopropyl, s-butyl, t-butyl, isobutyl, isopentyl, neopentyl, t-pentyl, pentane-3-yl, isohexyl, 1,1-dimethylbutyl, 3,3-dimethylbutyl, texyl, 3-methylpentane-3 -Il, heptane-4-yl, 2,4-dimethylpentane-3-yl, 3-ethylpentane-3-yl, 4,4-dimethylpentyl, 4-methylheptane-4-yl, 4-propylheptan- 4-Il and the like can be mentioned. Among them, methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, isopropyl and t-butyl are more preferable.

Among the linear or branched alkenyl groups having 2 to 20 carbon atoms or unsaturated double bond-containing groups, vinyl, allyl, buta-3-ene-1-yl, crotyl, metalryl, penta-4 are preferable. -En-1-yl, prenyl, penta-1,4-diene-3-yl, hexa-5-ene-1-yl, 2-methylpenta-4-en-2-yl, 2- (cyclopentadienyl) ) Propane-2-yl, 2- (cyclopentadienyl) ethyl and the like. Among them, vinyl, allyl, porcine-3-en-1-yl, penta-4-en-1-yl, prenyl and hexa-5-ene-1-yl are more preferable.

Among the linear or branched alkynyl groups having 2 to 20 carbon atoms or unsaturated triple bond-containing groups, ethynyl, propa-2-in-1-yl, propargyl, buta-2-in-1-yl are preferable. Il, porcine-3-in-1-yl, penta-3-in-1-yl, penta-4-in-1-yl, 3-methyl-but-1-in-1-yl, 3,3- Examples thereof include dimethyl-buta-1-in-1-yl, hexa-4-in-1-yl, hexa-5-in-1-yl and the like. Of these, propagyl-2-in-1-yl, propargyl, porcine-2-in-1-yl, and porcine-3-in-1-yl are more preferable.

Among the aromatic-containing linear or branched alkyl groups having 7 to 20 carbon atoms or unsaturated double bond-containing groups, benzyl, 2-methylbenzyl, 4-methylbenzyl, 2,4,6- Trimethylbenzyl, 3,5-dimethylbenzyl, cuminyl, 2,4,6-triisopropylbenzyl, 4-t-butylbenzyl, 3,5-di-t-butylbenzyl, benzhydryl, cumyl, 1,1-diphenylethyl , Trityl, 2-phenylethyl, 2- (4-methylphenyl) ethyl, 2- (2,4,6-trimethylphenyl) ethyl, 2- (3,5-dimethylphenyl) ethyl, 2- (2,4) , 6-Triisopropylphenyl) ethyl, 2- (4-t-butylphenyl) ethyl, 2- (3,5-di-t-butylphenyl) ethyl, styryl, 2-methyl-1-phenylpropan-2- Il, 3-phenylpropyl, 2-cinnamyl, neofil, cyclopentadienyldiphenylmethyl, 2- (1-indenyl) propan-2-yl, (1-indenyl) diphenylmethyl, 2- (1-indenyl) ethyl, Examples thereof include 2- (9-fluorenyl) propan-2-yl, (9-fluorenyl) diphenylmethyl, and 2- (9-fluorenyl) ethyl. Among them, benzyl, benzhydryl, cumyl, 1,1-diphenylethyl, trityl, 2-phenylethyl, 3-phenylpropyl and 2-cinnamyl are more preferable.

Among the cyclically saturated or unsaturated hydrocarbon groups having 3 to 20 carbon atoms, preferably, cyclopropyl, cyclobutyl, cyclopentyl, cyclopentenyl, cyclopentadienyl, methylcyclopentyl, allylcyclopentyl, benzylcyclopentyl, cyclohexyl, cyclohexenyl, methyl. Cyclohexyl, allylcyclohexyl, benzylcyclohexyl, cycloheptyl, cycloheptenyl, cycloheptatrienyl, methylcycloheptyl, allylcycloheptyl, benzylcycloheptyl, cyclooctyl, cyclooctenyl, cyclooctadienyl, 4-cyclohexyl-t-butyl, norbornyl, Examples thereof include 2-methylbicyclo [2.2.1] heptan-2-yl, bicyclo [2.2.2] octane-1-yl, 1-adamantyl, 2-adamantyl, pentarenyl, indenyl and fluorenyl. Among them, cyclopentyl, cyclopentenyl, 1-methylcyclopentyl, cyclohexyl, cyclohexenyl, 1-methylcyclohexyl and 1-adamantyl are more preferable.

Among the aryl groups having 6 to 20 carbon atoms, phenyl, tolyl, xsilyl, mesityl, cumenyl, 2,6-diisopropylphenyl, 2,4,6-triisopropylphenyl, 4-t-butylphenyl, 3, Examples thereof include 5-di-t-butylphenyl, allylphenyl, prenylphenyl, 4-adamantylphenyl, naphthyl, biphenyl, t-phenyl, binaphthyl, phenanthryl, anthracenyl, ferrosenyl and the like. More preferably, phenyl, trill, xsilyl, mesityl, cumenyl, 2,6-diisopropylphenyl, 2,4,6-triisopropylphenyl, 4-t-butylphenyl, 3,5-di-t-butylphenyl. , Allylphenyl, 4-adamantylphenyl, naphthyl, biphenyl, phenanthryl, anthrasenyl.

Examples of the monovalent halogen-containing group include fluorine atom, chlorine atom, bromine atom, iodine atom, fluoromethyl, trifluoromethyl, trichloromethyl, pentafluoroethyl, 2,2,2-trifluoroethyl and heptafluoro. Propyl, 3,3,3-trifluoropropyl, nonafluorobutyl, 4,4,4-trifluorobutyl, dodecafluorohexyl, 6,6,6-trifluorohexyl, chlorophenyl, fluorophenyl, difluorophenyl, trifluoro Phenyl, tetrafluorophenyl, pentafluorophenyl, di-t-butyl-fluorophenyl, trifluoromethylphenyl, bistrifluoromethylphenyl, trifluoromethoxyphenyl, bistrifluoromethoxyphenyl, trifluoromethylthiophenyl, bistrifluoromethylthiophenyl, fluoro Biphenyl, difluorobiphenyl, trifluorobiphenyl, tetrafluorobiphenyl, pentafluorobiphenyl, di-t-butyl-fluorobiphenyl, trifluoromethylbiphenyl, bistrifluoromethylbiphenyl, trifluoromethoxybiphenyl, bistrifluoromethoxybiphenyl, trifluoromethyldimethyl Cyril, trifluoromethoxy, pentafluoroethoxy, fluorophenoxy, difluorophenoxy, trifluorophenoxy, pentafluorophenoxy, di-t-butyl-fluorophenoxy, trifluoromethylphenoxy, bistrifluoromethylphenoxy, trifluoromethoxyphenoxy, bistrifluoro Methoxyphenoxy, difluoromethylenedioxyphenyl, trifluoroacetyl, pentafluorobenzoyl, fluorophenyliminomethyl, pentafluorophenyliminomethyl, trifluoromethylphenyliminomethyl, bistrifluoromethylphenyliminomethyl, trifluoromethylthio, trifuryl, nonafryl, Trifurate, nonafrate, bistrifurylimide, trifluoromethylfuryl, trifluoromethylbenzofuryl, trifluoromethyldibenzofuryl, trifluoromethylpyrrolill, pentafluorophenylpyrrolill, fluoropyridyl, tetrafluoropyridyl, fluoroquinolyl, fluoroiso Kinolyl, Fluoroindrill, Trifluoromethylindrill, Bistrifluoromethylcarbazolyl, Trifluo Examples thereof include lomethylimidazolyl, trifluoromethyloxazolyl, trifluoromethylthienyl, trifluoromethylbenzothienyl, trifluoromethyldibenzothienyl, trifluoromethylthiazolyl, and trifluoromethylbenzothiazolyl.

Preferably, fluorine atom, chlorine atom, fluoromethyl, trifluoromethyl, pentafluoroethyl, 2,2,2-trifluoroethyl, 3,3,3-trifluoropropyl, 4,4,4-trifluorobutyl, Fluorophenyl, difluorophenyl, trifluorophenyl, tetrafluorophenyl, pentafluorophenyl, trifluoromethylphenyl, bistrifluoromethylphenyl, trifluoromethoxyphenyl, pentafluorobiphenyl, trifluoromethylbiphenyl, bistrifluoromethylbiphenyl, trifluoromethoxy , Pentafluorophenoxy, bistrifluoromethylphenoxy, bistrifluoromethylphenoxy, difluoromethylenedioxyphenyl, trifluoroacetyl, pentafluorobenzoyl, fluorophenyliminomethyl, pentafluorophenyliminomethyl, trifluoromethylphenyliminomethyl, trifluoromethylthio , Trifuryl, Trifurate, Nonafrate, Bistrifurylimide, Trifluoromethylfuryl, Trifluoromethylbenzofuryl, Trifluoromethyldibenzofuryl, Trifluoromethylpyrrolill, Pentafluorophenylpyrrolill, Fluoropyridyl, Tetrafluoropyridyl, Trifluoromethyl Indrill, bistrifluoromethylcarbazolyl, trifluoromethylthienyl, trifluoromethylbenzothienyl, trifluoromethylthiazolyl. More preferably, it is trifluoromethyl, fluorophenyl, pentafluorophenyl, trifluoromethylphenyl, bistrifluoromethylphenyl, pentafluorobiphenyl, trifluoromethoxy, pentafluorophenoxy.

Examples of the monovalent oxygen-containing group include methoxy, ethoxy, n-propoxy, isopropoxy, allyloxy, n-butoxy, s-butoxy, isobutoxy, t-butoxy, metalryloxy, prenyloxy, benzyloxy, and methoxymethoxy. Methoxyethoxy, phenoxy, naphthoxy, toluyloxy, isopropylphenoxy, allylphenoxy, t-butylphenoxy, methoxyphenoxy, isopropoxyphenoxy, allyloxyphenoxy, biphenyloxy, binaphthyloxy, methoxymethyl, allyloxymethyl, benzyloxymethyl, phenoxy Methyl, methoxyethyl, allyloxyethyl, benzyloxyethyl, phenoxyethyl, methoxypropyl, allyloxypropyl, benzyloxypropyl, phenoxypropyl, methoxyvinyl, allyloxyvinyl, benzyloxyvinyl, phenoxyvinyl, methoxyallyl, allyloxyallyl , Benzyloxyallyl, phenoxyallyl, formyl, acetyl, isobutyryl, pivaloyl, benzoyl, naphthoyl, adamantancarbonyl, acetoxy, pivaloyloxy, benzoyloxy, dimethoxymethyl, diisopropoxymethyl, dioxolanyl, tetramethyldioxolanyl, dioxanyl, methylcarbo Nate, phenylcarbonate, dimethyldioxanyl, methylcarboxylate, ethylcarboxylate, methoxyphenyl, isopropoxyphenyl, allyloxyphenyl, phenoxyphenyl, methylenedioxyphenyl, frill, methylfuryl, tetrahydrofuryl, pyranyl, tetrahydropyrani Le, flofryl, benzofuryl, dibenzofuryl and the like can be mentioned.

Preferably, methoxy, ethoxy, isopropoxy, allyloxy, n-butoxy, t-butoxy, prenyloxy, benzyloxy, phenoxy, naphthoxy, toluyloxy, isopropylphenoxy, allylphenoxy, t-butylphenoxy, methoxyphenoxy, biphenyloxy, Binaphthyloxy, allyloxymethyl, benzyloxymethyl, phenoxymethyl, methoxyethyl, methoxyallyl, benzyloxyallyl, phenoxyallyl, formyl, acetyl, isobutyryl, pivaloyl, benzoyl, naphthoyl, dimethoxymethyl, dioxolanyl, tetramethyldioxolanyl, With dioxanyl, dimethyldioxanyl, methylcarboxylate, ethylcarboxylate, methoxyphenyl, isopropoxyphenyl, allyloxyphenyl, phenoxyphenyl, methylenedioxyphenyl, frill, methylfuryl, tetrahydropyranyl, flofuryl, benzofuryl, dibenzofuryl is there. More preferably, methoxy, isopropoxy, allyloxy, phenoxy, formyl, acetyl, benzoyl, dimethoxymethyl, dioxolanyl, methylcarboxylate, methoxyphenyl, isopropoxyphenyl, allyloxyphenyl, phenoxyphenyl, frill, methylfuryl, benzofuryl, dibenzo It is a frill.

Examples of the monovalent nitrogen-containing group include cyano, dimethylamino, diethylamino, allylamino, diallylamino, didecylamino, benzylamino, dibenzylamino, pyrrolidinyl, piperidinyl, moriphoryl, azepinyl, formamide, acetamide, pivalamide, benzamide and naphthamide. , Adamantane Carboxamide, Iminomethyl, Iminoethyl, phenyliminomethyl, phenyliminoethyl, dimethylhydrazonomethyl, pyrrolidinyl iminomethyl, imide, uryl, methyluryl, dimethyluryl, guanidinyl, dimethylguanidinyl, methylformimidamide, phenyl Form imidazole, carbamoyl, N-methylcarbamoyl, N-benzylcarbamoyl, N, N-dimethylcarbamoyl, pyrrolidinylcarbamoyl, N-phenylcarbamoyl, carbamoyloxy, N-methylcarbamoyloxy, N-benzylcarbamoyloxy, N, N -Dimethylcarbamoyloxy, pyrrolidinylcarbamoyloxy, N-phenylcarbamoyloxy, dimethylaminomethyl, dibenzylaminomethyl, pyrrolidinylmethyl, dimethylaminoethyl, benzylaminomethyl, benzylaminoethyl, pyrrolidinylethyl, dimethylaminovinyl , Benzylaminovinyl, pyrrolidinylvinyl, dimethylaminopropyl, benzylaminopropyl, pyrrolidinylpropyl, dimethylaminoallyl, benzylaminoallyl, pyrrolidinylallyl, nitrophenyl, dinitrophenyl, aminophenyl, cyanophenyl, dimethylamino Phenyl, pyrrolidinylphenyl, pyrrolylphenyl, pyridylphenyl, quinolylphenyl, isoquinolylphenyl, indolinylphenyl, indolylphenyl, carbazolylphenyl, di-t-butylcarbazolylphenyl, pyrrolyl, methylpyrrolill, Phenylpyrrolyl, pyridyl, quinolyl, tetrahydroquinolyl, isoquinolyl, tetrahydroisoquinolyl, indolyl, indolinyl, carbazolyl, di-t-butylcarbazolyl, imidazolyl, dimethylimidazolidinyl, benzoimidazolyl, oxazolyl, oxazolidinyl, Benzoxazolyl and the like can be mentioned.

Preferably, cyano, dimethylamino, diethylamino, allylamino, benzylamino, dibenzylamino, pyrrolidinyl, piperidinyl, morpholyl, formamide, acetamide, benzamide, iminomethyl, iminoethyl, phenyliminomethyl, phenyliminoethyl, dimethylhydrazonomethyl, pyrrolidini. Luiminomethyl, carbamoyl, N-methylcarbamoyl, N-benzylcarbamoyl, N, N-dimethylcarbamoyl, pyrrolidinylcarbamoyl, N-phenylcarbamoyl, carbamoyloxy, N-methylcarbamoyloxy, N, N-dimethylcarbamoyloxy, dimethyl Aminomethyl, benzylaminomethyl, pyrrolidinylmethyl, dimethylaminoethyl, pyrrolidinylethyl, dimethylaminopropyl, pyrrolidinylpropyl, dimethylaminoallyl, pyrrolidinylallyl, nitrophenyl, dinitrophenyl, aminophenyl, cyanophenyl , Dimethylaminophenyl, pyrrolidinylphenyl, pyrrolylphenyl, carbazolylphenyl, di-t-butylcarbazolylphenyl, pyrrolyl, pyridyl, quinolyl, tetrahydroquinolyl, isoquinolyl, tetrahydroisoquinolyl, indolyl, indolinyl Carbazolyl, di-t-butylcarbazolyl, imidazolyl, dimethylimidazolidinyl, benzoimidazolyl, oxazolyl, oxazolidinyl, benzoxazoly. More preferably, it is dimethylamino, diethylamino, pyrrolidinyl, dimethylaminophenyl, pyrrolidinylphenyl, pyrrolyl, pyridyl, carbazolyl and imidazolyl.

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

Examples of the monovalent sulfur-containing group include methylthio, ethylthio, benzylthio, phenylthio, naphthylthio, methylthiomethyl, benzylthiomethyl, phenylthiomethyl, naphthylthiomethyl, methylthioethyl, benzylthioethyl, phenylthioethyl and naphthylthio. Ethyl, methylthiovinyl, benzylthiovinyl, phenylthiovinyl, naphthylthiovinyl, methylthiopropyl, benzylthiopropyl, phenylthiopropyl, naphthylthiopropyl, methylthioallyl, benzylthioallyl, phenylthioallyl, naphthylthioallyl, mercaptophenyl, Methylthiophenyl, thienylphenyl, methylthienylphenyl, benzothienylphenyl, dibenzothienylphenyl, benzodithienylphenyl, methylsulfinyl, t-butylsulfinyl, phenylsulfinyl, mesyl, benzenesulfonyl, tosyl, methanesulfonate, 4-methylbenzenesulfo Nate, thiouryl, methylthiouryl, bis (methylthio) methyl, thienyl, tetrahydrothienyl, methylthienyl, thienofryl, thienothienyl, benzothienyl, dibenzothienyl, thienobenzofuryl, benzodithienyl, dithiolanyl, dithianol, oxathiolanyl, oxathianol, thiazolyl, benzothiazol , Thiazoridinyl and the like. Preferred are thienyl, methylthienyl, thienovryl, thienotienyl, benzothienyl, dibenzothienyl, thienobenzofuryl, benzodithienyl, thiazolyl and benzothiazolyl.

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

Examples of the monovalent silicon-containing group include trimethylsilyl, triethylsilyl, triisopropylsilyl, diphenylmethylsilyl, t-butyldimethylsilyl, t-butyldiphenylsilyl, triphenylsilyl, tris (trimethylsilyl) silyl, and cyclopentadi. Enyldimethylsilyl, di-n-butyl (cyclopentadienyl) silyl, cyclopentadienyldiphenylsilyl, indenyldimethylsilyl, di-n-butyl (indenyl) silyl, indenyldiphenylsilyl, fluorenyldimethylsilyl, Di-n-butyl (fluorenyl) silyl, fluorenyldiphenylsilyl, 4-trimethylsilylphenyl, 4-triethylsilylphenyl, 4-triisopropylsilylphenyl, 4-t-butyldiphenylsilylphenyl, 4-triphenylsilylphenyl, 4-Tris (trimethylsilyl) silylphenyl and the like can be mentioned. Preferably, trimethylsilyl, triethylsilyl, triisopropylsilyl, t-butyldimethylsilyl, triphenylsilyl, cyclopentadienyldimethylsilyl, cyclopentadienyldiphenylsilyl, indenyldimethylsilyl, indenyldiphenylsilyl, fluorenyldimethyl Silyl, fluorenyldiphenylsilyl, 4-trimethylsilylphenyl, 4-triethylsilylphenyl, 4-triisopropylsilylphenyl, 4-triphenylsilylphenyl. More preferably, it is trimethylsilyl, triethylsilyl, t-butyldimethylsilyl, 4-trimethylsilylphenyl, 4-triethylsilylphenyl, 4-triisopropylsilylphenyl.

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

R ² and R ³ may form a saturated or unsaturated hydrocarbon group having a 5- to 8-membered ring fused to the cyclopentadienyl ring moiety, preferably a 5- or 6-membered ring. In this case, as a structure combined with the cyclopentadienyl moiety of the mother nucleus, indene, 2-methylindene, 2-methyl-4-phenylindene, 2-methylbenzoindene, 4,5,6,7-tetrahydroindene, 2-Methyl-1,5,6,7-Tetrahydro-s-Indene, 6,7-Dihydro-5H-s-Indene, 6,7-Dihydro-8H-as-Indene, 1H-Benz [f] Indene, 5,6,7,8-Tetrahydro-1H-benz [f] indene, 3H-benz [e] indene, 6,7,8,9-tetrahydro-3H-benz [e] indene, 5,7-dihydro- 4H-cyclopenta [e] acenaftylene, 1,1,3-trimethyl-1,9-dihydrocyclopenta [b] fluorene, 1,1,3,6,8,8-hexamethyl-8,10-dihydro-1H- Dicyclopenta [b, h] fluorene, 1,3,3-trimethyl-3,9-dihydrocyclopenta [b] fluorene, 1,3,3,6,6,8-hexamethyl-6,10-dihydro-3H- Dicyclopenta [b, h] fluorene, 6,6-dimethyl-7,8,9,11-tetrahydro-6H-benzo [b] fluorene, 4,4,7,7-tetramethyl-2,3,4,7 , 8,9,10,12-octahydro-1H-dibenzo [b, h] fluorene, 6,6,9,9-tetramethyl-7,8,9,11-tetrahydro-6H-benzo [b] fluorene, 1,1,4,4,7,7,10,10-octamethyl-2,3,4,7,8,9,10,12-octahydro-1H-dibenzo [b, h] fluorene, 1,2, 2,4-Tetramethyl-2,10-dihydro-1H-indeno [1,2-g] quinoline, 1,2,2,4,7,9,9,10-octamethyl-2,9,10,12 -Tetrahydro-1H-cyclopenta [1,2-g: 5,4-g'] Diquinolin, azulene and the like can be mentioned.

In the formula (II), ^{it is preferable that R 2} , R ³ and R ⁴ are all hydrogen atoms. In the formula (III), ^{it is preferable that R 2} , R ³ and R ⁴ are all hydrogen atoms. In the formula (IV), ^{it is preferable that R 2} , R ³ and R ⁴ are all hydrogen atoms.

R ⁵ and R ⁶ may form a saturated or unsaturated hydrocarbon group having a 5- to 8-membered ring fused to the fluorene ring moiety, preferably a 5- or 6-membered ring. In this case, as a structure combined with the fluorenyl moiety of the mother nucleus, 1,1,3-trimethyl-1,9-dihydrocyclopenta [b] fluorene, 1,1,3,6,8,8-hexamethyl-8, 10-Dihydro-1H-dicyclopenta [b, h] fluorene, 1,3,3-trimethyl-3,9-dihydrocyclopenta [b] fluorene, 1,3,3,6,6,8-hexamethyl-6,6 10-Dihydro-3H-dicyclopenta [b, h] fluorene, 6,6-dimethyl-7,8,9,11-tetrahydro-6H-benzo [b] fluorene, 4,4,7,7-tetramethyl-2 , 3,4,7,8,9,10,12-octahydro-1H-dibenzo [b, h] fluorene, 6,6,9,9-tetramethyl-7,8,9,11-tetrahydro-6H- Benzo [b] fluorene, 1,1,4,4,7,7,10,10-octamethyl-2,3,4,7,8,9,10,12-octahydro-1H-dibenzo [b, h] Fluorene, 1,2,2,4-tetramethyl-2,10-dihydro-1H-indeno [1,2-g] quinoline, 1,2,2,4,7,9,9,10-octamethyl-2 , 9,10,12-Tetrahydro-1H-cyclopenta [1,2-g: 5,4-g'] Diquinolin and the like.

In the formulas (II), (III) and (IV), if R ⁵ and R ⁶ do not form a saturated or unsaturated hydrocarbon group having a 5- to 8-membered ring fused to the fluorene ring moiety, it is designated as ^{R 5.} Is a monovalent group, which is a hydrocarbon group, a halogen-containing group, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group or a tin-containing group. Is preferable. In this case, R ⁶ is not particularly limited as long as it exerts the effect of the present invention, but it is preferably a hydrogen atom.

In the formulas (II) and (III), Q ² and Q ³ are divalent groups that bind two ligands, and are independently hydrocarbon groups having 1 to 20 carbon atoms and halogen-containing groups, respectively. , Silicon-containing group, germanium-containing group or tin-containing group.

Examples of the divalent hydrocarbon group having 1 to 20 carbon atoms include an alkylene group having 1 to 20 carbon atoms, a substituted alkylene group, a cycloalkylene group and an alkylidene group. Specific examples include alkylene groups such as methylene, ethylene, propylene and butylene, isopropyridene, dimethylmethylene, diethylmethylene, dipropylmethylene, diisopropylmethylene, dibutylmethylene, methylethylmethylene, methylbutylmethylene and methyl-t-butylmethylene. , Dihexylmethylene, dicyclohexylmethylene, methylcyclohexylmethylene, methylphenylmethylene, diphenylmethylene, ditrilmethylene, methylnaphthylmethylene, dinaphthylmethylene, 1-methylethylene, 1,2-dimethylethylene, 1-ethyl-2-methylethylene Substituted alkylene groups such as cyclopropylidene, cyclobutylidene, cyclopentylidene, cyclohexylidene, cycloheptylidene, bicyclo [3.3.1] nonylidene, norbornylidene, adamantylidene, tetrahydronaphthylidene, dihydroin methylene Examples thereof include cycloalkylene groups such as lidene, and alkylidene groups such as ethylidene, propylidene, and butylidene.

Examples of the divalent silicon-containing group include silylene, methylsilylene, dimethylsilylene, diisopropylsilylene, dibutylsilylene, methylbutylcilylene, methyl-t-butylcilylene, dicyclohexylsilylene, methylcyclohexylcilylene, methylphenylcilylene, diphenylcilylene, and di. Examples thereof include trilylcyrylene, methylnaphthylcilylene, dinaphthylcilylene, cyclodimethylenesilylene, cyclotrimethylenecilylene, cyclotetramethylenesilylene, cyclopentamethylenesilylene, cyclohexamethylenecilylene, cycloheptamethylenecilylene group and the like. Preferred are dimethylsilylene, dibutylsilylene and diphenylsilylene.

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

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

Both Q ² and Q ³ are preferably an alkylene group having 1 to 20 carbon atoms, a substituted alkylene group, an alkylidene group, or a silicon-containing group. More preferably, alkylene groups such as methylene, ethylene, propylene and butylene, isopropyridene, dimethylmethylene, diethylmethylene, dipropylmethylene, diisopropylmethylene, dibutylmethylene, methylethylmethylene, methylbutylmethylene, methyl-t-butylmethylene, Dihexylmethylene, dicyclohexylmethylene, methylcyclohexylmethylene, methylphenylmethylene, diphenylmethylene, ditrilmethylene, methylnaphthylmethylene, dinaphthylmethylene, 1-methylethylene, 1,2-dimethylethylene, 1-ethyl-2-methylethylene, etc. It is a substituted alkylene group of.

Q ² or Q ³ may ^{form a 3- to 8-membered ring containing Q 2} or Q 3, preferably a 5- to 6-membered ring. Examples of the structure in this case include cyclopentane, cyclohexane, sirolan, and silinan ring.

In the formula (IV), Q ⁴ is carbon atom, silicon atom, germanium atom or a tin atom, preferably a carbon atom or a silicon atom.

In the above formula (IV), R ⁷ is a monovalent group, which is a hydrocarbon group, a halogen-containing group, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, and a germanium. It is preferably a containing group or a tin-containing group, more preferably a hydrocarbon group or a halogen-containing group, a linear or branched alkyl group having 1 to 20 carbon atoms, and an aromatic having 7 to 20 carbon atoms. More preferably, a linear or branched alkyl group containing or an unsaturated double bond containing group, or an aryl group having 6 to 20 carbon atoms is preferable.

R ³ and Q ² , R ³ and Q ³ , or R ³ and R ⁷ may combine with each other to form a ring. Examples of such a ring structure include a saturated 5-membered ring and a bicyclic saturated 5-membered ring. Specific examples thereof include a cyclopentane ring matrix, an octahydroindene ring matrix, and an octahydropentane ring matrix.

In the formulas (II), (III) and (IV), X is a monovalent group, and each of them independently has a hydrogen atom, a halogen atom, a hydrocarbon group, a halogen-containing group, a silicon-containing group and an oxygen-containing group. It is a sulfur-containing group, a nitrogen-containing group, a phosphorus-containing group, a boron-containing group or an aluminum-containing group, and may be the same or different from each other. X can be the same as X in the formula (I).

In the formulas (II), (III) and (IV), M is a titanium atom, a zirconium atom or a hafnium atom, preferably a zirconium atom or a hafnium atom, and particularly preferably a zirconium atom.

In the formulas (II), (III) and (IV), L is a divalent hydrocarbon group having a linear carbon chain having 1 to 10 carbon atoms, which is more active and has the above-mentioned extreme viscosity. From the viewpoint that [η] ₁ and [η] ₂ do not change, a divalent hydrocarbon group having a linear carbon chain having 1 to 3 carbon atoms is preferable. Specifically, methylene bridge, 1,2-ethane bridge, 1,3-propane bridge, 1,4-butane bridge, 1,5-pentane bridge, 1,6-hexane bridge, 1,7-heptane bridge, Examples thereof include 1,8-octane cross-linking, 1,9-nonane cross-linking, and 1,10-decane cross-linking. Preferred are methylene cross-linking, 1,2-ethane cross-linking, 1,3-propane cross-linking, and 1,4-butane cross-linking.

In the formulas (II), (III) and (IV), D ¹ , D ² and D ³ are the formulas (D-a), (D-b), (D-c), and (D-d, respectively). ), (D-e), (D-f), (D-g), (D-h) or (D-i).

In the formula (II), D ¹ refers to the formulas (D-a), (D-b), (D-c), (D-d), (D-e), (D-g), (. The group represented by Dh) or (Di) is preferable, and the group represented by the formulas (Da), (Db), (Dc) or (Dd) is more preferable. The group represented by the formula (D-a), (D-b) or (D-c) is more preferable, and the group represented by the formula (D-a) is particularly preferable.

In the formula (III), D ² is the formula (D-a), (D-b), (D-c), (D-d), (D-e), (D-g), (. The group represented by Dh) or (Di) is preferable, and the group represented by the formulas (Da), (Db), (Dc) or (Dd) is more preferable. The group represented by the formula (D-a), (D-b) or (D-c) is more preferable, and the group represented by the formula (D-a) is particularly preferable.

In the formula (IV), D ³ is the formula (Db), (Dc), (Dd), (Df), (Dg), (Dh) or (D). The group represented by D-i) is preferable, the group represented by the formula (D-b), (D-c) or (D-d) is more preferable, and the group represented by the formula (D-b) or (D-c) is more preferable. ) Is more preferable, and the group represented by the above formula (Db) is particularly preferable.

In the formulas (D-b), (D-c), (D-d), (D-e), (D-f) and (D-g), R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ And R ¹³ are monovalent groups, which are independently hydrogen atom, halogen atom, hydrocarbon group, halogen-containing group, silicon-containing group, oxygen-containing group, nitrogen-containing group, boron-containing group, sulfur-containing group, and phosphorus. It is a containing group, a silicon-containing group, a germanium-containing group or a tin-containing group, and may be the same or different from each other, and adjacent substituents may be bonded to each other to form a ring. These groups, the formula (II), include (III) in and ^{(IV), R 2, R} 3, R 4, R 5, those exemplified by ^{R 6} and ^{R 7} the same substituents ..

In the formula (D-b), it may form a 3-8 membered ring containing an unsaturated bond which is adjacent to R ⁸ have, taken together mother skeleton, preferably a 5- or 6-membered ring. Examples of the structure in this case include cyclopentene, cyclohexene, cyclooctene, cyclopentadiene, cyclohexadiene, cyclooctadiene and the like. R ⁸ is preferably a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom or a linear or branched alkyl group having 1 to 20 carbon atoms, and even more preferably a hydrogen atom or methyl. Particularly preferably, all are hydrogen atoms.

In the formula (D-c), Ch is an oxygen atom or a sulfur atom, preferably an oxygen atom. R ⁹ is a monovalent group, which is a linear or branched alkyl group having 1 to 20 carbon atoms, an aromatic-containing linear or branched alkyl group having 7 to 20 carbon atoms, or an unsaturated double bond. It is preferably an containing group or an aryl group having 6 to 20 carbon atoms, and more preferably methyl, ethyl, isopropyl, t-butyl, benzyl or allyl.

In the formula (Dd), Pn is a nitrogen atom or a phosphorus atom, preferably a nitrogen atom. R ¹⁰ to each other may be bonded to form a 3-8 membered ring containing a nitrogen atom together, preferably 5- or 6-membered ring. Examples of the structure in this case include pyrrolidine, pyrrole, piperidine, morpholine, indoline, and indole. R ¹⁰ is preferably methyl, ethyl, isopropyl, t-butyl, benzyl and allyl.

In the formulas (D-e) and (D-f), R ¹¹ is a monovalent group, and each of them independently has a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, and a halogen-containing hydrocarbon group. , A silicon-containing hydrocarbon group, an oxygen-containing hydrocarbon group, a sulfur-containing hydrocarbon group or a nitrogen-containing hydrocarbon group is preferable. Each of R ¹¹ may be the same or different, and in combination with one or more adjacent groups, the adjacent substituents are bonded to each other and a 5- to 8-membered ring condensing to the benzene ring portion which is the mother skeleton. Saturated or unsaturated hydrocarbon groups may be formed, preferably a 5- or 6-membered ring. Examples of the structure combined with the benzene ring portion of the mother nucleus include indacen, indene, naphthalene, benzofuran, benzothiophene, indole, and quinoline.

In R ^11, examples of the halogen atom, the formula (II), (III) in and ^(IV), are the same as those mentioned ^{R 2, R 3, R 4} , R 5, R 6 and ^{R 7} , Preferably a fluorine atom or a chlorine atom.

In R ¹¹ , the hydrocarbon groups having 1 to 20 carbon atoms are represented by R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ in the formulas (II), (III) and (IV). Substituents similar to those mentioned above are mentioned, preferably methyl, ethyl, isopropyl, t-butyl, vinyl, allyl, prenyl, phenyl.

In R ¹¹ , the halogen-containing hydrocarbon group contains the halogens listed ^{in R 2} , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ in the formulas (II), (III) and (IV). Substituents similar to the group can be mentioned, preferably trifluoromethyl.

In R ^11, examples of the silicon-containing hydrocarbon group, the formula (II), in (III) and ^(IV), silicon-containing mentioned in ^{R 2, R 3, R 4} , R 5, R 6 and ^{R 7} Substituents similar to the group can be mentioned, preferably trimethylsilyl.

In R ¹¹ , the oxygen-containing hydrocarbon group contains the oxygens listed ^{in R 2} , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ in the formulas (II), (III) and (IV). Substituents similar to the group can be mentioned, preferably a methoxy or frill group.

In R ^11, examples of the sulfur-containing hydrocarbon group, the formula (II), in (III) and ^(IV), sulfur-containing mentioned in ^{R 2, R 3, R 4} , R 5, R 6 and ^{R 7} Substituents similar to the group can be mentioned, preferably methylthio, thienyl.

In R ¹¹ , the nitrogen-containing hydrocarbon group contains the nitrogens listed ^{in R 2} , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ in the formulas (II), (III) and (IV). Substituents similar to the group are mentioned, preferably cyano, dimethylamino, diethylamino, pyrrolidinyl, pyrrolyl, pyridyl, indolyl, carbazolyl, imidazolyl.

In the formula (Df), R ¹² is a monovalent group, which is an oxygen-containing group, a nitrogen-containing group, a sulfur-containing group, or a phosphorus-containing group. These groups, the formula (II), include (III) in and ^{(IV), R 2, R} 3, R 4, R 5, those exemplified by ^{R 6} and ^{R 7} the same substituents .. R ¹² may be combined with adjacent R ¹¹ to form a ring, preferably a 3- to 8-membered ring, more preferably a 5- to 6-membered ring. Examples of the structure in this case include indoline, indole, benzofuran, benzothiophene, quinoline and the like. R ¹² is preferably an oxygen-containing hydrocarbon group, a nitrogen-containing hydrocarbon group, a sulfur-containing hydrocarbon group or a phosphorus-containing hydrocarbon group, and more preferably methoxy, ethoxy, isopropoxy, t-butoxy, frills, cyano, and the like. Dimethylamino, diethylamino, pyrrolidinyl, pyrrolyl, pyridyl, indolyl, carbazolyl, imidazolyl, methylthio, thienyl, diphenylphosphino.

In the formula ^{(D-g), R 13} is preferably methyl, isopropyl, t- butyl, phenyl, trimethylsilyl.

In the formulas (II) and (III), preferred examples of the fluorene ring 4-position substituent represented by LD ¹ and the cyclopentadienyl ring 3-position substituent represented by LD ^{2 are preferable.} n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, allyl, ω-butenyl, ω-pentenyl, ω-hexenyl, ω-heptenyl, ω-octenyl, 3-methoxypropyl , 4-methoxybutyl, 5-methoxypentyl, 3-dimethylaminopropyl, 4-dimethylaminobutyl, 2-methoxybenzyl, 2-methoxyphenethyl, 2-vinylbenzyl, 2-vinylphenethyl, 2-allylbenzyl, 2- Allyl phenethyl. Since ω indicates the end of the substituent, it means that it has a terminal unsaturated bond.

In the above formula (IV), ^{preferred examples of the cross-linking substituent represented by L-D 3} are allyl, ω-butenyl, ω-pentenyl, ω-hexenyl, ω-heptenyl, ω-octenyl and 3-methoxy. Propyl, 4-methoxybutyl, 5-methoxypentyl, 3-dimethylaminopropyl, 4-dimethylaminobutyl, 2-methoxybenzyl, 2-methoxyphenethyl, 2-vinylbenzyl, 2-vinylphenethyl, 2-allylbenzyl, 2 -Allyl phenethyl.

The method for producing the compound represented by the formulas (II), (III) and (IV) is not particularly limited as long as the compound exhibiting the effect of the present invention can be obtained, and can be produced by a known method, which is typical. An example of the synthetic route is 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. Examples of known production methods include the methods described in JP-A-2006-233208, JP-A-2009-143901, and JP-A-2009-144148.

The substituted fluorene compound can be produced by a known method, and the production method is not particularly limited. As a known production method, for example, the method described in "J. Org. Chem. 2000, 65, 3858.", International Publication No. 2001/0271124, International Publication No. 2004/029062, International Publication No. 2006/1260680, and the like. Can be mentioned.

The bromination product of the substituted fluorene compound and the coupling reaction product of the bromination product and the boron compound can be produced by a known method, and the production method is not particularly limited. Known manufacturing methods include, for example, the method described in US Pat. No. 7,470,759.

The precursor compound (ligand) of the compound represented by the formulas (II), (III) and (IV) is made from a substituted cyclopentadiene compound, a substituted fluorene compound, a substituted carbonyl compound or a halogenated substituted silicon compound as a raw material. It can be produced by a known method, and the production method is not particularly limited. Known production methods include, for example, the methods described in International Publication No. 2009/045301, International Publication No. 2004/029062, and JP-A-2009-143901.

The compound represented by the formula (II), (III) or (IV) can be produced by a known method using the precursor compound (ligand), and the production method is particularly limited. is not it. As a known production method, for example, the method described in International Publication No. 2004/029062 can be mentioned.

Hereinafter, specific examples of the compounds represented by the formulas (II), (III) or (IV) will be shown, but the scope of the present invention is not particularly limited thereto. In the present invention, as the component (B), two or more kinds of compounds having different chemical structures among the compounds represented by the formulas (II), (III) or (IV) may be used. Further, optical isomers having the same chemical structure may be used alone, or an optical isomer mixture having the same chemical structure (for example, a meso-form mixture or a racemic mixture) may be used.

Of the compounds represented by the formula (II), for convenience, the ligand structure excluding the MX 2 _(metal portion), the cyclopentadienyl ring moiety, the structure of the bridging moiety (Q ^2), fluorenyl ring 1 , 3, 5, 6, 7, 8 position substituents (R ^{4 to} R ⁶ ) and fluorenyl ring 4-position substituent (LD ¹ ). The abbreviation for the cyclopentadienyl ring moiety is II-α, the abbreviation for the structure of the crosslinked moiety is II-β, the abbreviation for the combined structure of the cyclopentadienyl ring and the crosslinked moiety is II-γ, and 2,3,6 of the fluorenyl ring. , The abbreviation of the combination structure of the 7-position substituent is II-δ, the abbreviation of the combination structure of the 4-position substituent of the fluorenyl ring is II-ε, and specific examples of each structure are shown in Tables 1 to 5 below.

表１〜表５に従えば、シクロペンタジエニル環部分が表１のＩＩ−α−６、架橋部分が表２のＩＩ−β−３、フルオレニル環部分が表４のＩＩ−δ−９、フルオレニル環の４位置換基が表５のＩＩ−ε−６の組み合わせで構成され、金属部分のＭＸ_２がＺｒＣｌ_２の場合は、下記式（ＩＩ−１）で表される化合物を例示している。

According to Tables 1 to 5, the cyclopentadienyl ring moiety is II-α-6 in Table 1, the crosslinked moiety is II-β-3 in Table 2, and the fluorenyl ring moiety is II-δ-9 in Table 4. When the 4-position substituent of the fluorenyl ring is composed of the combination of II-ε-6 in Table 5 and the MX _{2 of} the metal portion is ZrCl ₂ , the compound represented by the following formula (II-1) is exemplified. There is.

また、シクロペンタジエニル環部分が表１のＩＩ−α−３、架橋部分が表２のＩＩ−β−１２、フルオレニル環部分が表４のＩＩ−δ−５、フルオレニル環の４位置換基が表５のＩＩ−ε−８の組み合わせで構成され、金属部分のＭＸ_２がＨｆＣｌ_２の場合は、下記式（ＩＩ−２）で表される化合物を例示している。

The cyclopentadienyl ring moiety is II-α-3 in Table 1, the crosslinked moiety is II-β-12 in Table 2, the fluorenyl ring moiety is II-δ-5 in Table 4, and the 4-position substituent of the fluorenyl ring. Is composed of the combination of II-ε-8 in Table 5, _{and when MX 2 of} the metal portion is HfCl ₂ , the compound represented by the following formula (II-2) is exemplified.

また、シクロペンタジエニル環部分が表１のＩＩ−α−１、架橋部分が表２のＩＩ−β−１７、フルオレニル環部分が表４のＩＩ−δ−１３、フルオレニル環の４位置換基が表５のＩＩ−ε−１３の組み合わせで構成され、金属部分のＭＸ_２がＺｒ（ＮＭｅ_２）_２の場合は、下記式（ＩＩ−３）で表される化合物を例示している。

The cyclopentadienyl ring moiety is II-α-1 in Table 1, the crosslinked moiety is II-β-17 in Table 2, the fluorenyl ring moiety is II-δ-13 in Table 4, and the 4-position substituent of the fluorenyl ring. Is composed of the combination of II-ε-13 in Table 5, and when MX _{2 of} the metal portion is Zr (NMe ₂ ) ₂ , the compound represented by the following formula (II-3) is exemplified.

また、シクロペンタジエニル環と架橋部分の組み合わせ構造が表３のＩＩ−γ−８、フルオレニル環部分が表４のＩＩ−δ−１９、フルオレニル環の４位置換基が表５のＩＩ−ε−２３の組み合わせで構成され、金属部分のＭＸ_２がＨｆ（Ｍｅ）_２の場合は、下記式（ＩＩ−４）で表される化合物を例示している。

The combination structure of the cyclopentadienyl ring and the crosslinked moiety is II-γ-8 in Table 3, the fluorenyl ring moiety is II-δ-19 in Table 4, and the 4-position substituent of the fluorenyl ring is II-ε in Table 5. When it is composed of a combination of -23 and the MX _{2 of} the metal portion is Hf (Me) ₂ , the compound represented by the following formula (II-4) is exemplified.

前記式（ＩＩＩ）で表される化合物のうち、便宜上、ＭＸ_２（金属部分）を除いたリガンド構造を、シクロペンタジエニル環の２，３あるいは４，５位の置換基（Ｒ^２，Ｒ^３）、架橋部分の構造（Ｑ^３）、フルオレニル環部分の構造およびシクロペンタジエニル環の３あるいは４位の置換基（Ｌ−Ｄ^２）の４つに分ける。シクロペンタジエニル環の２，３あるいは４，５位の置換基の組み合わせ構造の略称をＩＩＩ−α、架橋部分の構造の略称をＩＩＩ−β、シクロペンタジエニル環と架橋部分の組み合わせ構造の略称をＩＩＩ−γ、フルオレニル環部分構造の略称をＩＩＩ−δ、シクロペンタジエニル環の３あるいは４位置換基の組み合わせ構造の略称をＩＩＩ−εとし、各構造の具体例を以下の表６〜表１０に示す。

Among the formula (III) compounds represented by, for convenience, the ligand structure excluding the MX ₂ (metal portion), 2,3 or 4,5-position substituent of the cyclopentadienyl ring ^(R 2, R ^3), the structure of the bridging moiety (Q ^3), divided into four structures and cyclopentadienyl 3 or 4 position substituent of the ring of the fluorenyl ring moiety (L-D ^2). The abbreviation of the combination structure of the substituents at the 2, 3 or 4, 5 positions of the cyclopentadienyl ring is III-α, the abbreviation of the structure of the crosslinked portion is III-β, and the abbreviation of the combination structure of the cyclopentadienyl ring and the crosslinked portion The abbreviation is III-γ, the abbreviation of the fluorenyl ring partial structure is III-δ, the abbreviation of the combination structure of the 3- or 4-position substituent of the cyclopentadienyl ring is III-ε, and specific examples of each structure are shown in Table 6 below. ~ Table 10 shows.

表６〜表１０に従えば、シクロペンタジエニル環部分が表６のＩＩＩ−α−２、架橋部分が表７のＩＩＩ−β−１、フルオレニル環部分が表９のＩＩＩ−δ−１０、シクロペンタジエニル環の３あるいは４位置換基が表１０のＩＩＩ−ε−１の組み合わせで構成され、金属部分のＭＸ_２がＺｒＣｌ_２の場合は、下記式（ＩＩＩ−１）で表される化合物を例示している。

According to Tables 6 to 10, the cyclopentadienyl ring moiety is III-α-2 in Table 6, the crosslinked moiety is III-β-1 in Table 7, and the fluorenyl ring moiety is III-δ-10 in Table 9. When the 3- or 4-position substituent of the cyclopentadienyl ring is composed of the combination of III-ε-1 in Table 10 and the MX _{2 of} the metal portion is ZrCl ₂ , it is represented by the following formula (III-1). The compound is illustrated.

また、シクロペンタジエニル環部分が表６のＩＩＩ−α−５、架橋部分が表７のＩＩＩ−β−１６、フルオレニル環部分が表９のＩＩＩ−δ−１７、シクロペンタジエニル環の３あるいは４位置換基が表１０のＩＩＩ−ε−２０の組み合わせで構成され、金属部分のＭＸ_２がＨｆ（ＮＭｅ_２）_２の場合は、下記式（ＩＩＩ−２）で表される化合物を例示している。

The cyclopentadienyl ring moiety is III-α-5 in Table 6, the crosslinked moiety is III-β-16 in Table 7, the fluorenyl ring moiety is III-δ-17 in Table 9, and cyclopentadienyl ring 3 Alternatively, when the 4-position substituent is composed of the combination of III-ε-20 in Table 10 and the MX _{2 of} the metal portion is Hf (NMe ₂ ) ₂ , the compound represented by the following formula (III-2) is exemplified. doing.

また、シクロペンタジエニル環部分が表６のＩＩＩ−α−１、架橋部分が表７のＩＩＩ−β−２０、フルオレニル環部分が表９のＩＩＩ−δ−１４、シクロペンタジエニル環の３あるいは４位置換基が表１０のＩＩＩ−ε−２５の組み合わせで構成され、金属部分のＭＸ_２がＴｉＣｌ_２の場合は、下記式（ＩＩＩ−３）で表される化合物を例示している。

The cyclopentadienyl ring moiety is III-α-1 in Table 6, the crosslinked moiety is III-β-20 in Table 7, the fluorenyl ring moiety is III-δ-14 in Table 9, and cyclopentadienyl ring 3 Alternatively, when the 4-position substituent is composed of the combination of III-ε-25 in Table 10 and the MX _{2 of} the metal portion is TiCl ₂ , the compound represented by the following formula (III-3) is exemplified.

また、シクロペンタジエニル環と架橋部分の組み合わせ構造が表８のＩＩＩ−γ−１、フルオレニル環部分が表９のＩＩＩ−δ−２０、シクロペンタジエニル環の３あるいは４位置換基が表１０のＩＩＩ−ε−３０の組み合わせで構成され、金属部分のＭＸ_２がＺｒＭｅ_２の場合は、下記式（ＩＩＩ−４）で表される化合物を例示している。

The combination structure of the cyclopentadienyl ring and the crosslinked moiety is III-γ-1 in Table 8, the fluorenyl ring moiety is III-δ-20 in Table 9, and the 3- or 4-position substituent of the cyclopentadienyl ring is shown. When it is composed of a combination of 10 III-ε-30 and the MX _{2 of} the metal portion is ZrMe ₂ , the compound represented by the following formula (III-4) is exemplified.

前記式（ＩＶ）で表される化合物のうち、便宜上、ＭＸ_２（金属部分）を除いたリガンド構造を、シクロペンタジエニル環部分、架橋部分の構造（Ｒ^７−Ｑ^４）、フルオレニル環部分の構造および架橋部分の置換基（Ｌ−Ｄ^３）の４つに分ける。シクロペンタジエニル環部分の構造の略称をＩＶ−α、架橋部分の構造の略称をＩＶ−β、シクロペンタジエニル環と架橋部分の組み合わせ構造の略称をＩＶ−γ、フルオレニル環部分構造の略称をＩＶ−δ、架橋部分の置換基の組み合わせ構造の略称をＩＶ−εとし、各構造の具体例を表１１〜表１５に示す。

Of the compounds represented by the formula (IV), for convenience, MX ₂ ligand structure excluding the (metal portion), the cyclopentadienyl ring moiety, the structure of the bridging moiety ^(R 7 ^-Q 4), fluorenyl ring portion The structure of the above and the substituent (LD ³ ) of the crosslinked portion are divided into four. The abbreviation for the structure of the cyclopentadienyl ring portion is IV-α, the abbreviation for the structure of the crosslinked moiety is IV-β, the abbreviation for the combined structure of the cyclopentadienyl ring and the crosslinked moiety is IV-γ, and the abbreviation for the fluorenyl ring partial structure. Is IV-δ, and the abbreviation of the combined structure of the substituent of the crosslinked portion is IV-ε, and specific examples of each structure are shown in Tables 11 to 15.

表１１〜表１５に従えば、シクロペンタジエニル環部分が表１１のＩＶ−α−４、架橋部分構造が表１２のＩＶ−β−２、フルオレニル環部分が表１４のＩＶ−δ−１、架橋部分の置換基が表１５のＩＶ−ε−２の組み合わせで構成され、金属部分のＭＸ_２がＴｉ（η^４−１，３−ペンタジエニル）の場合は、下記式（ＩＶ−１）で表される化合物を例示している。

According to Tables 11 to 15, the cyclopentadienyl ring moiety is IV-α-4 in Table 11, the crosslinked moiety structure is IV-β-2 in Table 12, and the fluorenyl ring moiety is IV-δ-1 in Table 14. , substituent groups of the crosslinking moiety is a combination of IV-epsilon-2 of Table 15, if MX ₂ metal parts of Ti (η ⁴ -1,3- pentadienyl) is the following formula (IV-1) The compounds represented are illustrated.

また、シクロペンタジエニル環部分が表１１のＩＶ−α−１、架橋部分構造が表１２のＩＶ−β−９、フルオレニル環部分が表１４のＩＶ−δ−７、架橋部分の置換基が表１５のＩＶ−ε−１１の組み合わせで構成され、金属部分のＭＸ_２がＨｆＢｎ_２の場合は、下記式（ＩＶ−２）で表される化合物を例示している。

The cyclopentadienyl ring moiety is IV-α-1 in Table 11, the crosslinked moiety structure is IV-β-9 in Table 12, the fluorenyl ring moiety is IV-δ-7 in Table 14, and the substituent of the crosslinked moiety is. When it is composed of the combination of IV-ε-11 in Table 15 and the MX _{2 of} the metal portion is HfBn ₂ , the compound represented by the following formula (IV-2) is exemplified.

また、シクロペンタジエニル環部分が表１１のＩＶ−α−８、架橋部分構造が表１２のＩＶ−β−１６、フルオレニル環部分が表１４のＩＶ−δ−１６、架橋部分の置換基が表１５のＩＶ−ε−２５の組み合わせで構成され、金属部分のＭＸ_２がＺｒ（ＯｉＰｒ）_２の場合は、下記式（ＩＶ−３）で表される化合物を例示している。

The cyclopentadienyl ring moiety is IV-α-8 in Table 11, the crosslinked moiety structure is IV-β-16 in Table 12, the fluorenyl ring moiety is IV-δ-16 in Table 14, and the substituents in the crosslinked moiety are. When it is composed of the combination of IV-ε-25 in Table 15 and the MX _{2 of} the metal portion is Zr (OiPr) ₂ , the compound represented by the following formula (IV-3) is exemplified.

また、シクロペンタジエニル環と架橋部分の組み合わせ構造が表１３のＩＶ−γ−５、フルオレニル環部分が表１４のＩＶ−δ−１８、架橋部分の置換基が表１５のＩＶ−ε−２７の組み合わせで構成され、金属部分のＭＸ_２がＺｒＢｒ_２の場合は、下記式（ＩＶ−４）で表される化合物を例示している。

The combination structure of the cyclopentadienyl ring and the crosslinked moiety is IV-γ-5 in Table 13, the fluorenyl ring moiety is IV-δ-18 in Table 14, and the substituent of the crosslinked moiety is IV-ε-27 in Table 15. When the MX _{2 of} the metal portion is ZrBr ₂ , the compound represented by the following formula (IV-4) is exemplified.

金属部分ＭＸ_２の具体的な例示としては、ＴｉＦ_２、ＴｉＣｌ_２、ＴｉＢｒ_２、ＴｉＩ_２、Ｔｉ（Ｍｅ）_２、Ｔｉ（Ｂｎ）_２、Ｔｉ（Ａｌｌｙｌ）_２、Ｔｉ（ＣＨ_２−ｔＢｕ）_２、Ｔｉ（η^４−１，３−ブタジエニル）、Ｔｉ（η^４−１，３−ペンタジエニル）、Ｔｉ（η^４−２，４−ヘキサジエニル）、Ｔｉ（η^４−１，４−ジフェニル−１，３−ペンタジエニル）、Ｔｉ（ＣＨ_２−Ｓｉ（Ｍｅ）_３）_２、Ｔｉ（ＯＭｅ）_２、Ｔｉ（ＯｉＰｒ）_２、Ｔｉ（ＮＭｅ_２）_２、Ｔｉ（ＯＭｓ）_２、Ｔｉ（ＯＴｓ）_２、Ｔｉ（ＯＴｆ）_２、ＺｒＦ_２、ＺｒＣｌ_２、ＺｒＢｒ_２、ＺｒＩ_２、Ｚｒ（Ｍｅ）_２、Ｚｒ（Ｂｎ）_２、Ｚｒ（Ａｌｌｙｌ）_２、Ｚｒ（ＣＨ_２−ｔＢｕ）_２、Ｚｒ（η^４−１，３−ブタジエニル）、Ｚｒ（η^４−１，３−ペンタジエニル）、Ｚｒ（η^４−２，４−ヘキサジエニル）、Ｚｒ（η^４−１，４−ジフェニル−１，３−ペンタジエニル）、Ｚｒ（ＣＨ_２−Ｓｉ（Ｍｅ）_３）_２、Ｚｒ（ＯＭｅ）_２、Ｚｒ（ＯｉＰｒ）_２、Ｚｒ（ＮＭｅ_２）_２、Ｚｒ（ＯＭｓ）_２、Ｚｒ（ＯＴｓ）_２、Ｚｒ（ＯＴｆ）_２、ＨｆＦ_２、ＨｆＣｌ_２、ＨｆＢｒ_２、ＨｆＩ_２、Ｈｆ（Ｍｅ）_２、Ｈｆ（Ｂｎ）_２、Ｈｆ（Ａｌｌｙｌ）_２、Ｈｆ（ＣＨ_２−ｔＢｕ）_２、Ｈｆ（η^４−１，３−ブタジエニル）、Ｈｆ（η^４−１，３−ペンタジエニル）、Ｈｆ（η^４−２，４−ヘキサジエニル）、Ｈｆ（η^４−１，４−ジフェニル−１，３−ペンタジエニル）、Ｈｆ（ＣＨ_２−Ｓｉ（Ｍｅ）_３）_２、Ｈｆ（ＯＭｅ）_２、Ｈｆ（ＯｉＰｒ）_２、Ｈｆ（ＮＭｅ_２）_２、Ｈｆ（ＯＭｓ）_２、Ｈｆ（ＯＴｓ）_２、Ｈｆ（ＯＴｆ）_２などが挙げられる。Ｍｅはメチル基、Ｂｎはベンジル基、ｔＢｕはｔｅｒｔ−ブチル基、Ｓｉ（Ｍｅ）_３はトリメチルシリル基、ＯＭｅはメトキシ基、ＯｉＰｒはｉｓｏ−プロポキシ基、ＮＭｅ_２はジメチルアミノ基、ＯＭｓはメタンスルホナート基、ＯＴｓはｐ−トルエンスルホナート基、ＯＴｆはトリフルオロメタンスルホナート基である。

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

In the formula (V), X is a monovalent group, and each of them independently has a hydrogen atom, a halogen atom, a hydrocarbon group, a halogen-containing group, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, and a nitrogen-containing group. It is a phosphorus-containing group, a boron-containing group, or an aluminum-containing group, and may be the same or different from each other. X can be the same as X in the above formula (I). M is a titanium atom, a zirconium atom or a hafnium atom. Cp ¹ and Cp ² represent a cyclopentadienyl group or a substituted cyclopentadienyl group that can form a sandwich structure with M and may be the same or different from each other. Cp ¹ and Cp ² may be the same as Cp ¹ and Cp ² in the formula (I).

When ethylene and 1-hexene are copolymerized using the catalyst and _{the extreme viscosity [η] 1 of the} polymer obtained when ethylene is homopolymerized using the catalyst containing the component (B) according to the present invention. When the relationship of the following formula (2) is established with the ultimate viscosity [η] ₂ of the obtained polymer, it is possible to produce an olefin polymer capable of forming a molded product having less fish eyes and a good appearance. Preferred from the point of view.

[Η] ₂ / [η] ₁ ≤ 1.1 (2)
[Η] ₂ / [η] ₁ is more preferably 1.07 or less, and further preferably 1.05 or less. The lower limit of [η] ₂ / [η] ₁ is not particularly limited, but can be, for example, 0.5 or more. Here, the "catalyst containing the component (B)" refers to a catalyst that may contain the component (C) in addition to the component (B). As a condition for homopolymerizing ethylene, polymerization is carried out at 75 ° C. and a hydrogen concentration condition of ethylene / hydrogen (0.45 mol%) at 0.65 MPa · G in the presence of 0.50 mmol / L of triisobutylaluminum. , The yield of the polymer is in the range of 10 to 120 g. The conditions for copolymerizing ethylene and 1-hexene are 0.50 mmol / L of triisobutylaluminum and 3.0 ml of 1-hexene at 75 ° C. and ethylene / hydrogen (0.45 mol%). Polymerization was carried out at 0.65 MPa · G under hydrogen concentration conditions, and the yield of the polymer was in the range of 10 to 120 g. Specifically, the ultimate viscosities [η] ₁ and [η] ₂ are obtained by the method described later.

Further, in the present invention, the component (B) includes compounds other than the compounds represented by the formulas (II), (III), (IV) and (V) and satisfying the formula (2).

(Component (C))
Ingredient (C) is
(C-1) An organometallic compound represented by the following formula (VI), (VII) or (VIII) (hereinafter, also referred to as component (c-1)),
(C-2) Organoaluminium oxy compound (hereinafter, also referred to as component (c-2)),
(C-3) A compound that reacts with the component (A) and the component (B) to form an ion pair (hereinafter, also referred to as a component (c-3)), and (c-4) the above (c-1). ), A solid component obtained by insolubilizing a component containing at least one selected from the group consisting of (c-2) and (c-3) (hereinafter, also referred to as component (c-4)).
It is at least one compound selected from the group consisting of. The component (C) is a component having a role of a scavenger or a co-catalyst.

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

_{^{M a AlR a 4 ··· (VII}} )
Wherein (VII), ^{M a} is lithium atom, sodium atom or a potassium atom. Ra represents ^a hydrogen atom or a hydrocarbon group having 1 to 15 carbon atoms.

R ^a _r M ^b R ^b _s X _t ... (VIII)
In formula (VIII), ^Ra and R ^b each independently represent a hydrocarbon group having 1 to 15 carbon atoms and may be the same or different from each other. ^Mb is a magnesium atom, a zinc atom or a cadmium atom. X represents a halogen atom. r satisfies 0 <r ≦ 2, s satisfies 0 ≦ s ≦ 1, t satisfies 0 ≦ t ≦ 1, and r + s + t = 2.

In the above formula (VI), ^{examples of the hydrocarbon group having 1 to 15 carbon atoms of Ra} and R ^b include methyl, ethyl, isopropyl, isobutyl, hexyl, octyl, and 2-ethylhexyl. Hydrocarbon group of 1 to 15 carbon atoms in R ^a in the formula (VII) may be the the same as the hydrocarbon group. ^{The hydrocarbon groups of Ra} and R ^b having 1 to 15 carbon atoms in the formula (VIII) can be the same as the hydrocarbon groups. Examples of the halogen atom of X in the formula (VI) and the formula (VIII) include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like.

Among the components (c-1) represented by the formula (VI), (VII) or (VIII), the organometallic compound represented by the formula (VI) is preferable. Specific examples of the organic metal compound represented by the formula (VI) include trialkylaluminum such as trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, and tri2-ethylhexylaluminum. Dialkylaluminum halides such as dimethylaluminum chloride, diethylaluminum chloride, diisopropylaluminum chloride, diisobutylaluminum chloride, dimethylaluminum bromide, methylaluminum sesquichloride, ethylaluminum sesquichloride, isopropylaluminum sesquichloride, butylaluminum sesquichloride, ethylaluminum sesquibromid, etc. Alkylaluminum sesquihalide, methylaluminum dichloride, ethylaluminum dichloride, isopropylaluminum dichloride, alkylaluminum dihalide such as ethylaluminum dibromid, dimethylaluminum hydride, diethylaluminum hydride, dihydrophenylaluminum hydride, diisopropylaluminum hydride, di-n- Alkylaluminum hydrides such as butylaluminum hydride, diisobutylaluminum hydride, diisohexyl aluminum hydride, diphenylaluminum hydride, dicyclohexylaluminum hydride, di-sec-heptyl aluminum hydride, di-sec-nonylaluminum hydride, dimethylaluminum ethoxide, diethylaluminum Examples thereof include dialkylaluminum alcoholides such as ethoxide, diisopropylaluminum methoxide, and diisobutylaluminum ethoxide. The component (c-1) may be one kind of compound or may contain two or more kinds of compounds.

Moreover, as an example of the organometallic compound represented by the said formula (VIII), the dialkylzinc compound described in JP-A-2003-171412 and the like can be mentioned, and it can also be used in combination with a phenol compound and the like.

As the component (c-2), an organoaluminum oxy compound prepared from trialkylaluminum or tricycloalkylaluminum is preferable, and aluminoxane prepared from trimethylaluminum or triisobutylaluminum is particularly preferable. For example, methylaluminoxane (MAO) is preferred. The component (c-2) may be one kind of compound or may contain two or more kinds of compounds.

Examples of the component (c-3) that reacts with the component (A) and the component (B) to form an ion pair include Japanese Patent Application Laid-Open No. 1-501950, Japanese Patent Application Laid-Open No. 1-502036, and Japanese Patent Application Laid-Open No. 3-179005. , JP-A-3-179006, JP-A-3-207703, JP-A-3-207704, US Pat. No. 5,321,106 and the like, as well as Lewis acids, ionic compounds, borane compounds and carborane compounds. Can use heteropoly compounds, isopoly compounds and the like. The component (c-3) may be one kind of compound or may contain two or more kinds of compounds.

In the olefin polymerization catalyst according to the present invention, the combined use of the components (A) and (B) together with the component (c-2) such as methylaluminoxane (MAO) as a co-catalyst component has high polymerization activity with respect to the olefin. It is preferable because the solid catalyst component containing the co-catalyst component can be easily prepared by reacting with the active hydrogen in the solid carrier (S) described later.

The component (c-4) is a solid component obtained by insolubilizing a component containing at least one selected from the group consisting of the component (c-1), the component (c-2) and the component (c-3). From the viewpoint of ease of preparation and cost of the component (c-4), it is preferably a solid component obtained by insolubilizing the component containing the component (c-2), and it is preferably a solid MAO component. More preferred.

Such a component (c-4) is described in, for example, JP-A-11-140113, JP-A-2000-38410, JP-A-2000-95810, International Publication No. 2010/55652, and the like. Can be prepared in. The component (c-4) may be one kind of compound or may contain two or more kinds of compounds.

In addition, "insolubilization" means insolubilizing a hydrocarbon, specifically, a component that dissolves in an inert hydrocarbon described in the column of the method for preparing an olefin polymerization catalyst described later, preferably at room temperature. It means that the component has a solubility of 0.5 g or less in 100 g of the inert hydrocarbon in the above.

(Solid support (S))
The catalyst for olefin polymerization according to the present invention preferably further contains a solid carrier (S) (hereinafter, also referred to as component (S)) from the viewpoint of stably producing a desired olefin polymer. It is preferable that the component (A), the component (B) and the component (C) are supported on the component (S). In this case, the component (S) may be one kind or two or more kinds. That is, the component (A), the component (B) and the component (C) may be supported on one kind of the component (S), and the component (A), the component (B) and the component (C) are different components (S). ) May be supported respectively. Examples of the component (S) include an inorganic compound or an organic compound, which is a solid in the form of granules or fine particles.

Examples of the inorganic compound include porous oxides, inorganic halides, clays, clay minerals, ion-exchange layered compounds and the like. Among these inorganic compounds, porous oxides are preferable.

Examples of the porous oxide include porous oxides having compositions such as _{SiO 2} , Al ₂ O ₃ , MgO, ZrO, TiO ₂ , B ₂ O ₃ , CaO, ZnO, BaO and ThO _{2, and these compositions.} Examples thereof include a composite oxide having the above, and a mixture of these porous oxides. Specifically, natural or synthetic zeolite, SiO _2- MgO, SiO _2- Al ₂ O ₃ , SiO _2- TiO ₂ , SiO _2- V ₂ O ₅ , SiO _2- Cr ₂ O ₃ and SiO _2- TiO ₂ Examples thereof include porous oxides having a composition such as −MgO. Of these, _{a porous oxide containing SiO 2} as a main component is preferable.

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

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

Examples of the inorganic halide include MgCl ₂ , MgBr ₂ , MnCl ₂ , and MnBr ₂ . The inorganic halide may be used as it is, or may be pulverized by a ball mill, a vibration mill or the like. 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 precipitant.

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

Clays and clay minerals include, for example, kaolin, bentonite, knot clay, gailome clay, allophane, hisingel stone, pyrophyllite, ummo group, montmorillonite group, vermiculite, ryokudei stone group, parigolskite, kaolinite, nacrite, deckite, halloysite. And so on.

The ion-exchange layered compounds, hexagonal close packing type, antimony type, CdCl ₂ type, and the like can be exemplified ionic crystalline compounds having a layered crystal structure of type _2, etc. CdI. _{Specifically, α-Zr (HAsO 4)} 2 · H 2 O, α-Zr (HPO 4) 2, α-Zr (KPO 4) 2 · 3H 2 O, α-Ti (HPO 4) 2, α -Ti (HAsO ₄ ) ₂ · H ₂ O, α-Sn (HPO ₄ ) ₂ · H ₂ O, γ-Zr (HPO ₄ ) ₂ , γ-Ti (HPO ₄ ) ₂ , γ-Ti (NH ₄ PO) ₄₎ crystalline acidic salts of polyvalent metals such as 2 _· H 2 _O and the like.

The clay, clay mineral or ion-exchange layered compound preferably has a pore volume of 0.1 cc / g or more, and more preferably 0.3 to 5 cc / g, as measured by the mercury intrusion method and having a radius of 20 Å or more. preferable. Here, the pore volume is measured in the range of a pore radius of 20 to 3 × 10 ^{4 Å by a mercury intrusion method using a mercury porosimeter.}

Clays and clay minerals are preferably chemically treated. Examples of the chemical treatment include a surface treatment for removing impurities adhering to the surface, a treatment for affecting the crystal structure of clay, and the like. Specific examples of the chemical treatment include acid treatment, alkali treatment, salt treatment, organic substance treatment and the like. In the acid treatment, in addition to removing impurities on the surface, the surface area can be increased by eluting cations such as Al, Fe, and Mg in the crystal structure. Alkaline treatment destroys the crystal structure of the clay and can change 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. Further, the introduction of another substance between the layers of the layered compound in this way is called intercalation. Examples of the intercalating guest compounds include cationic inorganic compounds such as _{TiCl 4} , ZrCl ₄ , and metal alkoxides such as _{Ti (OR) 4} , Zr (OR) ₄ , PO (OR) ₃ , and B (OR) _3. R is a hydrocarbon group, etc.), [Al ₁₃ O ₄ (OH) ₂₄ ] ⁷⁺ , [Zr ₄ (OH) ₁₄ ] ²⁺ , [Fe ₃ O (OCOCH ₃ ) ₆ ] ^{+, and} other metal ions. 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. A substance, a colloidal inorganic compound such as _{SiO 2, or the like can coexist.} Examples of pillars include oxides produced by intercalating the metal ions between layers and then heating and dehydrating the metal ions.

Clays, clay minerals, and ion-exchange layered compounds may be used as they are, or may be used after being subjected to treatments such as ball milling and sieving. Further, it may be used after water is added and adsorbed, or heat dehydration treatment is performed.

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

As the component (S), a porous oxide is preferable from the viewpoint of stable production. The component (S) may be used alone or in combination of two or more.

(Method for preparing catalyst for olefin polymerization)
The method for preparing the catalyst for olefin polymerization according to the present invention is not particularly limited, and for example, it can be roughly divided into the following three methods. In the following, the catalysts obtained will be referred to as the first to third catalysts according to the preparation method. Among these, the first catalyst, which is a catalyst when a component containing the component (c-4) is used as the component (C), is the first catalyst from the viewpoint of stably producing a desired olefin polymer. The second catalyst or the third catalyst is preferable.

The first catalyst is prepared by adding the component (A), the component (B) and the component (C) in an activated carbon or in a polymerization system using an activated carbon. When the first catalyst is added to the polymerization system and a component other than the component (c-4) is used as the component (C), the polymerization system includes the following main polymerization system. In particular, the solution main polymerization system is preferable. When the first catalyst is added to the polymerization system and a component containing the component (c-4) is used as the component (C), the polymerization system is not particularly limited, and the following preliminary It may be a polymerization system or a main polymerization system.

The method for preparing the first catalyst is not particularly limited, but preferred methods include the following methods i) to x), and more preferred methods are the following i), ii), v), vi) and vi). The method can be mentioned. When a plurality of components (C) are used in the following method, the components (C) may be the same or different from each other.
i) Method of adding the component (C), the component (A), and the component (B) in the activated carbon or in the polymerization system in this order ii) The component (C), the component (B), and the component (A) in this order. Method of adding to the inactive carbon or in the polymerization system in iii) A contact material obtained by mixing and contacting the component (A) and the component (C) is added in the inactive carbon or in the polymerization system, and then the component ( Method of adding B) to an activated carbon or a polymerization system iv) A contact material obtained by mixing and contacting the component (B) and the component (C) is added to the activated carbon or the polymerization system, and then. Method of adding component (A) to an activated carbon or a polymerization system v) Add the component (C) to an activated carbon or a polymerization system, and then add the component (A) and the component (B). Method of adding the contact material in mixed contact to the activated carbon or the polymerization system vi) Add the component (C), the component (A), and the component (B) to the activated carbon or the polymerization system in this order. Then, the method of adding the component (C) to the activated carbon or the polymerization system again vie) In the activated carbon or the polymerization system in the order of the component (C), the component (B), and the component (A). Method of adding and re-adding the component (C) to the activated carbon or the polymerization system viii) The contact material in which the component (A) and the component (C) are mixed and contacted is mixed and contacted with the activated carbon or the polymerization system. Method of adding the component (B) into the activated carbon, then adding the component (B) to the activated carbon or the polymerization system, and then adding the component (C) to the activated carbon or the polymerization system again ix) Component (B) A contact material obtained by mixing and contacting the component (C) and the component (C) is added to the activated carbon or the polymerization system, and then the component (A) is added to the activated carbon or the polymerization system, and then the component (A) is added again. Method of adding C) to an activated carbon or a polymerization system x) Add the component (C) to an activated carbon or a polymerization system, and then mix and contact the component (A) and the component (B). A method in which the treated contact material is added to the activated carbon or the polymerization system, and then the component (C) is added again to the activated carbon or the polymerization system.

The second catalyst is a component other than at least one component (hereinafter, also referred to as "component (S')") selected from the group consisting of the component (S) and the component (c-4), and the component (c-4). (C) (hereinafter, also referred to as "component (C')") and the solid catalyst component (K1) formed from the component (A), and the component (S'), the component (C') and the component (B) It is prepared by adding the solid catalyst component (K2) to be formed into an inert hydrocarbon or a polymerization system using an inert hydrocarbon. The second catalyst includes a solid catalyst component (K1) in which the component (A) is supported on the component (S') together with the component (C'), and a component (B) different from this component (K1). Preferably contains the solid catalyst component (K2) supported on the component (S') together with the component (C').

The method for preparing the second catalyst is not particularly limited, but preferred methods include the following methods xi) to xiv), and more preferred methods include the following xi) and xiii) methods. In the following method, a plurality of components (for example, component (C')) may be the same or different from each other (for example, components (C')).
xi) The solid catalyst component (K1) prepared by contacting the component (C') and the component (S') and then contacting the component (A), and the component (C') and the component (S'). Method using solid catalyst component (K2) prepared by contacting and contacting component (B) there xi) Component (A) and component (C') are mixed and contacted, and this is combined with component (S'). The solid catalyst component (K1) prepared by contacting with the component (K1), the component (B) and the component (C') are mixed and contacted, and the solid catalyst component (K2) is prepared by contacting the component (S'). With the solid catalyst component (K1) prepared by contacting the component (C') and the component (S') and then contacting the contact material of the component (A) and the component (C'). , A method using a solid catalyst component (K2) prepared by contacting the component (C') and the component (S') and contacting the contact material of the component (B) and the component (C') xiv). The solid catalyst component (K1) and the component (C) prepared by contacting the component (C') and the component (S'), contacting the component (A) there, and then contacting the component (C') again. A method using a solid catalyst component (K2) prepared by contacting') and a component (S'), contacting the component (B) there, and then contacting the component (C') again.

The third catalyst (solid catalyst component (K3)) is prepared by contacting component (A), component (B), component (C') and component (S') in an inert hydrocarbon. .. The third catalyst is preferably a solid catalyst component in which the component (A) and the component (B) are co-supported on the component (S') together with the component (C'). The method for preparing the third catalyst is not particularly limited, but preferred methods include the following methods xv) to xxix), and more preferred methods are the following xv), xvi), xvii), xxiii), xxiii) and The method of xxiv) can be mentioned. When a plurality of components (C') are used in the following method, the components (C') may be the same or different from each other.
xv) A method in which the component (C') is mixed and contacted with the component (S'), the component (A) is brought into contact with the component (C'), and then the component (B) is brought into contact with the component (B) to prepare the component (S'). (C') is mixed and contacted, the component (B) is brought into contact with the component (B), and then the component (A) is brought into contact with the preparation. Xvii) The component (C') is mixed and contacted with the component (S'). A method of contacting a contact mixture of the component (A) and the component (B) there xviii) The component (A) and the component (B) were mixed and contacted, and the component (C') was brought into contact with the component (C'). Method of continuously contacting the contact material with the component (S') xix) The component (C') is brought into contact with the component (S'), the component (C') is brought into contact with the component (C'), and then the component (A) and the component are further contacted. Method of contacting in the order of (B) xx) The component (C') is brought into contact with the component (S'), the component (C') is brought into contact with the component (C'), and then the component (B) and the component (A) are further contacted. Method of contacting in order xxi) The component (C') is brought into contact with the component (S'), the component (C') is brought into contact with the component (C'), and the contact mixture of the component (A) and the component (B) is further contacted. Method xxiii) A method in which a component (C') is mixed and contacted with a component (S'), and a contact mixture of the component (A), the component (B) and the component (C') is brought into contact with the component (C'). ) Is mixed and contacted with the component (C'), a contact mixture of the component (A) and the component (C') is brought into contact there, and the component (B) is further brought into contact with the component (S'). A method in which (C') is mixed and contacted, a contact mixture of the component (B) and the component (C') is brought into contact with the component (C'), and the component (A) is further brought into contact with the component (C'). ), Then the component (C') is contacted there, and then the contact mixture of the component (A) and the component (C'), and the contact mixture of the component (B) and the component (C'). Xxvi) Contact the component (C') with the component (S'), contact the component (C') there, and then further contact the mixture of the component (B) and the component (C'). Method of contacting component (A) and component (C') in the order of a contact mixture xxvii) Contact component (C') with component (S'), contact component (C') there, and then contact the component (C'). Further, a method of contacting a contact mixture of the component (A), the component (B) and the component (C') xxviii) A mixture of the component (A) and the component (C'), and the component (B) and the component (C') A method in which a mixture with and is previously mixed and brought into contact with a contact material between the component (S') and the component (C'). Xxix) A mixture of the component (A) and the component (C'). And a mixture of the component (B) and the component (C') is mixed in advance, and this is a contact product in which the contact material of the component (S') and the component (C') is further contacted with the component (C'). How to contact with.

In each of the above methods, a step including contact between the component (S') and the component (C'), a step including contact between the component (S') and the component (A), the component (S') and the component (B). In the step including contact with the component (S') and the step including contact with the component (S'), the component (A) and the component (B), the component (G) includes the component (g-1) polyalkylene oxide block and the component (g). -2) Higher aliphatic amide, component (g-3) polyalkylene oxide, component (g-4) polyalkylene oxide alkyl ether, component (g-5) alkyl diethanolamine, and component (g-6) polyoxyalkylene alkyl. At least one compound selected from amines may coexist. By coexisting the component (G), fouling during the polymerization reaction can be suppressed, and the particle properties of the produced polymer are improved. Among the components (G), the component (g-1), the component (g-2), the component (g-3) or the component (g-4) is preferable.

Specific examples of the inert hydrocarbon (solvent) include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene, cyclopentane, cyclohexane, and methylcyclopentane. Examples thereof include aliphatic hydrocarbons, aromatic hydrocarbons such as benzene, toluene and xylene, halogenated hydrocarbons such as ethylene chloride, chlorobenzene and dichloromethane, and mixtures thereof.

By contact between the component (C') and the component (S'), the reaction site in the component (C') and the reaction site in the component (S') react, and the component (C') and the component (S') react. ) Can be chemically bonded. The contact time between the component (C') and the component (S') is preferably 0 to 20 hours, more preferably 0 to 10 hours, and the contact temperature is preferably −50 to 200 ° C., more preferably −. It is 20 to 120 ° C. When the initial contact between the component (C') and the component (S') is abruptly performed, the structure of the component (S') is destroyed by the reaction heat generation and the reaction energy, and the morphology of the obtained solid catalyst component is lowered. .. When this is used for polymerization, continuous operation is often difficult due to poor polymer morphology. Therefore, in the initial contact between the component (C') and the component (S'), the reaction is brought into contact at a low temperature of -20 to 30 ° C. or the reaction heat generation is controlled to suppress the reaction heat generation, and the initial contact temperature is controlled. It is preferable to react so that These things are the same even when the component (C') and the component (S') are brought into contact with each other and the component (C') is brought into contact with the component (C').

The molar ratio of contact between the component (C') and the component (S') (component (C') / component (S')) can be arbitrarily selected, but the higher the molar ratio, the more the component (A) and the component (S'). The contact amount of the component (B) can be increased, and the activity per catalyst of the present invention can also be improved. The molar ratio of the component (C') to the component (S') [molar amount of the component (C') / molar amount of the component (S')] is preferably 0.2 to 2.0, preferably 0.4 to 2.0. 2.0 is more preferable.

In the contact between the contact material of the component (C') and the component (S') and the component (A) or the component (B), the contact time is preferably 0 to 5 hours, more preferably 0 to 2 hours. The contact temperature is preferably in the range of -50 to 200 ° C, more preferably -50 to 100 ° C. The contact amount (use ratio) of the component (A) and the component (B) with respect to the component (C) largely depends on the type and amount of the component (C). When the component (c-1) is used, the molar ratio [(c-1) / M] of the component (c-1) to the total transition metal atoms (M) in the component (A) and the component (B) is It is preferably 0.01 to 100,000, more preferably 0.05 to 50,000. When the component (c-2) is used, the molar ratio of the aluminum atom in the component (c-2) to the total transition metal atom (M) in the component (A) and the component (B) [(c-2) / M] is preferably 10 to 500,000, more preferably 20 to 100,000. When the component (c-3) is used, the molar ratio [(c-3) / M] of the component (c-3) to the total transition metal atoms (M) in the component (A) and the component (B) is 1 to 10 are preferable, and 1 to 5 are more preferable. The molar ratio of the component (C) to the total transition metal atoms (M) in the component (A) and the component (B) can be determined by inductively coupled plasma emission spectrometry (ICP analysis method).

The usage ratio of the component (A) and the component (B) can be arbitrarily determined from the molecular weight and the molecular weight distribution of the polyolefin to be produced. The molar ratio [(A) / (B)] of the component (A) to the component (B) may be determined in consideration of the olefin polymerization activity of each of the component (A) and the component (B). [(A) / (B)] is preferably 0.03 to 30, more preferably 0.06 to 15, further preferably 0.1 to 5, and particularly preferably 0.2 to 3.

When the (co) polymerization of the olefin is carried out using the catalyst obtained by the above method, the catalyst obtained by the above method can be used as it is, but when the second catalyst or the third catalyst is used, the catalyst obtained by the above method can be used as it is. Alternatively, when the first catalyst is used and a component containing the component (c-4) is used as the component (C), an olefin is prepolymerized in this catalyst in advance to prepare a prepolymerization catalyst component. It can also be used after that.

The prepolymerization catalyst component can be prepared, for example, by introducing an olefin into an inert hydrocarbon in the presence of the catalyst obtained by the above method. As the reaction method, any of a batch method, a semi-continuous method and a continuous method can be used. The reaction can be carried out under reduced pressure, normal pressure or pressure. By this prepolymerization, a polymer of preferably 0.01 to 1000 g, more preferably 0.1 to 800 g, still more preferably 0.2 to 500 g can be produced per 1 g of the catalyst obtained by the above method.

The prepolymerization catalyst component prepared in the inert hydrocarbon may be separated from the suspension, suspended in the inert hydrocarbon again, and the main polymerization may be carried out using the obtained suspension. Further, the main polymerization may be carried out after drying.

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

The form of the catalyst obtained by the above method used for prepolymerization is not particularly limited. Further, in the prepolymerization, the component (C) is further used if necessary, and in particular, the organoaluminum compound represented by the formula (VI) in the component (c-1) is preferably used. When the organoaluminum compound represented by the formula (VI) is further used in the prepolymerization, the organoaluminum compound used additionally is the aluminum atom (Al—C) and the component (A) in the compound. And (B) is used in an amount such that the molar ratio (Al—C / transition metal compound) with the transition metal compound is preferably 0.1 to 10000, more preferably 0.5 to 5000.

The concentration of the catalyst used in the prepolymerization obtained by the above method is preferably 0.0001 to 1000 g / liter, more preferably 0.001 to 500 g / liter, based on 1 liter of the polymerization volume. At the time of prepolymerization, the component (G) can coexist for the purpose of suppressing fouling or improving the particle properties of the obtained polymer.

Further, even if the component (G) is brought into contact with the prepolymerization catalyst component once generated by the prepolymerization for the purpose of improving the fluidity of the prepolymerization catalyst component, heat spot seating during the main polymerization, and suppressing the generation of polymer lumps. Good. At this time, as the component (G) to be used, the component (g-1), the component (g-2), the component (g-3) or the component (g-4) is preferable. The temperature at which the component (G) is mixed and contacted is preferably −50 to 50 ° C., more preferably −20 to 50 ° C. The contact time is preferably 1 to 1000 minutes, more preferably 5 to 600 minutes.

When the prepolymerization catalyst component and the component (G) are mixed and contacted, the component (G) is preferably 0.1 to 20 parts by mass, more preferably 0.3 to 20 parts by mass with respect to 100 parts by mass of the prepolymerization catalyst component. It is used in an amount of 10 parts by mass, more preferably 0.4 to 5 parts by mass. The mixed contact between the solid catalyst component and the component (G) can be carried out in an inert hydrocarbon solvent. Examples of the inert hydrocarbon solvent include compounds similar to the inert hydrogen used in the method for preparing the catalyst.

The olefin polymerization catalyst according to the present invention can be used as a dry prepolymerization catalyst in which the prepolymerization catalyst component is dried. The prepolymerization catalyst component can be dried after removing hydrocarbons as a dispersion medium from the obtained suspension of the prepolymerization catalyst by filtration or the like.

The prepolymerization catalyst component can be dried, for example, by holding the prepolymerization catalyst component at a temperature in the range of preferably 70 ° C. or lower, more preferably 20 to 50 ° C. under the flow of an inert gas. The amount of volatile components in the obtained dry prepolymerization catalyst is preferably 2.0% by mass or less, more preferably 1.0% by mass or less. The smaller the amount of volatile components in the dry prepolymerization catalyst is, the more preferable it is, and there is no particular lower limit, but practically it is 0.001% by mass or more. The drying time is preferably 3 to 8 hours, although it depends on the drying temperature. Here, the amount of the volatile component in the dry prepolymerization catalyst is measured by, for example, a weight loss method, a method using gas chromatography, or the like.

In the weight loss method, the weight loss when the dry prepolymerization catalyst is heated at 110 ° C. for 1 hour in an inert gas atmosphere is obtained, and the amount of the volatile components is expressed as a percentage of the weight loss to the dry prepolymerization catalyst before heating. Can be done.

In the method using gas chromatography, volatile components such as hydrocarbons are extracted from the dry prepolymerization catalyst, a calibration curve is prepared according to the internal standard method, and the volatile components are obtained from the peak area obtained by gas chromatography. The amount can be calculated as% by mass.

As a method for measuring the amount of volatile components in the dry prepolymerization catalyst, a weight loss method is adopted when the amount of volatile components in the dry prepolymerization catalyst is about 1% by mass or more, and the amount of volatile components in the dry prepolymerization catalyst is adopted. When is less than about 1% by mass, a method using gas chromatography is adopted.

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

Since the dry prepolymerization catalyst has excellent fluidity, it can be stably supplied to the polymerization reactor. Further, since the abundance of the solvent used when preparing the catalyst in the gas phase polymerization system can be reduced, the main polymerization can be stably carried out.

(Method for producing olefin polymer)
Next, a method for producing an olefin polymer using the catalyst according to the present invention will be described. In this method, an olefin polymer is obtained by polymerizing or copolymerizing an olefin in the presence of the catalyst for olefin polymerization according to the present invention. In this method, by using the catalyst for olefin polymerization according to the present invention, a polymer having high polymerization activity, excellent molding processability and mechanical strength, and having a good appearance when processed into a film or the like can be obtained.

In the above method, the polymerization can be carried out by any of a liquid phase polymerization method such as dissolution polymerization and suspension polymerization or a gas phase polymerization method, but the suspension polymerization method is preferable. When an inert hydrocarbon medium is used in the liquid phase polymerization method, specific examples thereof include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; cyclopentane, cyclohexane, and methyl. Aliphatic hydrocarbons such as cyclopentane; aromatic hydrocarbons such as benzene, toluene and xylene; halogenated hydrocarbons such as ethylene chloride, chlorobenzene and dichloromethane and mixtures thereof. Further, in the liquid phase polymerization method, the olefin itself can be used as a solvent.

When polymerizing an olefin using the catalyst for olefin polymerization according to the present invention, the components (A) and (B) are preferably ^10-12 to ^10-1 mol, more preferably 10-12 to 1 mol, per liter of the reaction volume. It is used in an amount of ^10-8 to ^{10-2 mol.} Further, among the component (C), the organoaluminum compound represented by the above formula (VI) of the component (c-1) is preferably used.

The polymerization temperature of the olefin is preferably −50 to + 200 ° C., more preferably 0 to 170 ° C., and even more preferably 60 to 170 ° C. The polymerization pressure is preferably normal pressure to 100 kg / cm ² , more 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 obtained polymer can be adjusted by the presence of hydrogen in the polymerization system or by changing the polymerization temperature. At the time of polymerization, the component (G) can coexist for the purpose of suppressing fouling or improving the particle properties.

The olefin supplied in the polymerization reaction is not particularly limited as long as the effects of the present invention are exhibited, but is preferably one or more monomers selected from olefins having 2 to 20 carbon atoms. Specific examples of olefins having 2 to 20 carbon atoms include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, and so on. Α-olefins such as 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene; cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene, 2-methyl-1,4,5, Cyclic olefins such as 8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene; and the like. Further, styrene, vinylcyclohexane, diene, acrylic acid, methacrylic acid, fumaric acid, maleic anhydride and the like; polar monomers such as methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate and methacrylic acid can also be mentioned. Hereinafter, a method for producing an ethylene-based copolymer according to the present invention, which uses ethylene and an olefin having 3 to 20 carbon atoms as the olefin, will be described in detail.

The method for producing an ethylene-based copolymer according to the present invention includes a step of copolymerizing ethylene and an olefin having 3 to 20 carbon atoms (hereinafter, also referred to as "the present polymerization") in the presence of the catalyst according to the present invention. .. In the present invention, the ethylene-based copolymer means a copolymer in which the content of ethylene-derived structural units in the polymer is 10 mol% or more.

The polymerization can be carried out by any of a liquid phase polymerization method such as dissolution polymerization and suspension polymerization or a gas phase polymerization method, but when the first catalyst is used, the component (C) is a component. When a component other than (c-4) is used, the liquid phase polymerization method is preferable, and the dissolution polymerization method is more preferable. When the second or third catalyst is used, or when the first catalyst is used and a component containing the component (c-4) is used as the component (C), the suspension weight is used. Legal or gas phase polymerization methods are preferred.

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

In the main polymerization, the component (A) and the component (B) are used in an amount such that the amount ^{is preferably 10-12} to ^10-1 mol, more preferably ^10-8 to ^{10-2 mol, per 1 liter of the reaction volume.} Be done. Further, in the present polymerization, as the component (C), the organoaluminum compound represented by the above formula (VI), which is the component (c-1), is preferably used.

The polymerization temperature of the present polymerization is preferably in the range of −50 to + 200 ° C, more preferably 0 to 170 ° C, and further preferably 60 to 170 ° C. The polymerization pressure is preferably normal pressure to 100 kgf / cm ² , more preferably normal pressure to 50 kgf / cm ² . The polymerization reaction can be carried out by any of a batch type, a semi-continuous type and a continuous type. Further, it is also possible to carry out the polymerization in two or more stages having different reaction conditions. When continuously polymerizing in two or more stages in order to produce an ethylene-based copolymer, for example, only ethylene may be homopolymerized in the first stage, and ethylene and olefin may be copolymerized in the second stage. ..

The molecular weight of the obtained ethylene-based copolymer can be adjusted by the presence of hydrogen in the polymerization system or by changing the polymerization temperature. At the time of polymerization, the component (G) can coexist for the purpose of suppressing fouling or improving particle properties.

Specific examples of olefins having 3 to 20 carbon atoms include propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, and 1-tetradecene. , 1-Hexadecene, 1-octadecene, 1-eicosene and other α-olefins; cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene, 2-methyl-1,4,5,8-dimethano Cyclic olefins such as −1,2,3,4,4a, 5,8,8a-octahydronaphthalene;

The olefin supplied to the present polymerization is preferably ethylene and an α-olefin having 4 to 10 carbon atoms, and more preferably ethylene and an α-olefin having 6 to 10 carbon atoms. When an α-olefin having 4 carbon atoms is used as the α-olefin, it is preferable to also use an α-olefin having 6 to 10 carbon atoms. Examples of the α-olefin having 4 to 10 carbon atoms used for copolymerization with ethylene include 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene and 1-decene.

When the number of carbon atoms of the olefin used is 5 or less, the probability that the olefin is incorporated into the crystal increases (see Polymer, vol. 31, 1999, 1990). As a result, when a hollow molded product is formed using the obtained polymer, the strength of the obtained hollow molded product tends to be weakened. Further, when the number of carbon atoms of the olefin used exceeds 10, the side chain (branch caused by the olefin copolymerized with ethylene) may crystallize. As a result, when a hollow molded product is formed by using the obtained polymer, an amorphous portion is formed in the obtained hollow molded product, and the amorphous portion tends to weaken the strength of the molded product.

The content of the structural unit derived from the olefin having 3 to 20 carbon atoms in the ethylene-based copolymer is preferably 2.0 mol% or less, more preferably 1.5 mol%, in all the structural units of the ethylene-based copolymer. Below, it is more preferably 1.3 mol% or less. The term "all constituent units of the ethylene-based copolymer" means that, when the ethylene-based copolymer is continuously polymerized in two or more stages, it is continuously polymerized in two or more stages and finally obtained. It means all the constituent units of the polymer.

The density of the ethylene-based copolymer obtained by the method according to the present invention is 910 kg / m ³ or more and 980 kg / m ³ or less. The density is preferably 920 to 970 kg / m ³ , more preferably 930 to 960 kg / m ³ , and even more preferably 940 to 950 kg / m ³ . When the density is within the above range, the strength is excellent when used as a packaging material or an industrial material. The density can be adjusted within the above range by changing, for example, the supply amount ratio of hydrogen, ethylene, and α-olefin to the polymer, and the polymerization amount ratio of the ethylene homopolymer and the ethylene / α-olefin copolymer. The value can be increased or decreased. The density is a value measured by a method described later.

The melt flow rate (MFR) of the ethylene-based copolymer obtained by the method according to the present invention under a load of 2.16 kg is preferably 0.01 to 20 g / 10 min, and is preferably 0.05 to 5 g / 10 min. More preferably, it is more preferably 0.1 to 1 g / 10 min. When the MFR is within the above range, the strength is excellent and the molding processability is excellent when used as a packaging material. The MFR is a value measured by a method described later.

The intrinsic viscosity [η] of the ethylene-based copolymer obtained by the method according to the present invention is preferably 0.5 to 8.0 dL / g, and more preferably 1.0 to 6.0 dL / g. It is preferably 1.5 to 4.0 dL / g, and more preferably 1.5 to 4.0 dL / g. When the ultimate viscosity [η] is within the above range, the strength is excellent and the molding processability is excellent when used as a packaging material. The ultimate viscosity [η] can be determined by, for example, changing the supply amount ratio of hydrogen, ethylene, and α-olefin to the polymer, the polymerization amount ratio of the ethylene homopolymer and the ethylene / α-olefin copolymer, and the like. The value can be increased or decreased within the range. The ultimate viscosity [η] is a value measured by a method described later.

(Molded body)
The ethylene-based copolymer obtained by the method according to the present invention can be widely used in known polyolefin applications, for example, sheets such as foam sheets, unstretched or stretched films, filaments, bottles, and other molded articles having various shapes. It can be used as. By processing the ethylene-based copolymer, a molded product having excellent moldability and excellent mechanical strength and appearance, preferably a film such as an inflation film, can be obtained.

When the sheet is a multilayer sheet, at least one surface layer can be a layer containing an ethylene-based copolymer obtained by the method according to the present invention. In the multilayer sheet, the layer containing the ethylene-based copolymer obtained by the method according to the present invention may be formed on only one side or on both sides. Furthermore, the layer may be formed as an intermediate layer. The base material constituting the multilayer sheet may be made of an ethylene-based copolymer obtained by the method according to the present invention.

The ethylene-based copolymer obtained by the method according to the present invention can be processed by general film molding, sheet molding, blow molding, injection molding, extrusion molding and the like.

Examples of the sheet molding method include an extrusion molding method such as an inflation method and a T die casting method, an injection molding method, a compression molding method, and a calendar molding method. The obtained sheet can be used as a single layer, but various functions can be further imparted by forming the sheet into multiple layers. Examples of the molding method used in that case include a coextrusion method and an extrusion coating method. When the sheet is a multi-layer sheet, a barrier layer for gas such as oxygen or water vapor, a sound absorbing layer, a light-shielding layer, an oxygen absorbing layer, an adhesive layer, an adhesive layer, a colored layer, a conductive layer, a recycled resin-containing layer, a foamed layer, etc. It may be provided.

The thickness of the sheet varies depending on the purpose, application and the like, and is not particularly limited, but is preferably 100 μm to 5 mm, more preferably 200 μm to 2 mm, still more preferably 300 μm to 1 mm.

Examples of the film molding method include extrusion laminating molding, T-die film molding, and inflation molding (air cooling, water cooling, multi-stage cooling, high-speed processing).

When the film is a stretched film, preferably, by satisfying the following two physical properties, the stretched film has better independence (film tension at the time of packaging), and the film is less likely to wilt during packaging. In addition, the stretched film has excellent strength, and the film is less likely to tear during packaging and after packaging.
(1) The Young's modulus in the flow direction (MD) of film molding when converted to a thickness of 100 μm is preferably in the range of 700 to 3500 MPa, more preferably 800 to 3500 MPa, and further preferably 850 to 3500 MPa.
(2) The dirt impact strength when converted to a thickness of 100 μm is preferably in the range of 300 to 800 g, more preferably 350 to 800 g, further preferably 400 to 800 g, particularly preferably 450 to 800 g, and most preferably 500 to 800 g. Is inside.

When the Young's modulus in the flow direction (MD) of film molding is 700 MPa or more, the rigidity is improved and the film is suitable for packaging. On the other hand, when the Young's modulus is 3500 MPa or less, the production can be easily performed. Further, when the dirt impact strength is 300 g or more, the strength is improved and the film is less likely to be torn. On the other hand, when the dirt impact strength is 800 g or less, the production can be easily performed.

The film may include a layer made of another ethylene-based resin composition or a resin composition such as a propylene-based resin composition, in addition to the layer containing the ethylene-based copolymer obtained by the method according to the present invention. .. When another layer is laminated on the film, the thickness of the layer containing the ethylene-based copolymer obtained by the method according to the present invention must be 1/3 or more of the total thickness of the film. It is preferably 1/2 or more, more preferably 2/3 or more.

The thickness of the film is appropriately determined depending on various uses, but is preferably 20 to 200 μm, more preferably 40 to 100 μm. When the film is composed of multiple layers, the thickness of the layer containing the ethylene-based copolymer obtained by the method according to the present invention is preferably 100 to 150 μm, more preferably 20 to 80 μm.

The film may be laminated with another base material, for example, a base material made of a sheet or film made of a thermoplastic resin, paper, an aluminum foil, or the like, depending on the application. When a thermoplastic resin is used as the material of the base material, a known thermoplastic resin can be used. For example, polyolefin (high pressure method low density polyethylene, linear low density polyethylene (LLDPE: ethylene / α-olefin random copolymer), medium density polyethylene, high density polyethylene and other polyethylene; propylene homopolymer, propylene / α-olefin Polypropylene such as random copolymer (propylene random copolymer); poly4-methyl-pentene; polybutene, etc.), polyester (polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, etc.), polyamide (nylon-6, nylon-66, etc.) , Polymethoxylen adipamide, etc.), Polyvinyl chloride, polyimide, ethylene / vinyl acetate copolymer or its saponified product, polyvinyl alcohol, polyacrylonitrile, polycarbonate, polystyrene, ionomer, or a mixture thereof. These may be used alone or in combination of two or more. Among these, thermoplastic resins having good stretchability and transparency, such as polypropylene, polyethylene terephthalate, and polyamide, are preferable.

Further, the film made of the thermoplastic resin as the base material may be a non-stretched film or a stretched film. Further, the film may be a laminate obtained by one type or two or more types of coextrusion molding, extrusion laminating, dry laminating, thermal laminating and the like. Among these, a biaxially stretched thermoplastic film is preferable, and a biaxially stretched thermoplastic film made of polypropylene, polyethylene terephthalate, or polyamide is more preferable.

As the stretched film, an ethylene-based copolymer obtained by the method according to the present invention is used, and a stretchable raw film is formed by, for example, a known melt extrusion method, and then the raw fabric film is formed in the vertical direction or in the vertical and horizontal directions 2. It can be obtained by stretching in the direction. In this melt extruder film forming method, a T die-cast molding method or an inflation method can be adopted. The thickness of the original film for stretching to be formed is preferably 100 to 700 μm, more preferably 200 to 600 μm. The method for cooling the molten resin may be either air cooling or water cooling.

As a method of stretching the raw film for stretching, a method of simultaneously or sequentially biaxially stretching in the vertical and horizontal directions by the tenter method, a method of simultaneously biaxially stretching in the vertical and horizontal directions by the tubular method, and a rotation speed ratio of two or more rolls. Depending on the difference, a method of uniaxially stretching in the flow direction of the film can be exemplified. The draw ratio is preferably 10 to 60 times in the case of biaxial stretching, and preferably 2 to 10 times in the case of uniaxial stretching. By stretching, a stretched film having a thickness of preferably 1 to 500 μm, more preferably 5 to 200 μm can be obtained. When the stretched film is a laminated film with another layer, a multilayer stretching raw film formed by co-extrusion using a multilayer die can be used.

The ethylene-based copolymer obtained by the method according to the present invention can also be used as a material for a blow molded article. Preferred embodiments of the blow molded article include a bottle container, an industrial chemical can, and the like. Examples of the bottle container include a bleach container, a detergent container, a softener container and the like. Specifically, it is used for containers such as cosmetics, laundry detergents, household detergents, fabric softeners, shampoos, conditioners, and conditioners. It can also be used for kettles, generators, lawnmowers, motorcycles, gasoline tanks for automobiles, pesticides, chemical storage cans, drums, and the like. It is also used as a food product for storing mayonnaise and cooking oil, and as a hollow molded product for storing medical products. Further, in these applications, a multi-layer molded product may be used for the purpose of protecting food from oxidation and suppressing permeation of contents such as gasoline.

Hereinafter, the present invention will be described in more detail based on Examples, but the present invention is not limited to these Examples. In the following examples, density, ultimate viscosity [η], MFR and bulk density were measured by the following methods. In addition, fisheye evaluation was performed by the following method.

(1) Density The density is a value measured according to JIS K 7112. Specifically, the obtained polymer was dried by removing hexane and unreacted monomers with a solvent separator. The obtained powder was formed into a sheet having a thickness of 0.5 mm at a pressure of ^{100 kg / cm 2} using a hydraulic heat press machine manufactured by Shinto Metal Industry Co., Ltd. set at 190 ° C. (spacer shape; 240 × 240 × thickness). 45 x 45 x 0.5 mm on a 0.5 mm plate, take 9 pieces). Then, using another hydraulic heat press machine manufactured by Shinto Metal Industry Co., Ltd. set at 20 ° C., the sample was cooled by compressing at a pressure of ^{100 kg / cm 2 to prepare a sample for measurement.} A SUS plate having a thickness of 5 mm was used as the hot plate. The measurement sample was heat-treated at 120 ° C. for 1 hour, slowly cooled to room temperature over 1 hour, and then the density was measured with a density gradient tube.

(2) Extreme viscosity [η]
The ultimate viscosity [η] is a value measured at 135 ° C. using a decalin solvent. That is, the obtained polymer was dried by removing hexane and unreacted monomers with a solvent separator. About 20 mg of the obtained powder was dissolved in 15 ml of decalin, and the specific viscosity η _sp was measured in an oil bath at 135 ° C. After diluting with 5 ml of a decalin solvent added to this decalin solution, the specific viscosity η _sp was measured in the same manner. _{This dilution operation was repeated twice more, and the value of η sp} / C when the concentration (C) was extrapolated to 0 was determined as the ultimate viscosity [η] (see the following formula (iii)).

[Η] = lim (η _sp / C) (C → 0) (iii).

(3) MFR
For the obtained polymer, MFR was measured according to ASTM D1238.

(4) Bulk Density The bulk density of the obtained polymer was measured according to the ASTM D 1895-96 A method.

(5) Fisheye evaluation 0.12 parts by mass of Sumilyzer GP (trade name, manufactured by Sumitomo Chemical Co., Ltd.) and calcium stearate (manufactured by NOF Corporation) 0 as a heat-resistant stabilizer with respect to 100 parts by mass of the obtained polymer. .03 parts by mass was added. After that, a single-screw extruder (manufactured by Tommy Kikai Kogyo Co., Ltd., screw diameter 65 mmΦ, L / D = 28, CR = 4.2, screen mesh # 40/60/500 × 2/60/40) was used to set the temperature. Granulation was performed at 200 ° C. and a resin extrusion rate of 50 kg / h to obtain a sample for measurement. Using the measurement sample, air-cooled inflation molding was performed under the following film molding conditions to produce a film having a thickness of 40 μm or 100 μm and a width of 320 mm. In the evaluation of fish eyes, if the number of fish eyes per 100 × 100 mm is 32 or less in any thickness film, it is judged as “○”, and in the case of any thickness film, if it is more than 32, “×”. ] Was judged.

<Film molding conditions>
Molding machine: 50mmΦ inflation molding machine (manufactured by Modern Machinery Co., Ltd.)
Screw: Barrier type screw Die: (Diameter) 100 mmΦ, (Lip width) 3.5 mm
Air ring: 2-gap type Molding temperature: 200 ° C
Extrusion amount: 28.8 kg / h
Pick-up speed: 20 m / min (when molding with a thickness of 40 μm), 8 m / min (when molding with a thickness of 100 μm).

[Evaluation _{of [η] 2} / [η] ₁ of component (A) and component (B)]
(Ingredient (A-1))
<Preparation of solid aluminoxane (C-1)>
Solid aluminoxane (C-1) was prepared according to the method described in WO 2010/055652 (preliminary experiment 1 and Example 5). However, the concentration was about 1/6 times that of the conditions disclosed in the document. Specifically, 100 mL of a toluene solution of trimethylaluminum adjusted to 0.5 mol / L was charged into a glass reactor having a stirrer. The solution was cooled to 15 ° C. and 2.18 g of benzoic acid was slowly added thereto at a rate such that the temperature of the solution was 25 ° C. or lower. Then, heat aging was carried out at 50 ° C. for 1 hour. At this time, the molar ratio of trimethylaluminum to the oxygen atom of benzoic acid was 1.40. The reaction mixture was heated at 70 ° C. for 4 hours, then at 60 ° C. for 6 hours, and then once cooled to room temperature. Then, it was heated at 100 ° C. for 8 hours to precipitate solid aluminoxane. After cooling the solution to 30 ° C. or lower, 100 mL of n-hexane was added under stirring for washing. After allowing to stand for 30 minutes, 150 mL of the supernatant was removed, and 150 mL of n-hexane was further added under stirring. After allowing to stand for 15 minutes, 150 mL of the supernatant was removed, and 150 mL of n-hexane was further added under stirring. Finally, after allowing to stand for 15 minutes, 180 mL of the supernatant was removed, and n-hexane was added so that the total amount was 14.6 mL. A part of the obtained hexane slurry of solid aluminum (C-1) was collected and the concentration was examined. As a result, the slurry concentration was 41.0 g / L and the Al concentration was 0.583 mol / L. Further, when the obtained solid aluminoxane (C-1) particles were observed with a scanning electron microscope, the average particle size was 6.8 μm and the specific surface area was 18.1 m ² / mmol-Al.

<Preparation of solid catalyst component (γ1)>
16.03 mL of dehydrated toluene was charged into a 40 mL glass container equipped with a magnetic stir bar and sufficiently nitrogen-substituted, and 5.71 mL (3.57 mmol in terms of Al atoms) of the hexane slurry of the solid aluminoxane (C-1) was added. I charged it. Next, di (p-tolyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride represented by the following formula (A-1) (hereinafter referred to as component (A-1)). 3.26 mL of the toluene solution (0.0210 mmol in terms of Zr atom) was added dropwise and reacted at room temperature for 30 minutes to obtain a solid catalyst component (γ1).

＜エチレンホモ重合＞
充分に窒素置換した内容積１リットルのＳＵＳ製オートクレーブに精製ヘプタン５００ｍＬを入れ、エチレンを流通し、液相および気相をエチレンで飽和させた。ここに、トリイソブチルアルミニウム（東ソー・ファインケム（株）製）のｎ−デカン溶液（Ａｌ＝１．０ｍｏｌ／Ｌ）０．２５ｍｌ、および前記固体触媒成分（γ１）を固体成分換算で４．５ｍｇ装入した。その後、７５℃に昇温して、０．６５ＭＰａ・Ｇとなるようにエチレン／水素混合ガス（水素濃度：０．４５ｍｏｌ％）を連続的に供給し、６０分間重合を行った。

<Ethylene homopolymerization>
500 mL of purified heptane was placed in a fully nitrogen-substituted SUS autoclave with an internal volume of 1 liter, ethylene was circulated, and the liquid and gas phases were saturated with ethylene. Here, 0.25 ml of an n-decane solution (Al = 1.0 mol / L) of triisobutylaluminum (manufactured by Toso Finechem Co., Ltd.) and the solid catalyst component (γ1) are loaded in 4.5 mg in terms of solid component. I entered. Then, the temperature was raised to 75 ° C., and an ethylene / hydrogen mixed gas (hydrogen concentration: 0.45 mol%) was continuously supplied so as to be 0.65 MPa · G, and polymerization was carried out for 60 minutes.

The autoclave was cooled and the residual gas was purged to terminate the polymerization. The obtained ethylene polymer (PE) slurry was filtered through a Kiriyama funnel (φ95 mm, filter paper No. 4). There was no clogging of the filter paper. The ethylene polymer was dried under reduced pressure at 80 ° C. for 10 hours. The obtained ethylene polymer weighed 95.67 g, had a polymerization activity of 21,400 g-PE / g-cat, and a productivity of 21,400 g-PE / g-cat · h. As a result of the analysis of the ethylene polymer, the bulk density was 417 kg / m ³ , and the ultimate viscosity [η] ₁ was 2.14 dL / g.

<Ethylene / 1-hexene copolymerization>
500 mL of purified heptane was placed in a fully nitrogen-substituted SUS autoclave with an internal volume of 1 liter, ethylene was circulated, and the liquid and gas phases were saturated with ethylene. Here, 0.25 ml of an n-decane solution (Al = 1.0 mol / L) of triisobutylaluminum (manufactured by Toso Finechem Co., Ltd.), 2.3 mg of the solid catalyst component (γ1) in terms of solid component, and 1-Hexene 3 ml was charged. Then, the temperature was raised to 75 ° C., and an ethylene / hydrogen mixed gas (hydrogen concentration: 0.45 mol%) was continuously supplied so as to be 0.65 MPa · G, and polymerization was carried out for 60 minutes.

The autoclave was cooled and the residual gas was purged to terminate the polymerization. The obtained ethylene polymer (PE) slurry was filtered through a Kiriyama funnel (φ95 mm, filter paper No. 4). There was no clogging of the filter paper. The ethylene polymer was dried under reduced pressure at 80 ° C. for 10 hours. The obtained ethylene / 1-hexene copolymer was 101.05 g, the polymerization activity was 44,000 g-PE / g-cat, and the productivity was 44,000 g-PE / g-cat · h. As a result of the analysis of the ethylene / 1-hexene copolymer, the bulk density was 435 kg / m ³ , and the ultimate viscosity [η] ₂ was 3.93 dL / g. The ratio of the ultimate viscosity [η] ₁ to the ultimate viscosity [η] ₂ ([η] ₂ / [η] ₁ ) was 1.84. The results are shown in Table 16.

(Component (A-2))
The solid catalyst component (γ2) was prepared in the same manner as the solid catalyst component (γ1) except that the component (A-2) represented by the following formula (A-2) was used instead of the component (A-1). did. Further, ethylene homopolymerization and ethylene / 1-hexene copolymerization were carried out in the same manner as in the case where the solid catalyst component (γ1) was used, except that the solid catalyst component (γ2) was used. The results are shown in Table 16.

（成分（Ｂ−１））
＜固体触媒成分（γ３）の調製＞
磁気攪拌子を備え、充分に窒素置換した４０ｍＬガラス容器に脱水トルエン１６．８０ｍＬを装入し、前記固体状アルミノキサン（Ｃ−１）のヘキサンスラリーを５．７１ｍＬ（Ａｌ原子換算で３．５７ｍｍｏｌ）装入した。次いで、下記式（Ｂ−１）で表される成分（Ｂ−１）のトルエン溶液２．４９ｍＬ（Ｚｒ原子換算で０．０２１０ｍｍｏｌ）を滴下装入し、室温で３０分反応させ、固体触媒成分（γ３）を得た。

(Ingredient (B-1))
<Preparation of solid catalyst component (γ3)>
16.80 mL of dehydrated toluene was charged into a 40 mL glass container equipped with a magnetic stir bar and sufficiently nitrogen-substituted, and 5.71 mL (3.57 mmol in terms of Al atoms) of the hexane slurry of the solid aluminoxane (C-1) was added. I charged it. Next, 2.49 mL (0.0210 mmol in terms of Zr atom) of a toluene solution of the component (B-1) represented by the following formula (B-1) was added dropwise and reacted at room temperature for 30 minutes to form a solid catalyst component. (Γ3) was obtained.

＜エチレンホモ重合＞
充分に窒素置換した内容積１リットルのＳＵＳ製オートクレーブに精製ヘプタン５００ｍＬを入れ、エチレンを流通し、液相および気相をエチレンで飽和させた。ここに、トリイソブチルアルミニウム（東ソー・ファインケム（株）製）のｎ−デカン溶液（Ａｌ＝１．０ｍｏｌ／Ｌ）０．２５ｍｌ、および前記固体触媒成分（γ３）を固体成分換算で３．６ｍｇ装入した。その後、７５℃に昇温して、０．６５ＭＰａ・Ｇとなるようにエチレン／水素混合ガス（水素濃度：０．４５ｍｏｌ％）を連続的に供給し、６０分間重合を行った。

<Ethylene homopolymerization>
500 mL of purified heptane was placed in a fully nitrogen-substituted SUS autoclave with an internal volume of 1 liter, ethylene was circulated, and the liquid and gas phases were saturated with ethylene. Here, 0.25 ml of an n-decane solution (Al = 1.0 mol / L) of triisobutylaluminum (manufactured by Toso Finechem Co., Ltd.) and the solid catalyst component (γ3) are loaded in 3.6 mg in terms of solid component. I entered. Then, the temperature was raised to 75 ° C., and an ethylene / hydrogen mixed gas (hydrogen concentration: 0.45 mol%) was continuously supplied so as to be 0.65 MPa · G, and polymerization was carried out for 60 minutes.

The autoclave was cooled and the residual gas was purged to terminate the polymerization. The obtained ethylene polymer (PE) slurry was filtered through a Kiriyama funnel (φ95 mm, filter paper No. 4). There was no clogging of the filter paper. The ethylene polymer was dried under reduced pressure at 80 ° C. for 10 hours. The obtained ethylene polymer weighed 92.32 g, had a polymerization activity of 25,500 g-PE / g-cat, and a productivity of 25,500 g-PE / g-cat · h. As a result of the analysis of the ethylene polymer, the bulk density was 404 kg / m ³ , and the ultimate viscosity [η] ₁ was 1.11 dL / g.

<Ethylene / 1-hexene copolymerization>
500 mL of purified heptane was placed in a fully nitrogen-substituted SUS autoclave with an internal volume of 1 liter, ethylene was circulated, and the liquid and gas phases were saturated with ethylene. Here, 0.25 ml of an n-decane solution (Al = 1.0 mol / L) of triisobutylaluminum (manufactured by Toso Finechem Co., Ltd.), 3.7 mg of the solid catalyst component (γ3) in terms of solid component, and 1-Hexene 3 ml was charged. Then, the temperature was raised to 75 ° C., and an ethylene / hydrogen mixed gas (hydrogen concentration: 0.45 mol%) was continuously supplied so as to be 0.65 MPa · G, and polymerization was carried out for 60 minutes.

The autoclave was cooled and the residual gas was purged to terminate the polymerization. The obtained ethylene polymer (PE) slurry was filtered through a Kiriyama funnel (φ95 mm, filter paper No. 4). There was no clogging of the filter paper. The ethylene polymer was dried under reduced pressure at 80 ° C. for 10 hours. The obtained ethylene / 1-hexene copolymer was 89.77 g, the polymerization activity was 24,200 g-PE / g-cat, and the productivity was 24,200 g-PE / g-cat · h. As a result of the analysis of the ethylene / 1-hexene copolymer, the bulk density was 415 kg / m ³ , and the ultimate viscosity [η] ₂ was 1.12 dL / g. The ratio of the ultimate viscosity [η] ₁ to the ultimate viscosity [η] ₂ ([η] ₂ / [η] ₁ ) was 1.01. The results are shown in Table 16.

(Component (B-2))
<Preparation of solid catalyst component (γ4)>
14.07 mL of dehydrated toluene was charged into a 40 mL glass container equipped with a magnetic stir bar and sufficiently nitrogen-substituted, and 5.71 mL (3.57 mmol in terms of Al atoms) of the hexane slurry of the solid aluminoxane (C-1) was added. I charged it. Next, 5.22 mL (0.0210 mmol in Zr atom equivalent) of a toluene solution of the component (B-2) represented by the following formula (B-2) was added dropwise and reacted at room temperature for 30 minutes to form a solid catalyst component. (Γ4) was obtained.

＜エチレンホモ重合＞
充分に窒素置換した内容積１リットルのＳＵＳ製オートクレーブに精製ヘプタン５００ｍＬを入れ、エチレンを流通し、液相および気相をエチレンで飽和させた。ここに、トリイソブチルアルミニウム（東ソー・ファインケム（株）製）のｎ−デカン溶液（Ａｌ＝１．０ｍｏｌ／Ｌ）０．２５ｍｌ、および前記固体触媒成分（γ４）を固体成分換算で３．７ｍｇ装入した。その後、７５℃に昇温して、０．６５ＭＰａ・Ｇとなるようにエチレン／水素混合ガス（水素濃度：０．４５ｍｏｌ％）を連続的に供給し、６０分間重合を行った。

<Ethylene homopolymerization>
500 mL of purified heptane was placed in a fully nitrogen-substituted SUS autoclave with an internal volume of 1 liter, ethylene was circulated, and the liquid and gas phases were saturated with ethylene. Here, 0.25 ml of an n-decane solution (Al = 1.0 mol / L) of triisobutylaluminum (manufactured by Toso Finechem Co., Ltd.) and 3.7 mg of the solid catalyst component (γ4) in terms of solid component are loaded. I entered. Then, the temperature was raised to 75 ° C., and an ethylene / hydrogen mixed gas (hydrogen concentration: 0.45 mol%) was continuously supplied so as to be 0.65 MPa · G, and polymerization was carried out for 60 minutes.

The autoclave was cooled and the residual gas was purged to terminate the polymerization. The obtained ethylene polymer (PE) slurry was filtered through a Kiriyama funnel (φ95 mm, filter paper No. 4). There was no clogging of the filter paper. The ethylene polymer was dried under reduced pressure at 80 ° C. for 10 hours. The obtained ethylene polymer weighed 92.26 g, had a polymerization activity of 25,500 g-PE / g-cat, and a productivity of 25,500 g-PE / g-cat · h. As a result of the analysis of the ethylene polymer, the bulk density was 340 kg / m ³ , and the ultimate viscosity [η] ₁ was 1.63 dL / g.

<Ethylene / 1-hexene copolymerization>
500 mL of purified heptane was placed in a fully nitrogen-substituted SUS autoclave with an internal volume of 1 liter, ethylene was circulated, and the liquid and gas phases were saturated with ethylene. Here, 0.25 ml of an n-decane solution (Al = 1.0 mol / L) of triisobutylaluminum (manufactured by Toso Finechem Co., Ltd.), 3.4 mg of the solid catalyst component (γ4) in terms of solid component, and 1-Hexene 3 ml was charged. Then, the temperature was raised to 75 ° C., and an ethylene / hydrogen mixed gas (hydrogen concentration: 0.45 mol%) was continuously supplied so as to be 0.65 MPa · G, and polymerization was carried out for 60 minutes.

The autoclave was cooled and the residual gas was purged to terminate the polymerization. The obtained ethylene polymer (PE) slurry was filtered through a Kiriyama funnel (φ95 mm, filter paper No. 4). There was no clogging of the filter paper. The ethylene polymer was dried under reduced pressure at 80 ° C. for 10 hours. The obtained ethylene / 1-hexene copolymer was 83.67 g, the polymerization activity was 24,500 g-PE / g-cat, and the productivity was 24,500 g-PE / g-cat · h. As a result of the analysis of the ethylene / 1-hexene copolymer, the bulk density was 370 kg / m ³ , and the ultimate viscosity [η] ₂ was 1.64 dL / g. The ratio of the ultimate viscosity [η] ₁ to the ultimate viscosity [η] ₂ ([η] ₂ / [η] ₁ ) was 1.01. The results are shown in Table 16.

(Ingredients (B-3) to (B-6))
For the components (B-3) to (B-6) represented by the following formulas (B-3) to (B-6), a solid catalyst component was prepared in the same manner as the component (B-1), and ethylene homopolymerization was performed. And ethylene / 1-hexene copolymerization were performed. The results are shown in Table 16.

［実施例１］
＜固体触媒成分（γ１１）の調製＞
充分に窒素置換した室温下（２０〜２５℃）の反応器中に、ヘキサン３１．０Ｌを投入し、固体状ＭＡＯ成分をアルミニウム原子換算で７．１５ｍｏｌ（９．３４Ｌ）入れ、その懸濁液を１０分攪拌した。成分（Ａ−１）２１．０ｍｍｏｌを、トリイソブチルアルミニウム１２６ｍｍｏｌを含むヘキサン溶液２．４０Ｌに溶解させ、反応器に加えた後、１０分攪拌した。続いて、成分（Ｂ−１）２１．０ｍｍｏｌを、トリイソブチルアルミニウム６３．０ｍｍｏｌを含むヘキサン溶液２．２０Ｌに溶解させ、反応器に加えた後、６０分攪拌した。続いて、トリイソブチルアルミニウム３１１ｍｍｏｌを含むヘキサン溶液２．７０Ｌを反応器に加えた後、６０分攪拌した。最後に、アデカプロニックＬ−７１（商品名、（株）ＡＤＥＫＡ製、以下Ｌ−７１とも示す）４０．０ｇを含むヘキサン溶液０．８００Ｌを加え、６０分間撹拌し、固体触媒成分（γ１１）を得た。

[Example 1]
<Preparation of solid catalyst component (γ11)>
31.0 L of hexane was placed in a fully nitrogen-substituted reactor at room temperature (20 to 25 ° C.), 7.15 mol (9.34 L) of the solid MAO component was placed in terms of aluminum atoms, and a suspension thereof was added. Was stirred for 10 minutes. 21.0 mmol of the component (A-1) was dissolved in 2.40 L of a hexane solution containing 126 mmol of triisobutylaluminum, added to the reactor, and then stirred for 10 minutes. Subsequently, 21.0 mmol of the component (B-1) was dissolved in 2.20 L of a hexane solution containing 63.0 mmol of triisobutylaluminum, added to the reactor, and then stirred for 60 minutes. Subsequently, 2.70 L of a hexane solution containing 311 mmol of triisobutylaluminum was added to the reactor, and the mixture was stirred for 60 minutes. Finally, 0.800 L of a hexane solution containing 40.0 g of ADEKA PRONIC L-71 (trade name, manufactured by ADEKA Corporation, hereinafter also referred to as L-71) was added, and the mixture was stirred for 60 minutes to obtain a solid catalyst component (γ11). Got

<Manufacturing of ethylene-based copolymer>
In the first polymerization tank, hexane was 53.0 L / hr, the solid catalyst component (γ11) was 0.034 mmol / hr in terms of zirconium atoms, triisobutylaluminum was 11.7 mmol / hr, and ethylene was 7.50 kg / hr. While continuously supplying hr and hydrogen molecules at 53.0 NL / hr and L-71 at 0.600 g / hr, and continuously extracting the contents of the polymerization tank so that the liquid level in the polymerization tank becomes constant. The polymerization was carried out under the conditions of a polymerization temperature of 75.0 ° C., a reaction pressure of 0.460 MPaG, and an average residence time of 2.60 hr. Unreacted ethylene and hydrogen molecules were substantially removed from the contents continuously extracted from the first polymerization tank in a flash drum maintained at an internal pressure of 0.030 MPaG and 40.0 ° C.

Then, the contents are continuously added to the second polymerization tank together with hexane 130 L / hr, ethylene 9.40 kg / hr, hydrogen molecule 16.8 NL / hr, L-71 0.740 g / hr, and 1-hexene 700 g / hr. The polymerization was continued under the conditions of a polymerization temperature of 75.0 ° C., a reaction pressure of 0.590 MPaG, and an average residence time of 1.05 hr. In the second polymerization tank as well, the contents of the polymerization tank were continuously extracted so that the liquid level in the polymerization tank became constant. In order to prevent unintended polymerization such as the formation of a polymer containing a large amount of 1-hexene, methanol was supplied to the contents extracted from the second polymerization tank at 2.50 L / hr to inactivate the catalyst. Then, the hexane and the unreacted monomer in the contents were removed by a solvent separator and dried to obtain an ethylene-based copolymer.

The resulting polymer in the first polymerization vessel, density 973kg ^/ m 3, MFR of 2.16kg load 18.8 g / 10min, an intrinsic viscosity [eta] was 0.99 dl / g. Component 45 wt% polymerized in the first polymerization vessel, component which is polymerized in the second polymerization vessel was adjusted to operating conditions to include 55 wt%, a density of 949kg ^/ m 3, of 2.16kg load MFR An ethylene-based copolymer having a specific viscosity of 0.32 g / 10 min and an ultimate viscosity [η] of 2.15 dL / g was obtained. When the obtained ethylene-based copolymer was evaluated according to the above-mentioned fisheye evaluation method, the evaluation was "○".

[Example 2]
<Preparation of solid catalyst component (γ12)>
A solid catalyst component (γ12) was prepared in the same manner as in Example 1 except that the amount of the component (A-1) was changed to 12.6 mmol and the amount of the component (B-1) was changed to 29.4 mmol.

<Manufacturing of ethylene-based copolymer>
Polymerization was conducted in in each polymerization tank as in Example 1, a density of 948kg ^/ m 3, MFR of 2.16kg load 0.32 g / 10min, an intrinsic viscosity [eta] is 2.33dL / g of the ethylene A polymer was obtained. When the obtained ethylene-based copolymer was evaluated according to the above-mentioned fisheye evaluation method, the evaluation was "○".

[Example 3]
<Preparation of solid catalyst component (γ13)>
A solid catalyst component (γ13) was prepared in the same manner as in Example 1 except that the amount of the component (A-1) was changed to 29.4 mmol and the amount of the component (B-1) was changed to 12.6 mmol.

<Manufacturing of ethylene-based copolymer>
Polymerization was carried out in each polymerization tank in the same manner as in Example 1 ^{to obtain an ethylene copolymer having a density of 949 kg / m 3} and an ultimate viscosity [η] of 2.21 dL / g. When the obtained ethylene-based copolymer was evaluated according to the above-mentioned fisheye evaluation method, the evaluation was "○".

[Example 4]
<Preparation of solid catalyst component (γ14)>
A solid catalyst component (γ14) was prepared in the same manner as in Example 1 except that the component (B-2) was used instead of the component (B-1).

<Manufacturing of ethylene-based copolymer>
Polymerization was carried out in each polymerization tank in the same manner as in Example 1 ^{to obtain an ethylene copolymer having a density of 948 kg / m 3} and an ultimate viscosity [η] of 2.18 dL / g. When the obtained ethylene-based copolymer was evaluated according to the above-mentioned fisheye evaluation method, the evaluation was "○".

[Comparative Example 1]
<Preparation of solid catalyst component (γ15)>
22.8 L of hexane was placed in a fully nitrogen-substituted reactor at room temperature (20 to 25 ° C.), 5.67 mol (9.46 L) of the solid MAO component was placed in terms of aluminum atoms, and a suspension thereof was added. Was stirred for 10 minutes. 33.3 mmol of the component (A-1) was dissolved in 2.00 L of a hexane solution containing 67.0 mmol of triisobutylaluminum, added to the reactor, and then stirred for 60 minutes. Subsequently, 2.60 L of a hexane solution containing 333 mmol of triisobutylaluminum was added to the reactor, and the mixture was stirred for 60 minutes. Finally, 1.00 L of a hexane solution containing 32.0 g of L-71 was added and stirred for 60 minutes to obtain a solid catalyst component (γ15).

<Manufacturing of ethylene-based copolymer>
In the first polymerization tank, hexane was 53.0 L / hr, the solid catalyst component (γ15) was 0.036 mmol / hr in terms of zirconium atoms, triisobutylaluminum was 11.7 mmol / hr, and ethylene was 7.60 kg / hr. While continuously supplying hr and hydrogen molecules at 37.3 NL / hr and L-71 at 0.600 g / hr, and continuously extracting the contents of the polymerization tank so that the liquid level in the polymerization tank becomes constant. The polymerization was carried out under the conditions of a polymerization temperature of 75.1 ° C., a reaction pressure of 0.600 MPaG, and an average residence time of 2.60 hr. Unreacted ethylene and hydrogen molecules were substantially removed from the contents continuously extracted from the first polymerization tank in a flash drum maintained at an internal pressure of 0.030 MPaG and 40.0 ° C.

Then, the contents are continuously added to the second polymerization tank together with hexane 130 L / hr, ethylene 9.30 kg / hr, hydrogen molecule 10.8 NL / hr, L-71 0.740 g / hr, and 1-hexene 550 g / hr. The polymerization was continued under the conditions of a polymerization temperature of 74.8 ° C., a reaction pressure of 0.580 MPaG, and an average residence time of 1.05 hr. In the second polymerization tank as well, the contents of the polymerization tank were continuously extracted so that the liquid level in the polymerization tank became constant. In order to prevent unintended polymerization such as the formation of a polymer containing a large amount of 1-hexene, methanol was supplied to the contents extracted from the second polymerization tank at 2.50 L / hr to inactivate the catalyst. Then, the hexane and the unreacted monomer in the contents were removed by a solvent separator and dried to obtain an ethylene-based copolymer.

The polymer obtained in the first polymerization tank had a density of 971 ^{kg / m 3} , an MFR of 2.16 kg load of 40.7 g / 10 min, and an ultimate viscosity [η] of 0.93 dL / g. Component 45 wt% polymerized in the first polymerization vessel, component which is polymerized in the second polymerization vessel was adjusted to operating conditions to include 55 wt%, a density of 948kg ^/ m 3, of 2.16kg load MFR An ethylene-based copolymer having a maximum viscosity of 0.48 g / 10 min and an ultimate viscosity [η] of 2.32 dL / g was obtained. When the obtained ethylene-based copolymer was evaluated according to the fisheye evaluation method, the evaluation was "x".

Claims (6)

A catalyst for olefin polymerization containing the following component (A), the following component (B), and the following component (C).
Component (A): At least one compound represented by the following formula (I), which is a compound other than the following component (B);

(In the formula (I), X is a monovalent group, and each of them independently has a hydrogen atom, a halogen atom, a hydrocarbon group, a halogen-containing group, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, and a nitrogen-containing group. phosphorus-containing group, a boron-containing group or an aluminum-containing group, good .M be the same or different from each other, .cp ¹ is a titanium atom, a zirconium atom or a hafnium atom, form a sandwich structure together with M and Cp ² Shows a cyclopentadienyl group or a substituted cyclopentadienyl group that can be, Cp ² represents a substituted cyclopentadienyl group that can form a sandwich structure with M and Cp ^{1, and the substituted cyclopentadi.} The enyl group is a group selected from an indenyl group, a fluorenyl group and an azurenyl group, and the fluorenyl group having one or more hydrogen atoms substituted with a hydrocarbon group having 1 to 20 carbon atoms is a fluorenyl group. It contains groups and azulenyl groups, but in these cases it does not include those in which some or all of the double bonds of the unsaturated ring fused to the cyclopentadienyl group are hydrogenated. Y has 1 to 1 carbon atoms. 30 divalent hydrocarbon groups, divalent halogenated hydrocarbon groups with 1 to 20 carbon atoms, divalent silicon-containing groups, divalent germanium-containing groups, divalent tin-containing groups, -O-,- CO-, _{-S-, -SO-, -SO 2-} , -Ge-, -Sn-, -NR ^a- , -P ( ^Ra )-, -P (O) (R ^a )-, -BR ^{Indicates a} − or −AlR ^a −. ^Ra has a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, a hydrogen atom, a halogen atom or a nitrogen atom having 1 to 20 carbon atoms. A nitrogen compound residue in which one or two hydrocarbon groups are bonded (-NRH or -NR ₂ ; R is a hydrocarbon group having 1 to 20 carbon atoms).
Component (B): At least one compound selected from the compounds represented by the following formulas (II), (III), (IV) and (V);

(Formula (II), in (III) and ^{(IV), R 2, R} 3, R 5, R 6 and ^{R 7} is a monovalent group, each independently, a hydrogen atom, a hydrocarbon group, a halogen-containing Groups, oxygen-containing groups, nitrogen-containing groups, boron-containing groups, sulfur-containing groups, phosphorus-containing groups, silicon-containing groups, germanium-containing groups or tin-containing groups, which may be the same or different from each other and adjacent substituents. They may be bonded to each other to form a ring. R ⁴ is a hydrogen atom. Q ² is a divalent group, which is a hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing group, a silicon-containing group, and germanium. It is a containing group or a tin-containing group, and R ³ and Q ² may be bonded to each other to form a ring. Q ³ is a divalent group, which is a hydrocarbon group having 1 to 20 carbon atoms and a halogen-containing group. , a silicon-containing group, a germanium-containing group or a tin-containing group, ^{R 3} and ^{Q 3} may be bonded to each other to form a ring, provided that, .Q ^{4 Q 3} are free of ^{-L-D 3} is , Carbon atom, silicon atom, germanium atom or tin atom, R ³ and R ⁷ may be bonded to each other to form a ring. X is a monovalent group, which are independently hydrogen atom and halogen. Atomic, hydrocarbon groups, halogen-containing groups, silicon-containing groups, oxygen-containing groups, sulfur-containing groups, nitrogen-containing groups, phosphorus-containing groups, boron-containing groups or aluminum-containing groups, which may be the same or different from each other. Is a titanium atom, a zirconium atom or a hafnium atom. L is a divalent hydrocarbon group having a linear carbon chain having 1 to 10 carbon atoms. D ¹ , D ² and D ³ are as follows, respectively. Formulas (D-a), (D-b), (D-c), (D-d), (D-e), (D-f), (D-g), (D-h) or ( It is a group represented by Di).)

(In formulas (Db), (Dc), (Dd), (D-e), (Df) and (Dg), R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ And R ¹³ are monovalent groups, which are independently hydrogen atom, halogen atom, hydrocarbon group, halogen-containing group, silicon-containing group, oxygen-containing group, nitrogen-containing group, boron-containing group, sulfur-containing group, and phosphorus. It is a containing group, a silicon-containing group, a germanium-containing group or a tin-containing group, which may be the same or different from each other, and adjacent substituents may be bonded to each other to form a ring. R ¹² is a monovalent group. , and the oxygen-containing group, a nitrogen-containing group, a sulfur-containing group or a phosphorus-containing group, may be bonded to each other to form a ring with the adjacent R ¹¹ .ch is an oxygen atom or a sulfur atom .Pn is It is a nitrogen atom or a phosphorus atom.)

(In the formula (V), X is a monovalent group, and each of them independently has a hydrogen atom, a halogen atom, a hydrocarbon group, a halogen-containing group, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, and a nitrogen-containing group. It is a phosphorus-containing group, a boron-containing group or an aluminum-containing group and may be the same or different from each other. M is a titanium atom, a zirconium atom or a hafnium atom. ^{Cp 1} and Cp ² form a sandwich structure with M. Indicates a cyclopentadienyl group or a substituted cyclopentadienyl group which can be the same or different from each other.)
Ingredient (C):
(C-1) An organometallic compound represented by the following formula (VI), (VII) or (VIII),
(C-2) Organoaluminium oxy compound,
(C-3) A compound that reacts with the component (A) and the component (B) to form an ion pair, and (c-4) the above (c-1), the above (c-2) and the above (c). At least one component selected from the group consisting of solid components obtained by insolubilizing a component containing at least one selected from the group consisting of -3);
_{^{R a m Al (OR b)}} n H p X q ··· (VI)
(In formula (VI), ^Ra and R ^b each independently represent a hydrocarbon group having 1 to 15 carbon atoms and may be the same or different from each other. X represents a halogen atom and m is 0. <m ≦ 3, n satisfies 0 ≦ n <3, p satisfies 0 ≦ p <3, q satisfies 0 ≦ q <3, and m + n + p + q = 3).
_{^{M a AlR a 4 ··· (VII}} )
(Formula (VII) in, ^{M a} is .R ^a lithium atom, sodium atom or a potassium atom represents a hydrogen atom or a hydrocarbon group having a carbon number 1 to 15.)
R ^a _r M ^b R ^b _s X _t ... (VIII)
(In formula (VIII), ^Ra and R ^b each independently represent a hydrocarbon group having 1 to 15 carbon ^{atoms and may be the same or different from each other. M b} may be a magnesium atom, a zinc atom or a zinc atom. It is a cadmium atom. X represents a halogen atom. R satisfies 0 <r ≦ 2, s satisfies 0 ≦ s ≦ 1, t satisfies 0 ≦ t ≦ 1, and r + s + t = 2.) The catalyst for olefin polymerization according to claim 1, wherein L is a divalent hydrocarbon group having a linear carbon chain having 1 to 3 carbon atoms in the formula (II), (III) or (IV). The catalyst for olefin polymerization according to claim 1 or 2, further comprising a solid carrier (S). _{It is obtained when the extreme viscosity [η] 1 of the} polymer obtained when ethylene is homopolymerized using a catalyst containing the component (A) and ethylene and 1-hexene are copolymerized using the catalyst. The catalyst for olefin polymerization according to any one of claims 1 to 3, wherein the relationship of the following formula (1) is established with the ultimate viscosity [η] _{2 of the polymer.}
[Η] ₂ / [η] ₁ > 1.1 (1) _{It is obtained when the extreme viscosity [η] 1 of the} polymer obtained when ethylene is homopolymerized using a catalyst containing the component (B) and ethylene and 1-hexene are copolymerized using the catalyst. The catalyst for olefin polymerization according to any one of claims 1 to 4, wherein the relationship of the following formula (2) is established with the ultimate viscosity [η] _{2 of the polymer.}
[Η] ₂ / [η] ₁ ≤ 1.1 (2) A method for producing an ethylene-based copolymer, which comprises a step of copolymerizing ethylene with an olefin having 3 to 20 carbon atoms in the presence of the catalyst for olefin polymerization according to any one of claims 1 to 5.
A method for producing an ethylene-based copolymer, wherein the density of the ethylene-based copolymer is 910 kg / m ³ or more and 980 kg / m ^{3 or less.}