JP2019059934A - Olefin polymerization catalyst and ethylene based polymer production method using that olefin polymerization catalyst - Google Patents

Abstract

To provide an olefin polymerization catalyst and an ethylene based polymer production method using the catalyst, which allow stable production of an ethylene based polymer that has many long chain branches and is excellent in moldability and mechanical strength.SOLUTION: The olefin polymerization catalyst comprises a component (A) being a transition metal compound represented by formula (1), a component (B) being a transition metal compound represented by formula (2), a component (C) being a specific organometallic compound, and a solid carrier (S).SELECTED DRAWING: None

Description

  The present invention relates to a catalyst for olefin polymerization and a method for producing an ethylene-based polymer using the catalyst, and more specifically, an ethylene-based polymer having many long-chain branches and excellent in moldability and mechanical strength. The present invention relates to a catalyst for olefin polymerization that can be stably produced and a method for producing an ethylene-based polymer using the catalyst.

It is well known that ethylene polymers obtained with Ziegler catalysts and metallocene catalysts generally have low melt tension and tend to be inferior in moldability to high pressure low density polyethylene.
In order to solve this problem, a method of blending high-pressure low-density polyethylene with ethylene polymer obtained by using Ziegler catalyst or metallocene catalyst (for example, Patent Document 1) or long chain branching type using a specific metallocene catalyst A method (for example, Patent Document 2) for producing an ethylene-based polymer is disclosed.

  Moreover, it is reported that many long-chain branches are introduce | transduced by using two types of specific bridge | crosslinking-type metallocene compounds, and the ethylene-type polymer which is excellent in molding processability can be manufactured (for example, patent documents 3 and 4). Furthermore, it is disclosed also about the manufacturing method which can reduce generation | occurrence | production of fouling etc. during superposition | polymerization including such an ethylene polymer (patent documents 5-7).

  Patent Documents 8 to 11 also report on a method for producing a long chain branched ethylene polymer using two metallocene compounds.

JP-A-7-026079 JP-A-4-213309 JP, 2006-233208, A JP, 2009-144148, A JP, 2013-224408, A JP, 2015-160858, A Unexamined-Japanese-Patent No. 2015-160859 Japanese Patent Application Publication No. 2007-520597 Unexamined-Japanese-Patent No. 2010-043152 JP, 2011-006674, A JP 2012-214780 A

  The above-mentioned Patent Documents 1 to 4 and 8 to 11 do not disclose any problems such as the occurrence of fouling during the polymerization reaction. Moreover, when the present inventors examined, even with the techniques of Patent Documents 5 to 7, the solution after slurry polymerization becomes cloudy, and if the polymer concentration during polymerization is increased, it is difficult to continue the operation due to fouling. The problem that it might become was discovered.

  As a result of further investigations by the present inventors, it is presumed that the cause is that the solution becomes turbid due to an increase in the amount of free polymer deposited in the solution after slurry polymerization, and fouling to the polymerization tank occurs. It came to

  The present invention has been made in view of the above-mentioned new problems, and stably produces an ethylene-based polymer having many long-chain branches and excellent in moldability and mechanical strength. It is an object of the present invention to provide a catalyst for olefin polymerization that can be used and a method for producing an ethylene-based polymer using the catalyst.

  As a result of intensive studies conducted in view of the above situation, the inventors of the present invention found that long chain branching is large, and moldability and machineability by using two types of bridged metallocene compounds having a specific structure in combination in the same polymerization system. It has been found that the amount of free polymer deposited in a solution after slurry polymerization can be reduced while maintaining the property of providing an ethylene polymer excellent in the mechanical strength, and fouling to the polymerization tank can be suppressed, and the present invention It came to complete.

That is, the catalyst for olefin polymerization of the present invention comprises the following component (A), the following component (B), the following component (C) and a solid carrier (S).
Component (A): transition metal compound represented by the following general formula (1);

［式（１）中、Ｍは周期表第４族遷移金属原子であり、
ｎはＭの価数を満たす１〜４の整数であり、
Ｘは水素原子、ハロゲン原子、炭化水素基、アニオン配位子、または孤立電子対で配位可能な中性配位子であり；該アニオン配位子はハロゲン含有基、ケイ素含有基、酸素含有基、硫黄含有基、窒素含有基、リン含有基、ホウ素含有基、アルミニウム含有基または共役ジエン系誘導体基であり；ｎが２以上の場合、複数存在するＸは、互いに同一でも異なっていてもよく、互いに結合して環を形成してもよく、
Ｑ¹は周期表第１４族遷移原子であり、
Ｒ¹〜Ｒ⁴およびＲ⁷〜Ｒ¹²は、それぞれ独立に水素原子、炭素数１〜４０の炭化水素基、ハロゲン含有基、ケイ素含有基、酸素含有基、窒素含有基または硫黄含有基であり、
Ｒ⁵は水素原子、炭素数１〜４０の炭化水素基、ハロゲン含有基、ケイ素含有基、酸素含有基、窒素含有基、硫黄含有基、または、窒素、酸素および硫黄から選ばれる原子を少なくとも１つ含む母骨格を５員環とする、置換基を有していてもよい複素環式芳香族基であり、
Ｒ⁶は、直鎖状部分の炭素数が３〜１０の飽和炭化水素基または直鎖状部分の炭素数が３〜１０の末端不飽和炭化水素基であり、
Ｒ¹とＲ²およびＲ³とＲ⁴は、互いに結合して置換基を有していてもよい飽和環を形成してもよく、
Ｒ²とＲ³、およびＲ⁷〜Ｒ¹⁰の隣接した置換基は、互いに結合して置換基を有していてもよい環を形成してもよく、
Ｒ¹¹とＲ¹²は、互いに結合してＱ¹を含む環を形成してもよく、該環は置換基を有していてもよい。］
成分（Ｂ）：下記一般式（２）で表される遷移金属化合物；

[In the formula (1), M is a group 4 transition metal atom of the periodic table,
n is an integer of 1 to 4 satisfying the valence of M,
X is a hydrogen atom, a halogen atom, a hydrocarbon group, an anionic ligand, or a neutral ligand that can be coordinated with a lone electron pair; the anionic ligand is a halogen-containing group, a silicon-containing group, an oxygen-containing group A sulfur-containing group, a nitrogen-containing group, a phosphorus-containing group, a boron-containing group, an aluminum-containing group or a conjugated diene-based derivative group; and when n is 2 or more, plural Xs may be the same or different from each other Well, they may be combined with each other to form a ring,
Q ¹ is a group 14 transition atom in the periodic table,
R ^{1 to} R ⁴ and R ^{7 to} R ¹² each independently represent a hydrogen atom, a hydrocarbon group having 1 to 40 carbon atoms, a halogen-containing group, a silicon-containing group, an oxygen-containing group, a nitrogen-containing group or a sulfur-containing group ,
R ⁵ represents a hydrogen atom, a hydrocarbon group having 1 to 40 carbon atoms, a halogen-containing group, a silicon-containing group, an oxygen-containing group, a nitrogen-containing group, a sulfur-containing group, or at least one atom selected from nitrogen, oxygen and sulfur A heteroaromatic group which may have a substituent, which has a 5-membered ring as a mother skeleton containing
R ⁶ is a saturated hydrocarbon group having 3 to 10 carbon atoms in the linear portion or a terminal unsaturated hydrocarbon group having 3 to 10 carbon atoms in the linear portion,
R ¹ and R ² and R ³ and R ⁴ may be bonded to each other to form a saturated ring which may have a substituent,
Adjacent substituents of R ² and R ³ and R ^{7 to} R ¹⁰ may combine with each other to form a ring which may have a substituent,
R ¹¹ and R ¹² may be bonded to each other to form a ring containing Q ^1, and the ring may have a substituent. ]
Component (B): transition metal compound represented by the following general formula (2);

［式（２）中、Ｍは周期表第４族遷移金属原子であり、
Ｘは、それぞれ独立に水素原子、ハロゲン原子、炭化水素基、ハロゲン含有炭化水素基、ケイ素含有基、酸素含有基、硫黄含有基、窒素含有基およびリン含有基から選ばれる原子または基であり、
Ｑ²は炭素数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およびスズ含有基から選ばれる基であり、
Ｒ¹³〜Ｒ²⁴は、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、硫黄含有基、リン含有基、ケイ素含有基、ゲルマニウム含有基およびスズ含有基から選ばれ、隣接する２個の基が連結して環を形成してもよい。］
成分（Ｃ）：下記一般式（３）〜（５）で表される有機金属化合物（ｃ−１）、有機アルミニウムオキシ化合物（ｃ−２）、ならびに、成分（Ａ）および成分（Ｂ）と反応してイオン対を形成する化合物（ｃ−３）からなる群より選ばれる少なくとも１種の化合物；
Ｒ^a _mＡｌ（ＯＲ^b)_n Ｈ_pＸ_q ・・・（３）
［式（３）中、Ｒ^aおよびＲ^bは、それぞれ独立に炭素原子数が１〜１５の炭化水素基を示し、Ｘはハロゲン原子を示し、ｍは０＜ｍ≦３、ｎは０≦ｎ＜３、ｐは０≦ｐ＜３、ｑは０≦ｑ＜３の数であり、かつｍ＋ｎ＋ｐ＋ｑ＝３である。］
Ｍ^a ＡｌＲ^a ₄ ・・・（４）
［式（４）中、Ｍ^aはＬｉ、ＮａまたはＫを示し、Ｒ^aは炭素原子数が１以上１５以下の炭化水素基を示す。］
Ｒ^a _rＭ^bＲ^b _sＸ_t ・・・（５）
［式（５）中、Ｒ^aおよびＲ^bは、それぞれ独立に炭素原子数が１以上１５以下の炭化水素基を示し、Ｍ^bはＭｇ、ＺｎおよびＣｄから選ばれ、Ｘはハロゲン原子を示し、rは０＜r≦２、ｓは０≦ｓ≦１、ｔは０≦ｔ≦１であり、かつｒ＋ｓ＋ｔ＝２である。］

[In the formula (2), M is a group 4 transition metal atom of the periodic table,
X is an atom or a group independently selected from a hydrogen atom, a halogen atom, a hydrocarbon group, a halogen-containing hydrocarbon group, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group and a phosphorus-containing group
Q ² is a group selected from a hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing group, a silicon-containing group, a germanium-containing group and a tin-containing group,
R ^{13 to} R ²⁴ each independently represent a hydrogen atom, 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 and tin Two adjacent groups selected from the contained groups may be linked to form a ring. ]
Component (C): an organic metal compound (c-1) represented by the following general formulas (3) to (5), an organic aluminum oxy compound (c-2), and a component (A) and a component (B) At least one compound selected from the group consisting of compounds (c-3) which react to form an ion pair;
_{^{R a m Al (OR b)}} n H p X q ··· (3)
[In Formula (3), R ^a and R ^b each independently represent a hydrocarbon group having 1 to 15 carbon atoms, X represents a halogen atom, m is 0 <m ≦ 3, n is 0 ≦ n <3, p is 0 ≦ p <3, q is a number of 0 ≦ q <3, and m + n + p + q = 3. ]
M ^a Al R ^a ₄ (4)
Wherein (4), M ^a represents a Li, Na or K, R ^a represents a hydrocarbon group having 1 to 15 carbon atoms. ]
R ^a _r M ^b R ^b _s X _t (5)
[In Formula (5), R ^a and R ^b each independently represent a hydrocarbon group having 1 to 15 carbon atoms, M ^b is selected from Mg, Zn and Cd, and X is a halogen atom , R is 0 <r ≦ 2, s is 0 ≦ s ≦ 1, t is 0 ≦ t ≦ 1, and r + s + t = 2. ]

  In the method for producing an ethylene-based polymer according to the present invention, ethylene is polymerized alone in the presence of the catalyst for olefin polymerization according to the present invention, or ethylene is copolymerized with an olefin having 3 to 20 carbon atoms. It is characterized by

The ethylene-based polymer obtained by the production method of the present invention is a copolymer of ethylene and an α-olefin having 4 to 20 carbon atoms, and satisfies the following requirements (1) to (4) preferable.
(1) The melt flow rate (MFR) at a load of 2.16 kg at 190 ° C. is 0.1 g / 10 min or more and 30 g / 10 min or less;
(2) The density is 875 kg / m ³ or more and 970 kg / m ³ or less;
(3) zero shear viscosity at 200 ° C. and [eta ₀ (P)], GPC-ratio (eta ₀ of viscosity detector method 6.8 square of weight average molecular weight determined by (GPC-VISCO) (Mw ^6.8) / Mw ^6.8 ) is not less than 0.03 × 10 ^{-30 and not} more than 7.5 × 10 ^-30 ;
(4) Intrinsic viscosity [[η] (dl / g)] measured in 135 ° C. decalin and weight-average molecular weight measured by GPC-viscosity detector method (GPC-VISCO): 0.776 (Mw ^0.776) Ratio ([η] / Mw ^0.776 ) is 0.90 × 10 ⁻⁴ or more and 1.65 × 10 ⁻⁴ or less.

  By using the catalyst for olefin polymerization of the present invention, the amount of free polymer deposited in the solution after slurry polymerization can be reduced, and fouling to the polymerization tank can be suppressed, so there are many long-chain branches, and molding processability And ethylene polymer excellent in mechanical strength can be manufactured stably.

  Hereinafter, a catalyst for olefin polymerization according to the present invention and a method for producing an ethylene-based polymer using the catalyst will be described in detail. In the present invention, the term "polymerization" is sometimes used to mean not only homopolymerization but also copolymerization, and the term "polymer" includes not only homopolymers but also copolymers. May be used in the same sense.

[Catalyst for olefin polymerization]
The olefin polymerization catalyst of the present invention comprises the component (A), the component (B), the component (C) and the solid carrier (S) described later.

<Component (A)>
Component (A) is a transition metal compound (hereinafter also referred to as “transition metal compound (1)”) represented by the following general formula (1). The olefin polymerization catalyst of the present invention contains at least one transition metal compound (1). That is, as the component (A), plural kinds of transition metal compounds (1) may be used.

前記式（１）において、Ｍは周期表第４族遷移金属原子であり、具体的にはチタン原子、ジルコニウム原子、ハフニウム原子であり、好ましくはジルコニウム原子またはハフニウム原子であり、より好ましくはジルコニウム原子である。

In the above formula (1), M is a Group 4 transition metal atom of the periodic table, specifically a titanium atom, a zirconium atom or a hafnium atom, preferably a zirconium atom or a hafnium atom, more preferably a zirconium atom It is.

In the formula (1), n is an integer of 1 to 4 satisfying the valence of M, and is preferably 2.
In the above formula (1), X is a hydrogen atom, a halogen atom, a hydrocarbon group, an anionic ligand, or a neutral ligand that can be coordinated with a lone electron pair; the anionic ligand contains a halogen A silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a phosphorus-containing group, a boron-containing group, an aluminum-containing group, or a conjugated diene-based derivative group; And may be the same as or different from each other, and may be combined with each other to form a ring. X is preferably a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group or an oxygen-containing group, and more preferably a halogen atom or a hydrocarbon group having 1 to 10 carbon atoms.

Examples of the halogen atom include fluorine, chlorine, bromine and iodine, and chlorine is particularly preferable.
Examples of the hydrocarbon group include
Methyl group, ethyl group, 1-propyl group, 1-butyl group, 1-pentyl group, 1-hexyl group, 1-heptyl group, 1-octyl group, iso-propyl group, sec-butyl group Group), tert-butyl group (2-methylpropan-2-yl group), iso-butyl group (2-methylpropyl group), pentan-2-yl group, 2-methylbutyl group, iso-pentyl group (3 -Methylbutyl group), neopentyl group (2,2-dimethylpropyl group), cyanyl group (1,2-dimethylpropyl group), iso-hexyl group (4-methylpentyl group), 2,2-dimethylbutyl group, 2 And a linear or branched alkyl group such as 3, 3-dimethylbutyl group, 3, 3-dimethylbutyl group, thexyl group (2,3-dimethylbut-2-yl group), 4, 4-dimethylpentyl group, etc. Kill group;
Vinyl group, allyl group, propenyl group (prop-1-en-1-yl group), iso-propenyl group (prop-1-en-2-yl group), allenyl group (prop-1,2-diene-1) -Yl group), but-3-en-1-yl group, crotyl group (but-2-en-1-yl group), but-3-en-2-yl group, methallyl group (2-methylallyl group) , Buta-1,3-dienyl group, penta-4-en-1-yl group, penta-3-en-1-yl group, penta-2-en-1-yl group, iso-pentenyl group (3- Methylbut-3-en-1-yl group), 2-methylbut-3-en-1-yl group, penta-4-en-2-yl group, prenyl group (3-methylbut-2-en-1-yl group) A straight or branched alkenyl group or unsaturated double bond-containing group such as
A linear or branched alkynyl group or unsaturated triple bond-containing group such as ethynyl group, prop-2-yn-1-yl group, propargyl group (prop-1-yn-1-yl group);
Benzyl, 2-methylbenzyl, 4-methylbenzyl, 2,4,6-trimethylbenzyl, 3,5-dimethylbenzyl, cuminyl (4-iso-propylbenzyl), 2,4,6 Aromatic-containing straight chain such as -tri-iso-propylbenzyl group, 4-tert-butylbenzyl group, 3,5-di-tert-butylbenzyl group, 1-phenylethyl group, benzhydryl group (diphenylmethyl group) Or branched alkyl groups and unsaturated double bond-containing groups;
Cyclic saturated hydrocarbon groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cycloheptatrienyl group, norbornyl group, norbornenyl group, 1-adamantyl group, 2-adamantyl group;
Phenyl group, tolyl group (methylphenyl group), xylyl group (dimethylphenyl group), mesityl group (2,4,6-trimethylphenyl group), cumenyl group (iso-propylphenyl group), duryl group (2,3, 5,6-Tetramethylphenyl group), 2,6-di-iso-propylphenyl group, 2,4,6-tri-iso-propylphenyl group, 4-tert-butylphenyl group, 3,5-di- Aromatic substituents such as tert-butylphenyl group, naphthyl group, biphenyl group, ter-phenyl group, binaphthyl group, acenaphthalenyl group, phenanthryl group, anthracenyl group, pyrenyl group, ferrocenyl group and the like can be mentioned.

  Among the above-mentioned hydrocarbon groups, methyl group, iso-butyl group, neopentyl group, cyanyl group, benzyl group, phenyl group, tolyl group, xylyl group, mesityl group and cumenyl group are preferable.

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

Among the halogen-containing groups, pentafluorophenyl group is preferable.
As the silicon-containing group, for example, trimethylsilyl group, triethylsilyl group, tri-iso-propylsilyl group, diphenylmethylsilyl group, tert-butyldimethylsilyl group, tert-butyldiphenylsilyl group, triphenylsilyl group, tris ( Examples include trimethylsilyl) silyl group and trimethylsilylmethyl group.

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

Among the above-mentioned oxygen-containing groups, methoxy group, ethoxy group, iso-propoxy group and tert-butoxy group are preferable.
Examples of the sulfur-containing group include mesyl group (methanesulfonyl group), phenylsulfonyl group, tosyl group (p-toluenesulfonyl group), tolylyl group (trifluoromethanesulfonyl group), nonafyl group (nonafluorobutanesulfonyl group), Mesylate group (methanesulfonate group), tosylate group (p-toluenesulfonate group), triflate group (trifluoromethanesulfonate group), nonaflate group (nonafluorobutanesulfonate group) can be mentioned.

Among the above-mentioned sulfur-containing groups, triflate (trifluoromethanesulfonate) is preferable.
Examples of the nitrogen-containing group include amino, cyano, methylamino, dimethylamino, ethylamino, diethylamino, diethylamino, allylamino, diallylamino, benzylamino, dibenzylamino, pyrrolidinyl and piperidinyl. Groups, morpholinyl groups, pyrrolyl groups, bis-triflylimide groups and the like.

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

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

で表される四員環（Ｍは、前記一般式（１）中のＭを表す。）を形成可能な、ＡｌＲ₄（Ｒは水素、アルキル基、置換基を有してもよいアリール基またはハロゲン原子等を示す。）で表される基が挙げられる。

AlR ₄ (R is hydrogen, an alkyl group, an aryl group which may have a substituent, or the like) capable of forming a four-membered ring represented by (where M represents M in the general formula (1)) And the like.

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

  Examples of neutral ligands that can be coordinated with lone electron pairs include ethers such as diethyl ether, tetrahydrofuran, dioxane, and 1,2-dimethoxyethane, amines such as triethylamine and diethylamine, pyridine, picoline, lutidine, Heterocyclic compounds such as oxazolines, oxazoles, thiazoles, imidazoles and thiophenes, and organic phosphorus compounds such as triphenylphosphine, tricyclohexylphosphine and tri-tert-butylphosphine.

In the above formula (1), Q ¹ is a group 14 transition atom of the periodic table, specifically a carbon atom, a silicon atom, a germanium atom or a tin atom, preferably a carbon atom or a silicon atom, particularly preferably Is a silicon atom.

In Formula (1), R ^{1 to} R ⁴ and R ^{7 to} R ¹² each independently represent a hydrogen atom, a hydrocarbon group having 1 to 40 carbon atoms, a halogen-containing group, a silicon-containing group, an oxygen-containing group, or a nitrogen-containing group R ⁵ is a hydrogen atom, a hydrocarbon group having 1 to 40 carbon atoms, a halogen-containing group, a silicon-containing group, an oxygen-containing group, a nitrogen-containing group, a sulfur-containing group, or nitrogen, oxygen and It is a heterocyclic aromatic group which may have a substituent and which has a 5-membered ring as a mother skeleton containing at least one atom selected from sulfur.

The hydrocarbon group having 1 to 40 carbon atoms as R ^{1 to} R ⁵ and R ^{7 to} R ¹² is preferably a hydrocarbon group having 1 to 20 carbon atoms (with the exception of aromatic hydrocarbon groups) or carbon It is several 6-40 aromatic hydrocarbon group. The above-mentioned hydrocarbon group having 1 to 20 carbon atoms is preferably an aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms. The hydrocarbon group having 1 to 20 carbon atoms also includes a substituent having an aromatic structure such as an arylalkyl group.

As said C1-C40 hydrocarbon group, for example,
Methyl group, ethyl group, 1-propyl group, 1-butyl group, 1-pentyl group, 1-hexyl group, 1-heptyl group, 1-octyl group, 1-nonyl group, 1-decanyl group, 1-undecanyl group 1-dodecanyl group, 1-eicosanyl group, iso-propyl group, sec-butyl group, tert-butyl group, iso-butyl group, pentan-2-yl group, 2-methylbutyl group, iso-pentyl group, neopentyl group Tert-pentyl group (1,1-dimethylpropyl group), cyanyl group, pentan-3-yl group, 2-methylpentyl group, 3-methylpentyl group, iso-hexyl group, 1,1-dimethylbutyl group 2-methylpentan-2-yl group), 3-methylpentan-2-yl group, 4-methylpentan-2-yl group, 2,2-dimethylbutyl group, 2,3-di A butyl butyl group, a 3,3-dimethylbutyl group, a texyl group, a 3-methylpentan-3-yl group, a 3,3-dimethylbut-2-yl group, a hexane-3-yl group, a 2-methylpentane-3- group Yl, heptane-4-yl, 2,4-dimethylpentan-2-yl, 3-ethylpentan-3-yl, 4,4-dimethylpentyl, 4-methylheptane-4-yl, Straight-chain having 1 to 40 carbon atoms, such as 4-propylheptan-4-yl group, 2,3,3-trimethylbutan-2-yl group, 2,4,4-trimethylpentan-2-yl group Or branched alkyl groups;
Vinyl, allyl, propenyl, iso-propenyl, allenyl, but-3-en-1-yl, crotyl, but-3-en-2-yl, methallyl, penta-4-ene -1-yl group, penta-3-en-1-yl group, penta-2-en-1-yl group, iso-pentenyl group, 2-methylbut-3-en-1-yl group, penta-4- En-2-yl group, prenyl group, 2-methyl-but-2-en-1-yl group, penta-3-en-2-yl group, 2-methyl-but-3-en-2-yl group , Penta-1-en-3-yl group, penta-2,4-diene-1-yl group, penta-1,3-dien-1-yl group, penta-1,4-dien-3-yl group , Iso-prenyl group (2-methyl-buta-1,3-dien-1-yl group), penta-2 4-dien-2-yl group, hexa-5-en-1-yl group, hexa-4-en-1-yl group, hexa-3-en-1-yl group, hexa-2-en-1-yl group Yl, 4-methyl-pent-4-en-1-yl, 3-methyl-pent-4-en-1-yl, 2-methyl-pent-4-en-1-yl, hexa- 5-en-2-yl group, 4-methyl-pent-3-en-1-yl group, 3-methyl-pent-3-en-1-yl group, 2,3-dimethyl-but-2-ene group -1-yl group, 2-methylpent-4-en-2-yl group, 3-ethylpent-1-en-3-yl group, hexa-3,5-dien-1-yl group, hexa-2,4 Dien-1-yl group, 4-methylpenta-1,3-dien-1-yl group, 2,3-dimethyl-buta-1,3-die Carbon atom such as -1-yl group, hexa-1,3,5-trien-1-yl group, 2- (cyclopentadienyl) propan-2-yl group, 2- (cyclopentadienyl) ethyl group 2 to 40 linear or branched alkenyl groups or unsaturated double bond-containing groups;
Ethynyl group, prop-2-yn-1-yl group, propargyl group, but-1-yn-1-yl group, but-2-yn-1-yl group, but-3-yn-1-yl group, Penta-1-yn-1-yl group, penta-2-yn-1-yl group, penta-3-yn-1-yl group, penta-4-yn-1-yl group, 3-methyl-buta- 1-in-1-yl group, penta-3-yn-2-yl group, 2-methyl-but-3-yn-1-yl group, penta-4-yn-2-yl group, hexa-1- In-1-yl group, 3,3-dimethyl-but-1-yn-1-yl group, 2-methyl-pent-3-yn-2-yl group, 2,2-dimethyl-but-3-yne A linear or branched group having 2 to 40 carbon atoms, such as -1-yl, hexa-4-yn-1-yl and hexa-5-yn-1-yl; Jo alkynyl group or unsaturated triple bond-containing group;
Benzyl group, 2-methylbenzyl group, 4-methylbenzyl group, 2,4,6-trimethylbenzyl group, 3,5-dimethylbenzyl group, cuminyl group, 2,4,6-tri-iso-propylbenzyl group, 4-tert-butylbenzyl group, 3,5-di-tert-butylbenzyl group, 1-phenylethyl group, benzhydryl group, cumyl group (2-phenylpropan-2-yl group), 2- (4-methylphenyl) ) Propan-2-yl group, 2- (3,5-dimethylphenyl) propan-2-yl group, 2- (4-tert-butylphenyl) propan-2-yl group, 2- (3,5-diethyl group) -Tert-Butylphenyl) propan-2-yl group, 3-phenylpentan-3-yl group, 4-phenylhepta-1,6-dien-4-yl group, 1,2,3-triphenyl group Lopan-2-yl group, 1,1-diphenylethyl group, 1,1-diphenylpropyl group, 1,1-diphenyl-but-3-en-1-yl group, 1,1,2-triphenylethyl group , Trityl group (triphenylmethyl group), tri- (4-methylphenyl) methyl group, 2-phenylethyl group, styryl group (2-phenylvinyl group), 2- (2-methylphenyl) ethyl group, 2- (4-methylphenyl) ethyl group, 2- (2,4,6-trimethylphenyl) ethyl group, 2- (3,5-dimethylphenyl) ethyl group, 2- (2,4,6-tri-iso-) Propylphenyl) ethyl group, 2- (4-tert-butylphenyl) ethyl group, 2- (3,5-di-tert-butylphenyl) ethyl group, 2-methyl-1-phenylpropan-2-yl group, 3- -Phenylpropyl group, cinnamyl group (3-phenylallyl group), neophyl group (2-methyl-2-phenylpropyl group), 3-methyl-3-phenylbutyl group, 2-methyl-4-phenylbutan-2-yl Group, cyclopentadienyldiphenylmethyl group, 2- (1-indenyl) propan-2-yl group, (1-indenyl) diphenylmethyl group, 2- (1-indenyl) ethyl group, 2- (tetrahydro-1-yl) Indacenyl) propan-2-yl group, (tetrahydro-1-indacenyl) diphenylmethyl group, 2- (tetrahydro-1-indacenyl) ethyl group, 2- (1-benzoindenyl) propan-2-yl group, (1 -Benzoindenyl) diphenylmethyl group, 2- (1-benzoindenyl) ethyl group, 2- (9-fluorenyl) propane -2-yl group, (9-fluorenyl) diphenylmethyl group, 2- (9-fluorenyl) ethyl group, 2- (1-azulenyl) propan-2-yl group, (1-azulenyl) diphenylmethyl group, 2- Aromatic-containing linear or branched alkyl group having 7 to 40 carbon atoms, such as (1-azulenyl) ethyl group, and unsaturated double bond-containing group;
Cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclopentenyl group, cyclopentadienyl group, dimethylcyclopentadienyl group, n-butylcyclopentadienyl group, n-butyl-methylcyclopentadienyl group, tetramethylcyclo Pentadienyl group, 1-methylcyclopentyl group, 1-allylcyclopentyl group, 1-benzylcyclopentyl group, cyclohexyl group, cyclohexenyl group, cyclohexadienyl group, 1-methylcyclohexyl group, 1-allylcyclohexyl group, 1-benzyl Cyclohexyl group, cycloheptyl group, cycloheptenyl group, cycloheptatrienyl group, 1-methylcycloheptyl group, 1-allylcycloheptyl group, 1-benzylcycloheptyl group, cyclooctyl group, cyclooctenyl group, cyclic Octadienyl group, cyclooctatrienyl group, 1-methylcyclooctyl group, 1-allylcyclooctyl group, 1-benzylcyclooctyl group, 4-cyclohexyl-tert-butyl group, norbornyl group, norbornenyl group, norbornadienyl group , 2-methylbicyclo [2.2.1] heptan-2-yl group, 7-methylbicyclo [2.2.1] heptane-7-yl group, bicyclo [2.2.2] octan-1-yl group Group, bicyclo [2.2.2] octan-2-yl group, 1-adamantyl group, 2-adamantyl group, 1- (2-methyladamantyl), 1- (3-methyladamantyl), 1- (4-) Methyladamantyl), 1- (2-phenyladamantyl), 1- (3-phenyladamantyl), 1- (4-phenyladamantyl), 1- 3,5-Dimethyladamantyl), 1- (3,5,7-trimethyladamantyl), 1- (3,5,7-triphenyladamantyl), pentalenyl group, indenyl group, fluorenyl group, indasenyl group, tetrahydroindase Cyclic saturated and unsaturated hydrocarbon groups having 3 to 40 carbon atoms, such as nyl, benzoindenyl and azulenyl groups;
Phenyl group, tolyl group, xylyl group, mesityl group, cumenyl group, duryl group, 2,6-di-iso-propylphenyl group, 2,4,6-tri-iso-propylphenyl group, 4-tert-butylphenyl Group, 3,5-di-tert-butylphenyl group, allylphenyl group, (but-3-en-1-yl) phenyl group, (but-2-en-1-yl) phenyl group, methallylphenyl group , Prenylphenyl group, 4-adamantylphenyl group, 3,5-di-adamantylphenyl group, naphthyl group, biphenyl group, ter-phenyl group, binaphthyl group, acenaphthalenyl group, phenanthryl group, anthracenyl group, pyrenyl group, ferrocenyl group, etc. And an aromatic substituent having 6 to 40 carbon atoms, and the like.

  Among the linear or branched alkyl group having 1 to 40 carbon atoms, methyl group, ethyl group, 1-propyl group, 1-butyl group, 1-pentyl group, 1-hexyl group, 1-heptyl group Group, 1-octyl group, iso-propyl group, sec-butyl group (butane-2-yl group), tert-butyl group, iso-butyl group, iso-pentyl group, neopentyl group, tert-pentyl group, pentane 3-yl, iso-hexyl, 1,1-dimethylbutyl, 3,3-dimethylbutyl, texyl, 3-methylpentan-3-yl, heptane-4-yl, 2,4- Dimethylpentan-2-yl group, 3-ethylpentan-3-yl group, 4,4-dimethylpentyl group, 4-methylheptan-4-yl group, 4-propylheptan-4-yl group, 2,4 4-trimethylpentan-2-yl group, etc. is preferable, and methyl group, ethyl group, 1-propyl group, 1-butyl group, 1-pentyl group, 1-hexyl group, iso-propyl group, tert-butyl group, Neopentyl group, 2,4-dimethylpentan-2-yl group and 2,4,4-trimethylpentan-2-yl group are more preferable.

  Among the linear or branched alkenyl group having a carbon number of 2 to 40 or the unsaturated double bond-containing group, vinyl group, allyl group, but-3-en-1-yl group, crotyl group, methallyl Group, penta-4-en-1-yl group, prenyl group, penta-1,4-dien-3-yl group, hexa-5-en-1-yl group, 2-methylpent-4-ene-2- group Preferred are vinyl, 2- (cyclopentadienyl) propan-2-yl, 2- (cyclopentadienyl) ethyl and the like, and vinyl, allyl, but-3-en-1-yl, penta The 4-en-1-yl group, the prenyl group and the hexa-5-en-1-yl group are more preferable.

  Among the linear or branched alkynyl group having a carbon number of 2 to 40 or the unsaturated triple bond-containing group, ethynyl group, prop-2-yn-1-yl group, propargyl group, but-2-yne -1-yl group, but-3-yn-1-yl group, penta-3-yn-1-yl group, penta-4-yn-1-yl group, 3-methyl-but-1-yne-1 -Yl group, 3,3-dimethyl-but-1-yn-1-yl group, hexa-4-yn-1-yl group, hexa-5-yn-1-yl group and the like, and prop-2- In-1-yl, propargyl, but-2-yn-1-yl and but-3-yn-1-yl are more preferred.

  Among the above-mentioned aromatic-containing linear or branched alkyl group having 7 to 40 carbon atoms and the unsaturated double bond-containing group, benzyl group, 2-methylbenzyl group, 4-methylbenzyl group, 2,4 , 6-trimethylbenzyl, 3,5-dimethylbenzyl, cuminyl, 2,4,6-tri-iso-propylbenzyl, 4-tert-butylbenzyl, 3,5-di-tert-butylbenzyl Group, benzhydryl group, cumyl group, 1,1-diphenylethyl group, trityl group, 2-phenylethyl group, 2- (4-methylphenyl) ethyl group, 2- (2,4,6-trimethylphenyl) ethyl group , 2- (3,5-dimethylphenyl) ethyl group, 2- (2,4,6-tri-iso-propylphenyl) ethyl group, 2- (4-tert-butylphenyl) ethyl group Group, 2- (3,5-di-tert-butylphenyl) ethyl group, styryl group, 2-methyl-1-phenylpropan-2-yl group, 3-phenylpropyl group, cinnamyl group, neophyl group, cyclopenta Dienyldiphenylmethyl, 2- (1-indenyl) propan-2-yl, (1-indenyl) diphenylmethyl, 2- (1-indenyl) ethyl, 2- (9-fluorenyl) propane-2- Group, (9-fluorenyl) diphenylmethyl group, 2- (9-fluorenyl) ethyl group, etc. are preferable, and benzyl group, benzhydryl group, cumyl group, 1,1-diphenylethyl group, trityl group, 2-phenylethyl group More preferred are 3-phenylpropyl and 2-cinnamyl (3-phenylallyl).

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

  Among the above-mentioned aromatic substituents having 6 to 40 carbon atoms, phenyl group, tolyl group, xylyl group, mesityl group, cumenyl group, 2,6-di-iso-propylphenyl group, 2,4,6-tri -Iso-propylphenyl group, 4-tert-butylphenyl group, 3,5-di-tert-butylphenyl group, allylphenyl group, prenylphenyl group, 4-adamantylphenyl group, naphthyl group, biphenyl group, ter-phenyl Group, binaphthyl group, phenanthryl group, anthracenyl group, ferrocenyl group and the like are preferable, and phenyl group, tolyl group, xylyl group, mesityl group, cumenyl group, 2,6-di-iso-propylphenyl group, 2,4,6- Tri-iso-propylphenyl group, 4-tert-butylphenyl group, 3,5-di-tert-butylphenyne Group, allyl phenyl group, 4-adamantyl phenyl group, a naphthyl group, a biphenyl group, phenanthryl group, anthracenyl group are more preferable.

Examples of the halogen-containing group as R ^{1 to} R ⁵ and R ^{7 to} R ¹² include, for example, fluoromethyl group, trifluoromethyl group, trichloromethyl group, pentafluoroethyl group, 2,2,2-trifluoroethyl group , Heptafluoropropyl group, 3,3,3-trifluoropropyl group, nonafluorobutyl group, 4,4,4-trifluorobutyl group, dodecafluorohexyl group, 6,6,6-trifluorohexyl group, chlorophenyl Group, fluorophenyl group, difluorophenyl group, trifluorophenyl group, tetrafluorophenyl group, pentafluorophenyl group, di-tert-butyl-fluorophenyl group, trifluoromethylphenyl group, bistrifluoromethylphenyl group, trifluoromethoxy Phenyl group, bis trifluoromethoxy , Trifluoromethylthiophenyl, bistrifluoromethylthiophenyl, fluorobiphenyl, difluorobiphenyl, trifluorobiphenyl, tetrafluorobiphenyl, pentafluorobiphenyl, di-tert-butyl-fluorobiphenyl, trifluoro Methylbiphenyl group, bistrifluoromethylbiphenyl group, trifluoromethoxybiphenyl group, bistrifluoromethoxybiphenyl group, trifluoromethyldimethylsilyl group, trifluoromethoxy group, pentafluoroethoxy group, fluorophenoxy group, difluorophenoxy group, trifluorophenoxy group Group, pentafluorophenoxy group, di-tert-butyl-fluorophenoxy group, trifluoromethylphenoxy group, bistrif The trifluoromethyl group, the trifluoromethoxy phenoxy group, the bis trifluoro methoxy phenoxy group, the difluoro methylene di oxyphenyl group, the bis trifluoromethyl phenyl imino methyl group, the trifluoromethyl thio group, etc. are mentioned.

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

Examples of the silicon-containing group as R ^{1 to} R ⁵ and R ^{7 to} R ¹² include, for example, trimethylsilyl group, triethylsilyl group, tri-iso-propylsilyl group, diphenylmethylsilyl group, tert-butyldimethylsilyl group, tert. -Butyldiphenylsilyl group, triphenylsilyl group, tris (trimethylsilyl) silyl group, cyclopentadienyldimethylsilyl group, di-n-butyl (cyclopentadienyl) silyl group, cyclopentadienyldiphenylsilyl group, indenyl Dimethyl silyl group, di-n-butyl (indenyl) silyl group, indenyl diphenyl silyl group, fluorenyl dimethyl silyl group, di-n-butyl (fluorenyl) silyl group, fluorenyl diphenyl silyl group, 4-trimethylsilyl phenyl group Group, 4-triethyl group -Phenyl, 4-tri-iso-propylsilylphenyl, 4-tert-butyldiphenylsilylphenyl, 4-triphenylsilylphenyl, 4-tris (trimethylsilyl) silylphenyl, 3,5-bis (trimethylsilyl) A phenyl group etc. are mentioned.

  Among the above silicon-containing groups, trimethylsilyl group, triethylsilyl group, tri-iso-propylsilyl group, tert-butyldimethylsilyl group, triphenylsilyl group, cyclopentadienyldimethylsilyl group, cyclopentadienyldiphenylsilyl group, Indenyldimethylsilyl group, indenyldiphenylsilyl group, fluorenyldimethylsilyl group, fluorenyldiphenylsilyl group, 4-trimethylsilylphenyl group, 4-triethylsilylphenyl group, 4-tri-iso-propylsilylphenyl group, 4-triphenylsilylphenyl group, 3,5-bis (trimethylsilyl) phenyl group, etc. are preferred, and trimethylsilyl group, triethylsilyl group, tert-butyldimethylsilyl group, 4-trimethylsilylphenyl group, 4-triylsilyl group Chill silyl phenyl group, 4-tri -iso- propyl silyl phenyl group, 3,5-bis (trimethylsilyl) phenyl group is more preferable.

Examples of the oxygen-containing group as R ^{1 to} R ⁵ and R ^{7 to} R ¹² include, for example, a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an allyloxy group, an n-butoxy group, and a sec-butoxy group , Iso-butoxy group, tert-butoxy group, methallyloxy group, prenyloxy group, benzyloxy group, methoxymethoxy group, methoxyethoxy group, phenoxy group, naphthoxy group, toluyloxy group, iso-propylphenoxy group, allylphenoxy group, tert-Butylphenoxy group, methoxyphenoxy group, iso-propoxyphenoxy group, allyloxyphenoxy group, biphenyloxy group, binaphthyloxy group, methoxymethyl group, allyloxymethyl group, benzyloxymethyl group, phenoxymethyl group, methoxyethyl group , Ryloxyethyl group, benzyloxyethyl group, phenoxyethyl group, methoxypropyl group, allyloxypropyl group, benzyloxypropyl group, phenoxypropyl group, methoxyvinyl group, allyloxyvinyl group, benzyloxyvinyl group, phenoxyvinyl group, Methoxyallyl, allyloxylyl, benzyloxyallyl, phenoxyallyl, dimethoxymethyl, di-iso-propoxymethyl, dioxolanyl, tetramethyldioxolanyl, dioxanyl, methoxyphenyl, iso-propoxy Phenyl group, allyloxyphenyl group, phenoxyphenyl group, methylenedioxyphenyl group, 3,5-dimethyl-4-methoxyphenyl group, 3,5-di-tert-butyl-4-methoxyphenyl group, furyl Groups, methyl furyl group, tetrahydrofuryl group, pyranyl group, tetrahydropyranyl group, furfuryl group, benzofuryl group, dibenzofuryl group and the like.

  Among the above-mentioned oxygen-containing groups, methoxy group, ethoxy group, iso-propoxy group, allyloxy group, n-butoxy group, tert-butoxy group, prenyloxy group, benzyloxy group, phenoxy group, naphthoxy group, toluyloxy group, iso -Propylphenoxy group, allylphenoxy group, tert-butylphenoxy group, methoxyphenoxy group, biphenyloxy group, binaphthyloxy group, allyloxymethyl group, benzyloxymethyl group, phenoxymethyl group, methoxyethyl group, methoxyallyl group, benzyl Oxyallyl group, phenoxyallyl group, dimethoxymethyl group, dioxolanyl group, tetramethyldioxolanyl group, dioxanyl group, dimethyldioxanyl group, methoxyphenyl group, iso-propoxyphenyl group, allyloxy group Group, phenoxyphenyl group, methylenedioxyphenyl group, 3,5-dimethyl-4-methoxyphenyl group, 3,5-di-tert-butyl-4-methoxyphenyl group, furyl group, methylfuryl group, tetrahydropyrani Preferred is a methoxy group, an iso-propoxy group, a tert-butoxy group, an allyloxy group, a phenoxy group, a dimethoxymethyl group, a dioxolanyl group, a methoxyphenyl group, an iso-propoxy group, etc. Phenyl group, allyloxyphenyl group, phenoxyphenyl group, 3,5-dimethyl-4-methoxyphenyl group, 3,5-di-tert-butyl-4-methoxyphenyl group, furyl group, methylfuryl group, benzofuryl group, The dibenzofuryl group is more preferred.

Examples of the nitrogen-containing group as R ^{1 to} R ⁵ and R ^{7 to} R ¹² include an amino group, a dimethylamino group, a diethylamino group, an allylamino group, a diallylamino group, a didecylamino group, a benzylamino group and a dibenzylamino group. , Pyrrolidinyl group, piperidinyl group, morpholinyl group, azepinyl group, dimethylaminomethyl group, dibenzylaminomethyl group, pyrrolidinylmethyl group, dimethylaminoethyl group, benzylaminomethyl group, benzylaminoethyl group, pyrrolidinylethyl group , Dimethylamino vinyl group, benzyl amino vinyl group, pyrrolidinyl vinyl group, dimethylamino propyl group, benzyl amino propyl group, pyrrolidinyl propyl group, dimethylamino allyl group, benzyl amino allyl group, pyrrolidinyl allyl group, amino Phenyl group, dime Aminophenyl group, 3,5-dimethyl-4-dimethylaminophenyl group, 3,5-di-iso-propyl-4-dimethylaminophenyl group, durolizinyl group, tetramethyldurolizinyl group, pyrrolidinylphenyl group , Pyrrolylphenyl group, pyridylphenyl group, quinolylphenyl group, isoquinolylphenyl group, indolinylphenyl group, indolylphenyl group, carbazolylphenyl group, di-tert-butylcarbazolylphenyl group, pyrrolyl group , Methylpyrrolyl group, phenylpyrrolyl group, pyridyl group, quinolyl group, tetrahydroquinolyl group, iso-quinolyl group, tetrahydro-iso-quinolyl group, indolyl group, indolinyl group, carbazolyl group, di-tert-butylcarbazolyl group , Imidazolyl group, dimethylimidazole Examples include dinyl, benzimidazolyl, oxazolyl, oxazolidinyl and benzoxazolyl groups.

  Among the above nitrogen-containing groups, amino group, dimethylamino group, diethylamino group, allylamino group, benzylamino group, dibenzylamino group, pyrrolidinyl group, piperidinyl group, morpholinyl group, dimethylaminomethyl group, benzylaminomethyl group, pyrrolidini group Methyl group, dimethylaminoethyl group, pyrrolidinyl ethyl group, dimethylaminopropyl group, pyrrolidinyl propyl group, dimethylaminoaryl group, pyrrolidinyl allyl group, aminophenyl group, dimethylaminophenyl group, 3,5- Dimethyl-4-dimethylaminophenyl group, 3,5-di-iso-propyl-4-dimethylaminophenyl group, dulolyzinyl group, tetramethyldiololyzinyl group, pyrrolidinylphenyl group, pyrrolylphenyl group, carbazolyl Phenyl group, di-tert-bu Lucarbazolyl phenyl group, pyrrolyl group, pyridyl group, quinolyl group, tetrahydroquinolyl group, iso-quinolyl group, tetrahydro-iso-quinolyl group, indolyl group, indolinyl group, carbazolyl group, di-tert-butylcarbazolyl Group, imidazolyl group, dimethylimidazolidinyl group, benzimidazolyl group, oxazolyl group, oxazolidinyl group, benzoxazolyl group, etc. are preferable, and amino group, dimethylamino group, diethylamino group, pyrrolidinyl group, dimethylaminophenyl group, 3,5-Dimethyl-4-dimethylaminophenyl group, 3,5-di-iso-propyl-4-dimethylaminophenyl group, durolizinyl group, tetramethyldiololizinyl group, pyrrolidinylphenyl group, pyrrolyl group, pyridyl Group, carbazolyl , Imidazolyl group is more preferable.

Examples of the sulfur-containing group as R ^{1 to} R ⁵ and R ^{7 to} R ¹² include a methylthio group, an ethylthio group, a benzylthio group, a phenylthio group, a naphthylthio group, a methylthiomethyl group, a benzylthiomethyl group and a phenylthiomethyl group. , Naphthylthiomethyl group, methylthioethyl group, benzylthioethyl group, phenylthioethyl group, naphthylthioethyl group, methylthiovinyl group, benzylthiovinyl group, phenylthiovinyl group, phenylthiovinyl group, naphthylthiovinyl group, methylthiopropyl group, benzylthio Propyl, phenylthiopropyl, naphthylthiopropyl, methylthioallyl, benzylthioallyl, phenylthioallyl, naphthylthioallyl, mercaptophenyl, methylthiophenyl, thienylphenyl, methylthienylphenyl , Benzothienylphenyl group, dibenzothienylphenyl group, benzodithienylphenyl group, thienyl group, tetrahydrothienyl group, methylthienyl group, thienofuryl group, thienothienyl group, benzothienyl group, dibenzothienyl group, thienobenzofuryl group, benzodithienyl group Groups, dithioranyl group, dithianyl group, oxathiolanyl group, oxathianyl group, thiazolyl group, benzothiazolyl group, thiazolidinyl group and the like.

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

An optionally substituted heterocyclic aromatic group having a 5-membered ring as a mother skeleton containing at least one atom selected from the group consisting of nitrogen, oxygen and sulfur which is one of R ⁵ options As a group, the group represented by the following general formula [5a]-[5h] is mentioned, for example.

前記式［５ａ］〜［５ｈ］中、Ｃｈは酸素原子あるいは硫黄原子であり、Ｒ^dはそれぞれ独立に、水素原子または炭素数１〜２０の炭化水素基であり、それぞれ同一でも異なっていてもよい。なお、前記式［５ａ］〜［５ｈ］中の波線はベンゼン環との結合部位を示す。

In the above formulas [5a] to [5h], Ch is an oxygen atom or a sulfur atom, and ^Rd is each independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, which may be the same or different Good. In addition, the wavy line in said Formula [5a]-[5h] shows a bonding site | part with a benzene ring.

Examples of the hydrocarbon group having 1 to 20 carbon atoms, among those listed as examples of the hydrocarbon group having 1 to 40 carbon atoms as R ¹ to R ⁵ and R ⁷ to R ¹² described above, the number of carbon atoms Is 1 to 20, preferably methyl, ethyl, 1-propyl, 1-butyl, 1-pentyl, 1-hexyl, 1-heptyl, 1-octyl, iso. -Propyl group, sec-butyl group, tert-butyl group, iso-butyl group, iso-pentyl group, neopentyl group, tert-pentyl group, allyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl Group, cyclooctyl group, cyclooctenyl group, norbornyl group, bicyclo [2.2.2] octan-1-yl group, 1-adamantyl group, 2-adaman Group, benzyl group, benzhydryl group, cumyl group, 1,1-diphenylethyl group, trityl group, 2-phenylethyl group, 3-phenylpropyl group, cinnamyl group, phenyl group, tolyl group, xylyl group, mesityl group, Cumenyl group, 2,6-di-iso-propylphenyl group, 2,4,6-tri-iso-propylphenyl group, 4-tert-butylphenyl group, 3,5-di-tert-butylphenyl group, 4 -Adamantylphenyl group, naphthyl group, biphenyl group, ter-phenyl group, binaphthyl group, phenanthryl group, anthracenyl group, ferrocenyl group, and more preferably methyl group, ethyl group, 1-propyl group, 1-butyl group , Iso-propyl group, sec-butyl group, tert-butyl group, iso-butyl group, allyl group, Examples include clopentyl group, cyclohexyl group, 1-adamantyl group, benzyl group, phenyl group, tolyl group, xylyl group, mesityl group, naphthyl group, biphenyl group and ter-phenyl group.

R ^d is a substituted or unsubstituted 5- to 8-membered saturated or unsaturated hydrocarbon group which may be substituted, and adjacent R ^{d 's} are bonded to each other to form a fused ring to a hetero 5-membered ring moiety independently. The ring is not particularly limited as long as the effects of the present invention can be obtained, but is preferably a 5- or 6-membered ring, and in this case, as a structure combined with the aromatic ring part of the mother nucleus, for example, benzofuran ring, benzo Thiophene ring, indole ring, carbazole ring, benzoxazole ring, benzothiazole ring, benzoimidazole ring, benzopyrazole ring and the like can be mentioned.

Among the heterocyclic aromatic groups represented by the above formulas [5a] to [5h], the heterocyclic aromatic group represented by the above formula [5a] is preferable.
Among the heterocyclic aromatic groups represented by the above formula [5a], 2-furyl group, 5-methyl-2-furyl group, 2-thienyl group and 5-methyl-2-thienyl group are preferable.

In the formula (1), R ¹ and R ² and R ³ and R ⁴ may be bonded to each other to form a saturated ring which may have a substituent. The ring formed in this case preferably forms a ring as a 5- to 8-membered saturated hydrocarbon group which may have a substituent which is condensed to a cyclopentadienyl ring portion. When a plurality of rings are present, they may be the same or different. The structure is not particularly limited as long as the effects of the present invention are exhibited, but is preferably a 6- or 7-membered ring, and in this case, as a structure combined with a cyclopentadienyl moiety of a mother nucleus Examples thereof include an octahydrofluorene ring and a substituted tetrahydroazulene ring, and a substituted tetrahydro-1-indene ring is preferable.

In the formula (1), adjacent substituents of R ² and R ³ may be bonded to each other to form a ring which may have a substituent. The ring formed in this case preferably forms a ring as a 5- to 8-membered saturated or unsaturated hydrocarbon group which may have a substituent which is condensed to a cyclopentadienyl ring portion. When a plurality of rings are present, they may be the same or different. The structure is not particularly limited as long as the effects of the present invention are exhibited, but is preferably a 6- or 7-membered ring, and in this case, as a structure combined with a cyclopentadienyl moiety of a mother nucleus, for example, a substituted tetrahydro-2-indene ring, a substituted A 2-indene ring is mentioned, It is preferable that it is a substituted 2-indene ring.

In the formula (1), adjacent substituents of R ^{7 to} R ¹⁰ may be bonded to each other to form a ring which may have a substituent. The ring formed in this case preferably forms a ring as a 5- to 8-membered saturated or unsaturated hydrocarbon group which may have a substituent which is condensed to an aromatic ring portion. When a plurality of rings are present, they may be the same or different. The structure is not particularly limited as long as the effects of the present invention are exhibited, but is preferably a 5- or 6-membered ring, and in this case, a structure combined with a cyclopentadienyl moiety and an aromatic ring moiety of a mother nucleus And a substituted tetrahydroindacene ring and a substituted cyclopentatetrahydronaphthalene, preferably a substituted benzoindenyl ring and a substituted tetrahydroindacene ring.

In the formula (1), R ¹¹ and R ¹² may be bonded to each other to form a ring containing Q ¹ , and these rings may have a substituent. The ring formed in this case preferably forms a 3- to 8-membered saturated or unsaturated ring which may have a substituent. It is not particularly limited as long as the effect of the present invention is preferably a 4- to 6-membered ring, as in this case, Q ¹ and combined structure, for example, substituted cyclobutane ring, a substituted cyclopentane ring, a substituted fluorene ring, substituted sila A cyclobutane (siletan) ring, a substituted silacyclopentane (silorane) ring, a substituted silacyclohexane (silinane) and a substituted silafluorene ring can be mentioned, and a substituted cyclopentane ring, a substituted silacyclobutane ring and a substituted silacyclopentane ring are preferable. .

In Formula (1), R ⁶ is a saturated hydrocarbon group having 3 to 10 carbon atoms in a linear portion or a terminal unsaturated hydrocarbon group having 3 to 10 carbon atoms in a linear portion.
The saturated hydrocarbon group having a carbon number of 3 to 10 in the linear portion is, for example, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group Group, n-nonyl group, n-decyl group, sec-butyl group, tert-pentyl group, 2-methylpentan-2-yl group, 1-ethylcyclopentyl group, 1- (n-propyl) cyclopentyl group, 1- Ethylcyclohexyl group, 1- (n-propyl) cyclohexyl group and the like can be mentioned, and n-propyl group, n-butyl group, n-pentyl group and n-hexyl group are preferable.

  Examples of the terminal unsaturated hydrocarbon group having 3 to 10 carbon atoms in the linear portion include an allyl group, a but-3-en-1-yl group, a methallyl group, a crotyl group, and a penta-4-ene-. 1-yl group, prenyl group, hexa-5-en-1-yl group, hept-6-en-1-yl group, octa-7-en-1-yl group, nona-8-en-1-yl group Group, deca-9-en-1-yl group, 2-methylbut-3-en-2-yl group, 2-methylpent-4-en-2-yl group, 1-vinylcyclopentyl group, 1-allylcyclopentyl group And 1-vinylcyclohexyl, 1-allylcyclohexyl and the like, and allyl, but-3-en-1-yl, penta-4-en-1-yl, and hexa-5-ene-1-l. It is preferable that it is an yl group.

In a preferred embodiment of the transition metal compound (1), Q ¹ is a silicon atom, and R ^{1 to} R ⁴ and R ^{7 to} R ¹² each independently represent a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, An oxygen-containing group having 1 to 20 carbon atoms or a nitrogen-containing group having 1 to 20 carbon atoms, R ⁵ is a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an oxygen containing group having 1 to 20 carbon atoms, the carbon number And Aspect (1-a) which is a nitrogen-containing group having 1 to 20, a substituted furan ring or a substituted thiophene ring,
As a more preferable embodiment, in the above embodiment (1-a), all of R ^{1 to} R ⁴ are hydrogen atoms, and R ⁵ and R ^{8 to} R ¹² are each independently a hydrogen atom or a carbon having 1 to 10 carbon atoms. Embodiment (1-b) is a hydrogen group, and R ⁷ is a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group having 1 to 20 carbon atoms, or a nitrogen-containing group having 1 to 20 carbon atoms And
A further preferred embodiment is the embodiment (1-c) in which all of R ^{7 to} R ¹⁰ in the above embodiment (1-b) are hydrogen atoms.

Although the specific example of transition metal compound (1) is shown below, the scope of the present invention is not limited in particular by this.
For convenience, the ligand structure of the transition metal compound (1) excluding MXn (metal part) is substituted with cyclopentadienyl ring part, indenyl ring part, cyclopentadienyl ring part R ¹ , R ² , R ³ , R ⁴ substitution Group and indenyl ring moiety R ⁵ substituent, indenyl ring moiety R ⁶ substituent, indenyl ring moiety R ⁷ and R ¹⁰ substituent, indenyl ring moiety R ⁸ and R ⁹ substituent, divided into seven of the structure of the bridging moiety. Abbreviation of cyclopentadienyl ring moiety α, abbreviation of indenyl ring moiety β, cyclopentadienyl ring moiety R ¹ , R ² , R ³ , R ⁴ substituent and indenyl ring moiety R ⁵ substituent abbreviation γ , An abbreviation of δ for an indenyl ring moiety R ⁶ substituent, an abbreviation for ε for an indenyl ring moiety R ⁷ and R ¹⁰ substituent, an abbreviation for an indenyl ring moiety R ⁸ and R ⁹ substituent, an abbreviation for a structure of a bridging moiety The abbreviation of each substituent is shown in [Table 1] to [Table 7].

なお、前記［表１］〜［表２］中の波線は架橋部分との結合部位を示す。

In addition, the wavy line in said [Table 1]-[Table 2] shows a coupling | bonding site | part with a bridge | crosslinking part.

前記［表３］中のＲ¹、Ｒ²、Ｒ³、Ｒ⁴およびＲ⁵置換基は、その組み合わせにおいて互いに同一でも異なっていてもよい。

The R ¹ , R ² , R ³ , R ⁴ and R ⁵ substituents in the above [Table 3] may be the same or different from each other in the combination.

前記［表５］中のＲ⁷およびＲ¹⁰置換基は、その組み合わせにおいて互いに同一でも異なっていてもよい。

The R ⁷ and R ¹⁰ substituents in the above [Table 5] may be the same or different from each other in the combination.

前記［表６］中のＲ⁸およびＲ⁹置換基は、その組み合わせにおいて互いに同一でも異なっていてもよい。

The R ⁸ and R ⁹ substituents in the above [Table 6] may be the same or different from each other in the combination.

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

According to the above notation, the cyclopentadienyl ring moiety is α-1 in [Table 1], the indenyl ring moiety is β-1 in [Table 2], the cyclopentadienyl ring moiety R ¹ , R ² , The R ³ and R ⁴ substituents are both γ-1 in [Table 3], the indenyl ring portion R ⁵ substituent is γ-17 in [Table 3], and the indenyl ring portion R ⁶ substituent is [Table 4] Δ, the indenyl ring moiety R ⁷ substituent is ε-38 in [Table 5], the indenyl ring moiety R ⁸ and R ⁹ substituents are all ζ-1, in the [table 6], indenyl ring moiety When the R ¹⁰ substituent is a combination of ε-1 in [Table 5] and the bridging part is 部分 -20 in [Table 7], and the MXn of the metal part is ZrCl ₂ , the following compound [6] It is illustrated.

In addition, the cyclopentadienyl ring moiety is [alpha] -2 in [Table 1], the indenyl ring moiety is [beta] -2 in [Table 2], and the cyclopentadienyl ring moiety R ³ and R ⁴ substituents are all [ Γ-1 in Table 3], Indenyl ring portion R ⁵ substituent is γ-1 in [Table 3], Indenyl ring portion R ⁶ substituent is δ-18 in [Table 4], Bridge portion is [Table 7] is a combination of eta-4 in, MXn metal parts in the case of Zr (NMe _{2) 2,} illustrates the following compounds [7].

In addition, the cyclopentadienyl ring moiety is α-6 in [Table 1], the indenyl ring moiety is β-1 in [Table 2], and the cyclopentadienyl ring moiety R ¹ and R ⁴ substituents are all [ Γ-1 in Table 3], Indenyl ring portion R ⁵ substituent is γ-2 in [Table 3], Indenyl ring portion R ⁶ substituent is δ-1 in [Table 4], Indenyl ring portion R ⁷ And R ¹⁰ substituents are each ε-2 in [Table 5], and indenyl ring moieties R ⁸ and R ⁹ substituents are all ζ-1 in [Table 6], and the bridging portion is in [Table 7] is a combination of eta-31, MXn metal parts in the case of HfMe _2, illustrates the following compounds [8].

In addition, the cyclopentadienyl ring moiety is α-5 in [Table 1], the indenyl ring moiety is β-3 in [Table 2], and the cyclopentadienyl ring moiety R ¹ and R ⁴ substituents are all [ Γ-1 in Table 3], indenyl ring portion R ⁵ substituent is γ-5 in [Table 3], indenyl ring portion R ⁶ substituent is δ-2 in [Table 4], indenyl ring portion R ⁷ And the R ¹⁰ substituent is a combination of ε-1 in [Table 5] and the cross-linking moiety is η-29 in [Table 7], and the metal moiety MXn is Ti (1,3-pentadienyl) In the case, the following compound [9] is exemplified.

前記遷移金属化合物（１）従来公知の方法を利用して製造することができ、代表的な合成経路の例を以下に示すが、特に製造法が限定されるわけではない。

The transition metal compound (1) can be produced using a conventionally known method, and examples of representative synthetic routes are shown below, but the production method is not particularly limited.

  The starting substituted cyclopentadiene compound can be prepared by known methods, and the preparation method is not particularly limited. As known production methods, for example, “Tetrahedron Lett. 1989, 30, 3513.”, “J. Org. Chem. 1990, 55, 3395.”, “Inorg. Chem. 1991, 30, 853.”, “Organometallics 1997”. J. Organomet. Chem. 1999, 577, 211. "J. Organomet. Chem. 1999, 590, 169.", JP 2002-535339, "J. Organomet. Chem. 2003, 677, 133. "," J. Organomet. Chem. 2005, 690, 952. "," Org. Lett. 2008, 10, 2545. "and the like.

  The starting substituted substituted indene compound can be prepared by known methods, and the preparation method is not particularly limited. As well-known manufacturing methods, for example, “Organometallics 1994, 13, 954.”, “Eur. J. Org. Chem. 2005, 1058.”, “Organometallics 2006, 25, 1217.”, JP 2006-509059A, "Bioorg. Med. Chem. 2008, 16, 7399.", WO 2009/0802216, "Organometallics 2011, 30, 5744.", JP-A 2011-500800, "Organometallics 2012, 31, 4962." Chem. Eur. J. 2012, 18, 4174. ”, JP 2012-012307, JP 2012-121882, JP 2014-196319, JP 201 JP-A-4-513735, JP-A-2015-063495, JP-A-2016-501952 and the like.

  Among the above-mentioned substituted indene compounds, substituted indene compounds in which a branched alkyl substituent is introduced at the 1- or 3-position can be produced, for example, by a known method as shown in the following reaction formula [1]. Is not limited. Examples of known production methods include "J. Organomet. Chem. 2002, 650, 114.", "Eur. J. Inorg. Chem. 2005, 1759."

なお、前記反応式［１］中、ｂａｓｅは、インデニルアニオンを生成可能な塩基性物質であり、例えば水素化ナトリウム、ｎ−ブチルリチウム、Ｇｒｉｇｎａｒｄ試薬のような有機金属化合物や、水酸化ナトリウム、水酸化カリウムのような無機塩基や、ジエチルアミン、ピロリジンのような有機塩基が挙げられるが、特に限定されるわけではない。Ｒ⁶−Ｍは、アルキルリチウム試薬、芳香族リチウム試薬、アルキルＧｒｉｇｎａｒｄ試薬、芳香族Ｇｒｉｇｎａｒｄ試薬などの有機金属化合物であり、特に限定されるわけではない。置換インデン化合物とカルボニル化合物よりフルベン化合物を合成し、有機金属化合物と反応させることで目的化合物を製造可能であるが、フルベン化合物と有機金属化合物との反応で生じる反応溶液を、そのまま後述する遷移金属化合物（１）の前駆体化合物（配位子）合成に用いてもよい。

In the reaction formula [1], base is a basic substance capable of producing an indenyl anion, such as sodium hydride, n-butyllithium, an organic metal compound such as Grignard reagent, sodium hydroxide, Examples include inorganic bases such as potassium hydroxide, and organic bases such as diethylamine and pyrrolidine, but are not particularly limited. R ⁶ -M is an organometallic compound such as an alkyllithium reagent, an aromatic lithium reagent, an alkyl Grignard reagent, and an aromatic Grignard reagent, and is not particularly limited. The target compound can be produced by synthesizing a fulvene compound from a substituted indene compound and a carbonyl compound and reacting it with an organic metal compound, but the reaction solution produced by the reaction of the fulvene compound with the organic metal compound is described in its entirety as a transition metal. You may use for the precursor compound (ligand) synthesis | combination of a compound (1).

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

なお、前記反応式［２］中、ＮＢＳはＮ−ブロモこはく酸イミドを示し、ＰＴＳＡはｐ−トルエンスルホン酸およびその一水和物を示している。インデン化合物には、５員環部分二重結合位置異性体が存在するが、それら異性体の混合物を用いてもよい。公知の製造方法として例えば、前記で示した特開２０１２−１２１８８２号公報、特開２０１５−０６３４９５号公報の他に、特開２０１４−１１１５６８号公報などが挙げられる。

In the reaction formula [2], NBS represents N-bromosuccinimide, and PTSA represents p-toluenesulfonic acid and a monohydrate thereof. As indene compounds, 5-membered ring partial double bond regioisomers exist, but a mixture of these isomers may be used. Examples of known production methods include JP-A-2014-111568, as well as JP-A-2012-121882 and JP-A-2015-063495 described above.

  The 2-position brominated substituted indene compound and the 4-position brominated substituted indene compound are subjected to corresponding coupling, for example, by a known method such as a Suzuki-Miyaura coupling reaction catalyzed by palladium as shown by the following reaction formula [3]. The product can be produced, and the production method is not particularly limited.

前記同様に、インデン化合物５員環部分二重結合位置異性体が存在するが、それら異性体の混合物を用いてもよい。

Similarly to the above, although the indene compound 5-membered ring partial double bond regioisomer exists, a mixture of these isomers may be used.

  It should be noted that instead of boronic acid, other boron compounds such as various boronate esters and boroxine may be used, and a reaction mixture of a halogenated compound and a metal reagent and then a boron compound may be used without isolation and purification. Instead of a palladium catalyst, a nickel catalyst or an iron catalyst may be used. As well-known manufacturing methods, Unexamined-Japanese-Patent No. 2014-196274 etc. are mentioned other than what was shown above, for example.

  In addition, instead of Suzuki-Miyaura coupling with a boron compound, Negishi coupling with an organozinc reagent, Mizorogi-Heck reaction with an alkene compound, and Anzan coupling with an organosilicon compound for production of a coupling product, Sonogashira-Sasahara coupling with terminal alkyne compounds, rightfield-Kosugi-Stille coupling with organotin compounds, Kumada-Tamao-Corriu coupling with organomagnesium compounds, Buchwald-Hartwig coupling, Goldberg amination reaction or Ullmann ether synthesis may be used. As a well-known manufacturing method, in addition to what was shown above, Unexamined-Japanese-Patent No. 8-183814, Unexamined-Japanese-Patent No. 2005-529865, the Japanese-Patent No. 2006-509046 etc. are mentioned, for example.

  For the production of the coupling product, for example, as shown in the following reaction formula [4], using a 2-position unsubstituted indene compound and an aromatic halide, a known method such as a direct coupling reaction with a palladium catalyst is used May be

前記反応式［４］中、Ａｒは芳香族置換基を示し、インデン化合物５員環部分二重結合位置異性体の混合物を用いてもよい。公知の製造方法として例えば、特表２０００−５１２６６１号公報、特開２０１４−２０１５１９号公報などが挙げられる。

In said Reaction Formula [4], Ar shows an aromatic substituent and may use the mixture of the indene compound 5-membered ring partial double bond positional isomer. Examples of known production methods include JP-A-2000-512661 and JP-A-2014-201519.

The transition metal compound (1) and the precursor compound (ligand) can be produced by known methods using various substituted cyclopentadienyl compounds and various substituted indene compounds prepared by the above-mentioned method and the like. When Q ¹ is a silicon atom, a germanium atom or a tin atom, it can be produced, for example, by the method shown in the following reaction formula [5], and the production method is not particularly limited.

In the reaction formula [5], an organolithium reagent prepared from a substituted cyclopentadienyl compound and an organolithium reagent prepared from a substituted indene compound in the precursor compound (ligand) synthesis are stepwisely Q It is preferable to react with the chloride containing ^1. The order may be arbitrary. After the reaction with the organometallic reagent in the first step, the by-product inorganic compound may be removed by inert atmosphere, and the reaction product is isolated by an operation such as distillation, crystallization or washing and then used. It is also good. In the reaction with the second step organometallic reagent, DMI (1,3-dimethyl-2-imidazolidinone), DMPU (N, N'-dimethylpropylene urea) or HMPA (hexamethyl phosphate triamide) etc. It is preferable to add 0.1-5.0 equivalent with respect to an organometallic reagent, More preferably, it is DMI and is 1.0 equivalent. In addition, although a 5-membered ring partial double bond regioisomer exists in the substituted cyclopentadienyl compound, the substituted indene compound and the precursor compound (ligand), a mixture of these isomers may be used. When the substituted cyclopentadienyl compound is the 2-position brominated substituted indene compound, a Grignard reagent using magnesium may be used.

  As known methods for producing the transition metal compound (1) and the precursor compound (ligand), for example, in addition to those described above, “Macromolecules 1995, 28, 3771.”, JP-A-11-315089, Japanese Patent Application Laid-Open Nos. 2001-302687, 2001-220404, "Polymer Articles 2002, 59, 243.", Japanese Patent Application Laid-Open No. 2003-522194, "Macromolecules 2004, 37, 2342." -320935 gazette, Unexamined-Japanese-Patent No. 2011-126813 gazette etc. are mentioned.

When Q ¹ is a carbon atom, it can be produced, for example, by the method shown in the following reaction formula [6], and the production method is not particularly limited.

  In the reaction formula [6], base is a basic substance capable of forming a cyclopentadienyl anion, and examples thereof include those shown in the reaction formula [1], and are not particularly limited. A precursor compound (ligand) can be synthesized by a reaction with an organolithium reagent prepared from a substituted cyclopentadienyl compound and a carbonyl compound by a known method in the presence of a basic substance and prepared from a substituted indene compound It is possible to manufacture. In addition, although a 5-membered ring partial double bond regioisomer exists in the substituted cyclopentadienyl compound, the substituted indene compound and the precursor compound (ligand), a mixture of these isomers may be used. In the case of the 2-position brominated substituted indene compound, the substituted cyclopentadienyl compound can be produced, for example, by the method shown in the following reaction formula [7], and the production method is particularly limited. Absent.

  In the reaction formula [7], base is a basic substance capable of forming an indenyl anion, and examples thereof include those shown in the reaction formula [1], and the base is not particularly limited. The precursor compound can be prepared by reaction with an organomagnesium reagent in which a fulvene compound can be synthesized from a substituted 1-indene compound and a carbonyl compound by a known method in the presence of a basic substance and prepared from a 2-brominated substituted indene compound. It is possible to produce In addition, although a 5-membered ring partial double bond positional isomer exists in the substituted indene compound and the precursor compound (ligand), a mixture of these isomers may be used.

  As well-known production methods of the transition metal compound (1) and the precursor compound (ligand), for example, in addition to those described above, "Macromolecules 2001, 34, 2072.", "Macromolecules 2003, 36, 9325." “Organometallics 2004, 23, 5332.”, “Eur. J. Inorg. Chem. 2005, 1003.”, “Eur. J. Inorg. Chem. 2009, 1759.”, and the like.

  In addition, in the transition metal compound (1) of the present invention, the faces of the cyclopentadienyl ring portion bonded to the central metal via the crosslinking portion are present in two directions (front and back). Therefore, when a plane of symmetry does not exist in the cyclopentadienyl ring portion, two structural isomers represented by the following general formula [10a] or [10b] exist as an example.

同様に、架橋部分の置換基Ｒ¹¹とＲ¹²が同一でない場合にも、一例として下記一般式［１１ａ］あるいは［１１ｂ］で示される２種類の構造異性体が存在する。

Similarly, when the substituents R ¹¹ and R ¹² in the cross-linking moiety are not the same, two structural isomers represented by the following general formula [11a] or [11b] exist as an example.

  Purification of these structural isomer mixtures, separation, or selective production of structural isomers is possible by known methods, and the production method is not particularly limited. As well-known manufacturing methods, in addition to the ones mentioned as the manufacturing method of the transition metal compound (1), JP-A No. 10-109996, “Organometallics 1999, 18, 5347”, “Organometallics 2012, 31, 4340. And Japanese Patent Application Publication No. 2011-502192.

  In the present invention, one type of transition metal compound (1) may be used alone, or two or more types of transition metal compounds having different chemical structures may be used in combination among the transition metal compounds (1). Further, one structural isomer having the same chemical structure may be used alone, a structural isomer mixture having the same chemical structure may be used, or a combination of these may be used.

<Component (B)>
The component (B) is a transition metal compound represented by the following general formula (2) (hereinafter also referred to as “transition metal compound (2)”). The olefin polymerization catalyst of the present invention contains at least one transition metal compound (2). That is, a plurality of transition metal compounds (2) may be used as the component (B).

式（２）中の各記号の定義は以下のとおりである。
Ｍは、周期表第４族遷移金属原子であり、具体的にはチタン原子、ジルコニウム原子、ハフニウム原子であり、好ましくはジルコニウム原子である。

The definition of each symbol in Formula (2) is as follows.
M is a transition metal atom of Group 4 of the periodic table, and specifically, is a titanium atom, a zirconium atom, or a hafnium atom, preferably a zirconium atom.

  X is a monovalent atom or group, each independently a hydrogen atom, a halogen atom, a hydrocarbon group, a halogen-containing hydrocarbon group, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group and a phosphorus-containing group It is an atom or a group selected from, preferably a halogen atom or a hydrocarbon group. Specific examples of the halogen atom, the hydrocarbon group, the halogen-containing hydrocarbon group, the silicon-containing group, the oxygen-containing group, the sulfur-containing group, the nitrogen-containing group and the phosphorus-containing group are the same as those exemplified in the formula (1). The ones of

Q ² is a divalent group binding two ligands and is a group selected from a hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing group, a silicon-containing group, a germanium-containing group and a tin-containing group And is preferably a hydrocarbon group having 1 to 20 carbon atoms such as an alkylene group, a substituted alkylene group and an alkylidene group, and a silicon-containing group, and particularly preferably 1 to 6 carbon atoms such as an alkylene group, a substituted alkylene group and an alkylidene group. 10 hydrocarbon groups.

  As said C1-C20 hydrocarbon group (Divalent C1-C20 hydrocarbon group), Alkylene groups, such as a methylene, ethylene, propylene, a butylene; isopropylidene, dimethyl methylene, diethyl methylene, a dipropyl Methylene, diisopropylmethylene, dibutylmethylene, methylethylmethylene, methylbutylmethylene, methyl-t-butylmethylene, dihexylmethylene, dicyclohexylmethylene, methylcyclohexylmethylene, methylphenylmethylene, diphenylmethylene, ditolylmethylene, methylnaphthylmethylene, dinaphthyl Substituted alkylene groups such as methylene, 1-methylethylene, 1,2-dimethylethylene, 1-ethyl-2-methylethylene and the like; cyclopropylidene, cyclobutylidene, cyclopentylidene, benzene Cycloalkylene groups such as lohexylidene, cycloheptylidene, bicyclo [3.3.1] nonylidene, norbornylidene, adamantylidene, tetrahydronaphthylidene, dihydroindanylidene and the like; alkylidene groups such as ethylidene, propylidene and butylidene etc. .

  Examples of the silicon-containing group (divalent silicon-containing group) include silylene, methylsilylene, dimethylsilylene, diisopropylsilylene, dibutylsilylene, methylbutylsilylene, methyl-t-butylsilylene, dicyclohexylsilylene, methylcyclohexylsilylene and methylphenylsilylene. And diphenylsilylene, ditolylsilylene, methylnaphthylsilylene, dinaphthylsilylene, cyclodimethylenesilylene, cyclotrimethylenesilylene, cyclotetramethylenesilylene, cyclopentamethylenesilylene, cyclohexamethylenesilylene and cycloheptamethylenesilylene groups. And preferably dimethylsilylene, dibutylsilylene and diphenylsilylene.

  As said germanium containing group (divalent germanium containing group) or said tin containing group (tin containing group), the group etc. which converted silicon into germanium or tin in the said silicon containing group are mentioned.

  As the halogen-containing group (divalent halogen-containing group), one or more of hydrogen atoms in the above-mentioned alkylene group, substituted alkylene group, cycloalkylene group, alkylidene group or silicon-containing group are substituted with an appropriate halogen atom Groups (halogen-containing silicon-containing groups), for example, bis (trifluoromethyl) methylene, 4,4,4-trifluorobutylmethylmethylene, bis (trifluoromethyl) silylene, 4,4,4-tri A fluorobutyl methyl silylene group etc. are mentioned.

R ^{13 to} R ^{24 each} represent a monovalent atom or group, and each independently represent a hydrogen atom, 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, Two adjacent groups selected from a silicon-containing group, a germanium-containing group and a tin-containing group may be linked to form a ring. Specific examples of the hydrocarbon group, the halogen-containing group, the oxygen-containing group, the nitrogen-containing group, the boron-containing group, the sulfur-containing group, the phosphorus-containing group and the silicon-containing group are the same as those exemplified in the formula (1). The thing is mentioned. Moreover, as said germanium containing group and tin containing group, the group etc. which converted silicon into germanium or tin in the said silicon containing group are mentioned.

  Specific examples of the transition metal compound (2) include isopropylidene (cyclopentadienyl) (fluorenyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (2, 7-di-t-butyl-9-fluorenyl) Zirconium dichloride, isopropylidene (cyclopentadienyl) (3,6-di-t-butylfluorenyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (octamethyloctahydridodibenzfluorenyl) zirconium dichloride, Dibutyl methylene (cyclopentadienyl) (fluorenyl) zirconium dichloride, dibutyl methylene (cyclopentadienyl) (2,7-di-t-butyl fluorenyl) zirconium dichloride, dibutyl methylene (cyclopentadienyl) (3,6-di-t-butylfluorenyl) zirconium dichloride, dibutyl methylene (cyclopentadienyl) (octamethyl octahydrido dibenzfluorenyl) zirconium dichloride, cyclohexylidene (cyclopentadienyl) (fluorenyl) ) Zirconium dichloride, cyclohexylidene (cyclopentadienyl) (2,7-di-tert-butylfluorenyl) zirconium dichloride, cyclohexylidene (cyclopentadienyl) (3,6-di-tert-butylfulcyl) Olenyl) zirconium dichloride, cyclohexylidene (cyclopentadienyl) (octamethyl octahydrido dibenzfluorenyl) zirconium dichloride, dimethylsilyl (cyclopentadienyl) (fluorenyl) zirconium dichloride, dime Silyl (cyclopentadienyl) (2,7-di-tert-butylfluorenyl) zirconium dichloride, dimethylsilyl (cyclopentadienyl) (3,6-di-tert-butylfluorenyl) zirconium dichloride and dimethyl And silyl (cyclopentadienyl) (octamethyl octahydrido dibenz fluorenyl) zirconium dichloride, more preferably isopropylidene (cyclopentadienyl) (2,7-di-t-butyl-9). -Fluorenyl) zirconium dichloride and the like, but it is not limited thereto.

  The transition metal compound (2) and the method for producing the same are not particularly limited as long as the effects of the present invention are exhibited, but specific examples thereof include those exemplified in JP-A-2006-233208 and the like.

  In the present invention, one type of transition metal compound (2) may be used alone, or two or more types of transition metal compounds having different chemical structures may be used among the transition metal compounds (2). In addition, structural isomers having the same chemical structure may be used alone or in a mixture of structural isomers having the same chemical structure (for example, a meso mixture or a racemic mixture).

<Component (C)>
The component (C) is an organometallic compound (c-1) represented by the following general formulas (3) to (5), an organoaluminum oxy compound (c-2), and the component (A) and the component (B) And at least one compound selected from the group consisting of compounds (c-3) which react with each other to form an ion pair.
_{^{R a m Al (OR b)}} n H p X q ··· (3)
In formula (3), R ^a and R ^b each independently represent a hydrocarbon group having 1 to 15 carbon atoms, X represents a halogen atom, m is 0 <m ≦ 3, n is 0 ≦ n <3, p is 0 ≦ p <3, q is a number of 0 ≦ q <3, and m + n + p + q = 3.
M ^a Al R ^a ₄ (4)
Wherein (4), M ^a represents a Li, Na or K, R ^a represents a hydrocarbon group having 1 to 15 carbon atoms.
R ^a _r M ^b R ^b _s X _t (5)
In formula (5), R ^a and R ^b each independently represent a hydrocarbon group having 1 to 15 carbon atoms, M ^b is selected from Mg, Zn and Cd, and X is a halogen atom, r is 0 <r ≦ 2, s is 0 ≦ s ≦ 1, t is 0 ≦ t ≦ 1, and r + s + t = 2.

  Among the organometallic compounds (c-1), those represented by the above formula (3) are preferable, and specifically, trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, trihexylaluminum, trioctyl Aluminum, trialkylaluminums such as tri-2-ethylhexylaluminum; dialkylaluminum halides such as dimethylaluminum chloride, diethylaluminum chloride, diisopropylaluminum chloride, diisobutylaluminum chloride, dimethylaluminum bromide, etc .; methylaluminum sesquichloride, ethylaluminum sesquichloride, isopropylaluminum Sesquichloride, butylaluminum sesquichloride, ethylaluminum Alkyl aluminum sesquihalides such as sesquibromide; alkyl aluminum dihalides such as methyl aluminum dichloride, ethyl aluminum dichloride, isopropyl aluminum dichloride, ethyl aluminum dibromide; dimethyl aluminum hydride, diethyl aluminum hydride, dihydrophenyl aluminum hydride, diisopropyl aluminum hydride, dialuminum Alkylaluminums such as n-butylaluminum hydride, diisobutylaluminum hydride, diisohexylaluminum hydride, diphenylaluminum hydride, dicyclohexylaluminum hydride, di-sec-heptylaluminum hydride, di-sec-nonylaluminum hydride, etc. Arm hydride; dimethyl aluminum ethoxide, diethyl aluminum ethoxide, diisopropylaluminum methoxide and dialkylaluminum alkoxide such as diisobutylaluminum ethoxide and the like.

  Examples of the formula (4) include lithium aluminum hydride, and examples of the formula (5) include dialkyl zinc compounds described in JP-A No. 2003-171412 and the like, and phenol It can also be used in combination with a compound or the like.

  As the organoaluminum oxy compound (c-2), an organoaluminum oxy compound prepared from trialkylaluminum or tricycloalkylaluminum is preferable, and an aluminoxane prepared from trimethylaluminum or triisobutylaluminum is particularly preferable. Such organoaluminum oxy compounds are used singly or in combination of two or more.

  As a compound (c-3) which reacts with the said component (A) and a component (B), and forms an ion pair, Unexamined-Japanese-Patent No. 1-501950, Unexamined-Japanese-Patent No. 1-502036, Unexamined-Japanese-Patent No. 3-179005 are mentioned. Lewis acids, ionic compounds, borane compounds, carborane compounds, and further heteropoly compounds described in JP-A-3-179006, JP-A-3-207703, JP-A-3-207704 and US Pat. No. 5,321,106 etc. And isopoly compounds can be used.

  In the catalyst for olefin polymerization according to the present invention, when an organoaluminum oxy compound such as methylaluminoxane is used in combination as a co-catalyst component, it not only exhibits a very high polymerization activity with respect to the olefin compound but also active hydrogen in the solid support The component (C) preferably contains at least an organoaluminum oxy compound (c-2) because a solid support component containing a reacted cocatalyst component can be easily prepared.

<Solid carrier (S)>
The solid carrier (S) used in the present invention is an inorganic compound or an organic compound, and is a granular or particulate solid.

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

Examples of the porous oxide include SiO ₂ , Al ₂ O ₃ , MgO, ZrO, TiO ₂ , B ₂ O ₃ , CaO, ZnO, BaO and ThO _2, etc., or a composite or mixture thereof. Are natural or synthetic zeolites, SiO ₂ -MgO, SiO ₂ -Al ₂ O ₃ , SiO ₂ -TiO ₂ , SiO ₂ -V ₂ O ₅ , SiO ₂ -Cr ₂ O ₃ and SiO ₂ -TiO ₂ -MgO, etc. Is used. Among these, one having SiO ₂ as a main component is preferable.

In addition, 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 (NO) _{3) 2, Al (NO 3} ) 3, Na 2 O, K 2 O, Li 2 carbonates O etc., sulfate, nitrate, no problem also contain oxide components.

Such a porous oxide has different properties depending on the type and production method, but the solid carrier (S) used in the present invention has a particle size of usually 0.2 to 300 μm, preferably 1 to 200 μm. Te, the specific surface area is usually 50~1200m ² / g, preferably in the range of 100~1000m ² / g, which pore volume is in the range of usually 0.3~30cm ³ / g are preferred. Such a carrier is used after being calcined, for example, at 100 to 1000 ° C., preferably 150 to 700 ° C., as necessary.

  As the solid aluminoxane compound, an aluminoxane having a structure represented by the following general formula (S-a), an aluminoxane having a structure represented by the following general formula (S-b), and a table represented by the following general formula (S-c) And an aluminoxane having a repeating unit represented by the following general formula (S-d) as a structure.

In the above formulas (S-a) to (S-d), R ^e each independently represents a hydrocarbon group having 1 to 10, preferably 1 to 4 carbon atoms, and more specifically a methyl group or an ethyl group Group, propyl group, isopropyl group, isopropenyl group, n-butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, octyl group, decyl group, dodecyl group, tridecyl group, tetradecyl group, hexadecyl group And hydrocarbon groups such as octadecyl group, eicosyl group, cyclohexyl group, cyclooctyl group, phenyl group, tolyl group, ethylphenyl group etc., methyl group, ethyl group and isobutyl group are preferable, and methyl group is particularly preferable. preferable. In addition, part of R ^e may be substituted with a halogen atom such as chlorine or bromine, and the halogen content may be 40% by weight or less based on R ^e . The straight line in which one side is not connected to the atom in the above formulas (S-c) and (S-d) indicates a bond with another atom not shown.

  In the formulas (S-a) and (S-b), r is an integer of 2 to 500, preferably 6 to 300, and particularly preferably 10 to 100. In the formulas (S-c) and (S-d), s and t each represent an integer of 1 or more. r, s and t are selected such that the aluminoxane can maintain a substantially solid state under the reaction environment used.

  The solid aluminoxane compound does not contain an inorganic solid component such as silica or alumina and an organic polymer component such as polyethylene or polystyrene, unlike the conventionally known support for an olefin polymerization catalyst, and is a solid containing an alkylaluminum compound as a main component It is "Solid" means that the aluminoxane component substantially maintains a solid state under the reaction environment used. More specifically, when preparing the catalyst for olefin polymerization (example: catalyst for ethylene polymerization) by bringing the transition metal compound [A] into contact with an aluminoxane component as described later, and the prepared catalyst for olefin polymerization The aluminoxane component is substantially maintained in a solid state when polymerization (for example, suspension polymerization) of an olefin (eg, ethylene) is performed using

  Although the visual inspection is the easiest method to determine whether the aluminoxane component is in a solid state, for example, in many cases, visual confirmation is difficult during polymerization. In that case, it is possible to judge, for example, from the properties of the polymer powder obtained after the polymerization and the adhesion state to the reactor. On the contrary, if the properties of the polymer powder are good and adhesion to the reactor is small, even if a part of the aluminoxane component is eluted to some extent in the polymerization environment, it does not deviate from the spirit of the present invention. Examples of the index for determining the properties of the polymer powder include bulk density, particle shape, surface shape, degree of presence of amorphous polymer, and the like, but polymer bulk density is preferable from the viewpoint of quantitative property. The bulk density is usually 0.01 to 0.9, preferably 0.05 to 0.6, and more preferably 0.1 to 0.5.

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

  The dissolution rate is as follows: 2 g of solid aluminoxane compound carrier is added to 50 ml of n-hexane kept at 25 ° C., stirring is carried out for 2 hours, and then the solution is separated using a filter made of G-4 glass, It is determined by measuring the aluminum concentration in the filtrate. Thus, the dissolution rate is determined as the ratio of aluminum atoms present in the filtrate to the amount of aluminum atoms corresponding to 2 g of aluminoxane used.

  As the solid aluminoxane compound, a known solid aluminoxane can be used without limitation, and for example, the solid polyaluminoxane composition described in WO 2014/123212 can also be used. Examples of known manufacturing methods include, for example, Japanese Patent Publication Nos. 7-42301, 6-220126, 6-220128, 11-140113 and 11-310607. The manufacturing method described in the open 2000-38410 gazette, Unexamined-Japanese-Patent No. 2000-95810, international publication 2010/55652 etc. is mentioned.

The average particle size of the solid aluminoxane compound is generally in the range of 0.01 to 50000 μm, preferably 0.1 to 1000 μm, and particularly preferably 1 to 200 μm. The average particle size of the solid aluminoxane compound can be determined by observing the particles with a scanning electron microscope, measuring the particle size of 100 or more particles, and performing weight averaging. First, the particle diameter d of each particle is obtained by measuring the length of the particle image across two parallel lines in the horizontal direction and in the vertical direction, respectively, according to the following equation.
Particle size d = ((horizontal length) ² + (vertical length) ² ) ^0.5

Next, the weight average particle size of the solid aluminoxane compound can be determined by the following equation using the particle size d determined above and the number n of particles.
Average particle size = ndnd ⁴ / ndnd ³

The solid aluminoxane compound preferably has a specific surface area of 50 to 1000 m ² / g, preferably 100 to 800 m ² / g, and a pore volume of 0.1 to 2.5 cm ³ / g.

Examples of the inorganic halide include MgCl ₂ , MgBr ₂ , MnCl ₂ , MnBr _{2 and the} like. The inorganic halide may be used as it is or after being crushed by a ball mill or a vibration mill. Moreover, after dissolving an inorganic halide in solvent, such as alcohol, what was made to precipitate in fine particle shape with a precipitation agent can also be used.

  Clay is usually composed mainly of clay minerals. In addition, the ion exchangeable layered compound is a compound having a crystal structure in which planes constituted by ionic bonds etc. are stacked in parallel with each other by 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 naturally occurring ones but also artificially synthesized ones can be used.

Also, as clay, clay mineral or ion exchange layered compound, clay, clay mineral, ionic crystalline compound having layered crystal structure such as hexagonal close packing type, antimony type, CdCl ₂ type, CdI ₂ type, etc. It can be illustrated.

Such clays, clay minerals such as kaolin, bentonite, cypress clay, gilome clay, allophane, hisingerite, pyrophyllite, ummo group, montmorillonite group, vermiculite, ryokdeite group, palygorskite, kaolinite, nacrite, dickite And ion exchangeable layered compounds such as 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} ), crystalline acid salts of polyvalent metals such as γ-Ti (NH ₄ PO ₄ ) ₂ .H ₂ O, and the like.

Such clay, clay mineral or ion exchangeable layered compound preferably has a pore volume of at least 0.1 cc / g and a radius of at least 20 Å as measured by mercury porosimetry, preferably 0.3 to 5 cc / g. Particularly preferred. Here, the pore volume is measured in the range of a pore radius of 20 to 3 × 10 ⁴ Å by mercury porosimetry using a mercury porosimeter. When a pore volume of a radius of 20 Å or more and a pore volume smaller than 0.1 cc / g is used as a carrier, it tends to be difficult to obtain high polymerization activity.

  Chemical treatments are also preferably applied to clays and clay minerals. As the chemical treatment, any of surface treatment for removing impurities attached to the surface, treatment for affecting the crystal structure of clay, and the like can be used. Specific examples of the chemical treatment include acid treatment, alkali treatment, salt treatment, organic matter treatment and the like. The acid treatment not only removes surface impurities but also increases the surface area by eluting cations such as Al, Fe and Mg in the crystal structure. The alkali treatment destroys the crystal structure of the clay, resulting in a change in the structure of the clay. In the salt treatment and the organic substance treatment, an ion complex, a molecular complex, an organic derivative or the like can be formed to change the surface area and the interlayer distance.

The ion exchangeable layered compound may be a layered compound in which the interlayer is expanded by utilizing the ion exchangeability and exchanging exchangeable ions between the layers with another large bulky ion. Such bulky ions play the role of a pillar supporting a layered structure, and are usually called pillars. Also, introducing another substance between the layers of the layered compound in this way is called intercalation. The guest compounds to be intercalated include cationic inorganic compounds such as TiCl ₄ and ZrCl ₄ , and metal alkoxides such as Ti (OR) ₄ , Zr (OR) ₄ , PO (OR) ₃ and B (OR) ₃ R represents a metal hydroxide ion such as a hydrocarbon group, [Al ₁₃ O ₄ (OH) ₂₄ ] ⁷⁺ , [Zr ₄ (OH) ₁₄ ] ²⁺ , [Fe ₃ O (OCOCH ₃ ) ₆ ] ⁺ etc. Etc. These compounds may be used alone or in combination of two or more. Also, when intercalating these compounds, polymerization obtained by hydrolyzing metal alkoxides (R is a hydrocarbon group etc.) such as Si (OR) ₄ , Al (OR) ₃ , Ge (OR) ₄ etc. Or a colloidal inorganic compound such as SiO ₂ can be coexistent. Moreover, as a pillar, the oxide etc. which are produced | generated by heat-dehydrating are said after intercalating the said metal hydroxide ion between layers.

  The clay, clay mineral and ion exchangeable layered compound may be used as they are, or may be used after treatment such as ball milling and sieving. In addition, water may be newly added and adsorbed, or may be used after being subjected to heat dehydration treatment. Furthermore, they may be used alone or in combination of two or more.

As an organic compound used as said solid-like carrier (S), the granular form thru | or the fine particulate solid which have a particle size in the range of 10-300 micrometers are mentioned, for example. Specific examples of the organic compound include polymers formed mainly from olefins having 2 to 14 carbon atoms such as ethylene, propylene, 1-butene, 4-methyl-1-pentene, or vinylcyclohexane, There may be mentioned granular or particulate solids composed of styrene, polymers and reactants formed mainly of divinylbenzene, and their modified products.
As the solid carrier (S), a porous oxide is preferable from the viewpoint of preventing foreign substances at the time of molding.

<Preparation Method of Olefin Polymerization Catalyst>
The olefin polymerization catalyst according to the present invention comprises the addition of component (A), component (B), component (C) and solid carrier (S) in an inert hydrocarbon or in a polymerization system using an inert hydrocarbon. The solid catalyst component (X) prepared by conducting is one of the preferred embodiments.

  Examples of the solid catalyst component (X) include a solid support (S), a solid catalyst component (X-A) formed from the component (C) and the component (A), a solid support (S), a component (X) C) and a solid catalyst component (X-B) formed from component (B); a catalyst for olefin polymerization; and a solid carrier (S), component (A), component (B) and component (C) The catalyst for olefin polymerization which consists of a solid catalyst component (X-C) formed from is mentioned. Among these, the olefin polymerization catalyst consisting of the solid catalyst component (X-C) is more preferable.

Although the contact order of each component is arbitrary, as a preferable method for preparing a catalyst for olefin polymerization, for example,
(I) Contacting the component (C) with the solid carrier (S) and then bringing the component (A) into contact to prepare the solid catalyst component (X-A), the component (C) and the solid carrier (S) B) contacting, and then contacting component (B) to prepare a solid catalyst component (X-B),
(Ii) The component (A) and the component (C) are mixed and brought into contact, and then brought into contact with the solid carrier (S) to prepare a solid catalyst component (X-A), and the component (B) and the component (C) Mixed catalyst, and then contacted with a solid support (S) to prepare a solid catalyst component (X-B),
(Iii) Component (C) is brought into contact with the solid carrier (S), and then the contact product of component (A) and component (C) is brought into contact to prepare a solid catalyst component (X-A). C) Contacting the solid carrier (S), and then bringing the contact product of component (B) and component (C) into contact to prepare a solid catalyst component (X-B),
(Iv) Contacting the component (C) with the solid carrier (S) and then contacting the component (A), and then contacting the component (C) to prepare a solid catalyst component (X-A) A method of preparing the solid catalyst component (X-B) by contacting the component (C) with the solid carrier (S) and then bringing the component (B) into contact and then contacting the component (C) further;
(V) Contacting the solid carrier (S) with the component (C) and then bringing the component (A) into contact, followed by bringing the component (B) into contact to prepare a solid catalyst component (X-C),
(Vi) Contacting the solid carrier (S) with the component (C) and then bringing the component (B) into contact, followed by contacting the component (A) to prepare a solid catalyst component (X-C),
(Vii) A method of preparing solid catalyst component (X-C) by contacting solid carrier (S) with component (C) and then contacting the contact mixture of component (A) with component (B),
(Viii) Contacting the component (A) with the component (B) and then bringing the component (C) into contact, followed by contacting the solid carrier (S) to prepare a solid catalyst component (X-C),
(Ix) After contacting the solid carrier (S) with the component (C), the component (C) is further contacted, and then the component (A) and the component (B) are contacted in this order to obtain a solid catalyst component ( Method of preparing X-C),
(X) After contacting the solid carrier (S) with the component (C), the component (C) is further contacted, and then the component (B) and the component (A) are contacted in this order to obtain a solid catalyst component ( Method of preparing X-C),
(Xi) After contacting the solid carrier (S) with the component (C), the component (C) is further contacted, and then the contact mixture of the component (A) and the component (B) is contacted to obtain a solid catalyst component ( Method of preparing X-C),
(Xii) contacting solid carrier (S) with component (C), then contacting a contact mixture of component (A) with component (B) and component (C) to prepare a solid catalyst component (X-C) how to,
(Xiii) The solid carrier (S) is brought into contact with the component (C), then the contact mixture of the component (A) and the component (C) is brought into contact, and then the component (B) is brought into contact to obtain a solid catalyst component (X). A method of preparing -C),
(Xiv) The solid carrier (S) is brought into contact with the component (C), then the contact mixture of the component (B) and the component (C) is brought into contact, and then the component (A) is brought into contact to obtain a solid catalyst component (X). A method of preparing -C),
(Xv) After contacting the solid carrier (S) with the component (C), the component (C) is further contacted, and then the contact mixture of the component (A) and the component (C) and the component (B) and the component (C) (C) contacting the contacting mixture of C) in this order to prepare a solid catalyst component (X-C);
(Xvi) After contacting the solid carrier (S) with the component (C), the component (C) is further contacted and then the contact mixture of the component (B) with the component (C) and the component (A) with the component (C) (C) contacting the contacting mixture of C) in this order to prepare a solid catalyst component (X-C);
(Xvii) After contacting the solid carrier (S) with the component (C), the component (C) is further contacted, and then the contact mixture of the component (A), the component (B) and the component (C) is contacted Method for preparing the solid catalyst component (X-C),
(Xviii) The mixture of the component (A) and the component (C) and the mixture of the component (B) and the component (C) are mixed beforehand, and then brought into contact with the solid carrier (S) and the component (C) Method for preparing the solid catalyst component (X-C),
(Xix) The mixture of the component (A) and the component (C) and the mixture of the component (B) and the component (C) are mixed beforehand, and then the solid carrier (S) is brought into contact with the component (C) The method of making it contact with the contact mixture which contacted (C), and preparing solid catalyst component (X-C) etc. are mentioned.

When a plurality of components (C) are used, the components (C) may be the same or different. Among these, particularly preferred contact sequences include (xi), (xiii) and (xv).
And (xvi), (xvii), (xxii), (xxiii) and (xxiv).

  The component (C) and the solid carrier (S) are obtained by the reaction of the reaction site in the component (C) with the reaction site in the solid carrier (S) by the contact of the component (C) with the solid carrier (S). Chemically bound, a contact of component (C) and solid carrier (S) is formed. The contact time of the component (C) with the solid carrier (S) is usually 0 to 20 hours, preferably 0 to 10 hours, and the contact temperature is usually -50 to 200 ° C, preferably -20 to 120 ° C. It is. When the initial contact of the component (C) with the solid support (S) is rapidly made, the solid support (S) collapses due to the reaction heat and reaction energy, and the morphology of the solid catalyst component (X) obtained deteriorates. However, when it is used for polymerization, polymer morphology defects often make continuous operation difficult. Therefore, the initial stage of contact between the component (C) and the solid support (S) is contacted at a low temperature of -20 to 30 ° C for the purpose of suppressing the reaction heat, or the reaction heat is controlled and the initial contact temperature is It is preferred to react at a maintainable rate. The same applies to the case where the component (C) and the solid carrier (S) are brought into contact and the component (C) is further brought into contact. The molar ratio (Component (C) / solid carrier (S)) of the contact of the component (C) with the solid carrier (S) can be arbitrarily selected, but the higher the molar ratio, the component (A) and the solid carrier (S) The contact amount of the component (B) can be increased, and the activity of the solid catalyst component (X) can be improved. Specifically, the molar ratio of the component (C) to the solid carrier (S) [= the molar amount of the component (C) / the molar amount of the solid carrier (S)] is preferably 0.2 to 2.0. , Particularly preferably 0.4 to 2.0.

  With respect to the contact of the component (C) with the solid carrier (S) and the component (A) and the component (B), the contact time is usually 0-5 hours, preferably 0-2 hours, The temperature is usually in the range of -50 to 200 ° C, preferably -50 to 100 ° C. The contact amount of component (A) and component (B) with respect to component (C) largely depends on the type and amount of component (C). In the case of the component (c-1), the molar ratio [(c-1) / M] of the component (c-1) to the component (A) and all transition metal atoms (M) in the component (B) is Usually, it is used in an amount of 0.01 to 100,000, preferably 0.05 to 50,000. In the case of the component (c-2), the molar ratio of the aluminum atom in the component (c-2) to all the transition metal atoms (M) in the component (A) and the component (B) [(c-2) / M] is used usually in an amount of 10 to 500,000, preferably 20 to 100,000. In the case of the component (c-3), the molar ratio [(c-3) / M] of the component (c-3) to all the transition metal atoms (M) in the component (A) and the component (B) is Usually, it is used in an amount of 1 to 10, preferably 1 to 5. The molar ratio of the component (C) to all the transition metal atoms (M) in the component (A) and the component (B) can be determined by inductively coupled plasma emission spectrometry (ICP analysis).

  As a solvent used for preparation of solid catalyst component (X), an inert hydrocarbon solvent is mentioned, and, specifically, aliphatic carbonization such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, kerosene and the like Alicyclic hydrocarbons such as hydrogen, cyclopentane, cyclohexane and methylcyclopentane, aromatic hydrocarbons such as benzene, toluene and xylene, halogenated hydrocarbons such as ethylene chloride, chlorobenzene and dichloromethane, and mixtures thereof Be

  In each of the methods showing the contact sequence form, a step comprising contacting the solid support (S) with the component (C), a step comprising contacting the solid support (S) with the component (A), a solid support (S) And (g-1) a polyalkylene oxide block as component (G) in the step including the contact of component (B) with the solid support (S) and the step of contact with component (A) and component (B) , (G-2) higher aliphatic amide, (g-3) polyalkylene oxide, (g-4) polyalkylene oxide alkyl ether, (g-5) alkyl diethanolamine, and (g-6) polyoxyalkylene alkyl amine And at least one compound selected from the group consisting of By coexistence of such component (G), fouling during the polymerization reaction can be suppressed, and the particle properties of the formed polymer are improved. Among the components (G), (g-1), (g-2), (g-3) and (g-4) are preferable.

The use ratio of the component (A) to the component (B) can be appropriately determined according to the molecular weight and molecular weight distribution of the polymer to be produced.
The solid catalyst component (X) as described above can be used as it is for the polymerization of olefin, but this solid catalyst component (X) is used after prepolymerization of the olefin to form a prepolymerization catalyst component (XP) It can also be done.

  The prepolymerized catalyst component (XP) can be prepared by introducing an olefin, usually in an inert hydrocarbon solvent, in the presence of the solid catalyst component (X). As a reaction system, any of a batch system, a semicontinuous system and a continuous system can be used. The reaction can be carried out under reduced pressure, normal pressure or under pressure. This prepolymerization produces usually 0.01 to 1000 g, preferably 0.1 to 800 g, more preferably 0.2 to 500 g of polymer per 1 g of the solid catalyst component.

  The prepolymerization catalyst component (XP) prepared in an inert hydrocarbon solvent is separated from the suspension, suspended again in the inert hydrocarbon, and an olefin is introduced into the obtained suspension. Also, after drying, the olefin may be introduced.

The prepolymerization temperature is usually -20 to 80 ° C, preferably 0 to 60 ° C. The prepolymerization time is usually 0.5 to 100 hours, preferably 1 to 50 hours.
As the form of the solid catalyst component (X) used for the prepolymerization, those described above can be used without limitation. Moreover, a component (C) is used as needed, and the organoaluminum compound especially shown by said Formula (3) in (c-1) is used preferably. When the organoaluminum compound of the formula (3) is used as the component (C), the molar ratio of the aluminum atom (Al) in the component (C) to the transition metal compound which is the components (A) and (B) C) / transition metal compound), usually used in an amount of 0.1 to 10000, preferably 0.5 to 5000.

  The concentration of the solid catalyst component (X) in the prepolymerization system is desirably 1 to 1000 g / l, preferably 10 to 500 g / l, as a ratio of solid catalyst component (X) / polymerization volume 1 liter. At the time of prepolymerization, the above-mentioned component (G) can be made to coexist for the purpose of fouling suppression or particle property improvement.

  In order to improve the flowability of the prepolymerization catalyst component (XP) and to suppress the generation of heat spots, sheeting and polymer lumps during polymerization, the component (G) is added to the prepolymerization catalyst component (XP) once produced by prepolymerization. You may make it contact. At this time, as the component (G) to be used, the above (g-1), (g-2), (g-3) and (g-4) are preferable.

The temperature at which the component (G) is mixed and contacted is usually -50 to 50 ° C, preferably -20 to 50 ° C, and the contact time is 1 to 1000 minutes, preferably 5 to 600 minutes.
When the solid catalyst component (X) and the component (G) are mixed and brought into contact with each other, the component (G) is generally 0.1 to 20 parts by weight, preferably 0. 0 to 100 parts by weight of the solid catalyst component (X). It is used in an amount of 3 to 10 parts by weight, more preferably 0.4 to 5 parts by weight.

  Mixed contact of the solid catalyst component (X) with the component (G) can be carried out in an inert hydrocarbon solvent, and as the inert hydrocarbon solvent, it is the same as the solvent used for the preparation of the solid catalyst component (X) The ones of

  The olefin polymerization catalyst according to the present invention can be used as a dry prepolymerization catalyst by drying the prepolymerization catalyst component (XP). Drying of the prepolymerized catalyst component (XP) is usually carried out after removing the dispersing medium hydrocarbon from the suspension of the prepolymerized catalyst obtained by filtration or the like.

  Drying of the prepolymerized catalyst component (XP) is carried out by maintaining the prepolymerized catalyst component (XP) at a temperature of 70 ° C. or less, preferably in the range of 20 to 50 ° C., under a flow of inert gas. It is desirable that the volatile component amount of the obtained dry prepolymerized catalyst is 2.0% by weight or less, preferably 1.0% by weight or less. The amount of volatile component of the dry prepolymerization catalyst is preferably as small as possible, and there is no lower limit, but practically it is 0.001% by weight. The drying time is usually 3 to 8 hours depending on the drying temperature. When the volatile component amount of the dry prepolymerized catalyst exceeds 2.0% by weight, the flowability of the dry prepolymerized catalyst may be reduced, and the catalyst may not be stably supplied to the polymerization reactor.

Here, the volatile component amount of the dry prepolymerized catalyst is measured, for example, by a weight loss method, a method using gas chromatography, or the like.
In the weight loss method, the weight loss when the dry prepolymerized catalyst is heated at 110 ° C. under an inert gas atmosphere for 1 hour is determined and expressed as a percentage relative to the dry prepolymerized catalyst before heating.

  In the method using gas chromatography, volatile components such as hydrocarbons are extracted from the dried prepolymerization catalyst, and after preparing a calibration curve according to the internal standard method, it is calculated as weight% from GC area.

  As a method of measuring the amount of volatile component of the dry prepolymerization catalyst, when the amount of volatile component of the dry prepolymerization catalyst is about 1% by weight or more, the weight loss method is adopted, and the amount of volatile component of the dry prepolymerization catalyst is about 1 In the case of weight percent or less, a method using gas chromatography is employed.

  Examples of the inert gas used for drying the prepolymerization catalyst component (XP) include nitrogen gas, argon gas, neon gas and the like. Such inert gas has an oxygen concentration of 20 ppm or less, preferably 10 ppm or less, more preferably 5 ppm or less (by volume), a water content of 20 ppm or less, preferably 10 ppm or less, more preferably 5 ppm or less (by weight) Is desirable. When the oxygen concentration and the water content in the inert gas exceed the above ranges, the olefin polymerization activity of the dry prepolymerization catalyst may be greatly reduced.

  The dry prepolymerization catalyst is excellent in fluidity, so that the supply to the polymerization reactor can be stably performed. In addition, since it is not necessary to carry the solvent used for suspension in the gas phase polymerization system, the polymerization can be carried out stably.

[Method for producing ethylene polymer]
Next, the method for producing an ethylene-based polymer according to the present invention will be described. An ethylene-based polymer is obtained by polymerizing (homopolymerizing or copolymerizing) ethylene in the presence of the above-described olefin polymerization catalyst of the present invention. By using the olefin polymerization catalyst of the present invention, it is possible to efficiently produce an ethylene-based copolymer having high polymerization activity, excellent in moldability and mechanical strength, and having many long-chain branches. The ethylene-based polymer of the present invention refers to one having an ethylene content of 10 mol% or more in the polymer.

  In the present invention, the polymerization can be carried out in any of liquid phase polymerization methods such as solution polymerization and suspension polymerization or gas phase polymerization methods, but in the suspension polymerization method and the gas phase polymerization method, the solid catalyst component (X) is used. It is preferred to use.

  Specific examples of the inert hydrocarbon medium used in the liquid phase polymerization method include, for example, aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane and kerosene; cyclopentane, cyclohexane, methyl Alicyclic hydrocarbons such as cyclopentane; aromatic hydrocarbons such as benzene, toluene and xylene; halogenated hydrocarbons such as ethylene chloride, chlorobenzene and dichloromethane, and mixtures thereof. In addition, in the liquid phase polymerization method, olefin itself can also be used as a solvent.

When ethylene is polymerized using the above-mentioned catalyst for olefin polymerization, component (A) and component (B) are generally 10 ^-12 to 10 ^-1 mol, preferably 10 ^-8 to 10 mol, per liter of reaction volume. ^{-Used in} an amount such that it becomes ² moles. Component (C) is also used, and in particular, the organoaluminum compound represented by the formula (3) in (c-1) is preferably used.

The polymerization temperature of ethylene using the above-mentioned solid catalyst component (X) is usually in the range of -50 to + 200 ° C, preferably 0 to 170 ° C, and particularly preferably 60 to 170 ° C. The polymerization pressure is usually under the conditions of normal pressure to 100 kg / cm ² , preferably normal pressure to 50 kg / cm ² , and the polymerization reaction is carried out in any of batch system, semi-continuous system and continuous system. Can. Furthermore, it is also possible to divide the polymerization into two or more stages under different reaction conditions.

  The molecular weight of the resulting polymer can be controlled by the presence of hydrogen in the polymerization system or by varying the polymerization temperature. Generally, as the low molecular weight component increases, the adhesion to the polymerization reactor wall and the stirring blade also increases, which may cause a decrease in productivity due to the load on the cleaning process. At the time of polymerization, the component (G) can be made to coexist for the purpose of fouling suppression or particle property improvement.

  In the present invention, the olefin supplied to the copolymerization reaction is at least one monomer selected from olefins having 3 to 20 carbon atoms. Specific examples of the olefin having 3 to 20 carbon atoms include, for example, propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene 1-tetradecene, 1-hexadecene, 1-octadecene, α-olefins such as 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, etc. are mentioned. Further, as the above-mentioned olefin, for example, styrene, vinylcyclohexane, diene, acrylic acid, methacrylic acid, fumaric acid, maleic anhydride etc .; methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, methacrylic acid etc. Monomers etc. are also mentioned.

  Obtained by copolymerizing ethylene and an α-olefin having 4 to 20 carbon atoms, preferably 6 to 10 carbon atoms, in the presence of the catalyst for olefin polymerization of the present invention, which is a preferred embodiment of the present invention The ethylene-based polymer preferably satisfies the following requirements (1) to (4). In addition, the measuring method of these requirements is as having described in the Example.

(1) The melt flow rate (MFR) at a load of 2.16 kg at 190 ° C. is 0.1 g / 10 min or more and 30 g / 10 min or less.
The lower limit is preferably 0.5 g / 10 min, more preferably 1.0 g / 10 min, and the upper limit is preferably 25 g / 10 min, more preferably 20 g / 10 min. When the melt flow rate (MFR) is in the above range, the shear viscosity of the ethylene-based polymer is not too high, and the moldability is good, and mechanical strength such as tensile strength and heat seal strength of the ethylene-based polymer Will be better.

  The melt flow rate (MFR) strongly depends on the molecular weight, and the smaller the melt flow rate (MFR), the larger the molecular weight, and the larger the melt flow rate (MFR), the smaller the molecular weight. In addition, it is known that the molecular weight of the ethylene-based polymer is determined by the composition ratio of hydrogen and ethylene (hydrogen / ethylene) in the polymerization system (for example, Kazuo Soga et al., "Catalytic Olefin Polymerization", Kodansha Scientific, 1990, p. 376). For this reason, it is possible to increase or decrease the melt flow rate (MFR) of the ethylene-based polymer by increasing or decreasing hydrogen / ethylene.

(2) The density is 875 kg / m ³ or more and 970 kg / m ³ or less.
The lower limit is preferably 885 kg / m ³ , more preferably 900 kg / m ³ , and the upper limit is preferably 960 kg / m ³ , more preferably 950 kg / m ³ . When the density is in the above range, the film formed from the ethylene-based polymer has little surface stickiness and is excellent in blocking resistance, and the impact strength of the film is good, and mechanical strength such as heat seal strength and bag breaking strength is improved. It is good.

  In general, the density depends on the α-olefin content of the ethylene polymer, the lower the α-olefin content, the higher the density, and the higher the α-olefin content, the lower the density. Also, it is known that the α-olefin content in ethylene polymer is determined by the composition ratio of α-olefin to ethylene (α-olefin / ethylene) in the polymerization system (for example, Walter Kaminsky, Makromol. Chem. 193, p. 606 (1992)). For this reason, the ethylene polymer which has the density of the said range can be manufactured by increasing / decreasing alpha-olefin / ethylene.

(3) zero shear viscosity at 200 ° C. and [eta ₀ (P)], GPC-ratio (eta ₀ of viscosity detector method 6.8 square of weight average molecular weight determined by (GPC-VISCO) (Mw ^6.8) / Mw ^6.8 ) is 0.03 × 10 ⁻³⁰ or more and 7.5 × 10 ⁻³⁰ or less. That is, in the ethylene polymer, η ₀ and Mw have the following formula (Eq-1)
0.03 × 10 ^-30 ≦ η ₀ / Mw ^6.8 ≦ 7.5 × 10 ^-30 --(Eq-1)
Meet. Here, the lower limit is preferably 0.05 × 10 ^-30 , more preferably 0.8 × 10 ^-30 , and the upper limit is preferably 5.0 × 10 ^-30 , more preferably 3.0 × 10 ^-30 .

When η ₀ / Mw ^6.8 is 0.03 × 10 ^-30 or more and 7.5 × 10 ^-30 or less, when η ₀ and Mw are plotted logarithmically, log (η ₀ ) and log Mw are as follows It is synonymous with existing in the region defined by (Eq-1 ').
6.8 Log (Mw)-31.523? Log (? ₀ )? 6.8 Log (Mw)-29.125--(Eq-1 ')

When a zero-shear viscosity [η ₀ (P)] is plotted logarithmically with respect to the weight-average molecular weight (Mw), it is a linear polymer without long-chain branching, and an ethylene-based polymer which does not exhibit strain hardening. , The slope follows the power law of 3.4. On the other hand, an ethylene-based polymer having many relatively short long-chain branches and having an elongation viscosity exhibiting strain rate curability exhibits a zero shear viscosity [η ₀ (P)] lower than that of the power law, and its inclination is It is known that the value is larger than 3.4 (C Gabriel, H. Munstedt, J. Rheol., 47 (3), 619 (2003), H. Munstedt, D. Auhl, J. Non- Newtonian Fluid Mech. 128, 62-69, (2005), slope 6.8 may be selected empirically. The ratio of η ₀ to Mw ^6.8 is also disclosed in Japanese Patent Application Publication No. 2011-1545.

When the zero shear viscosity [η ₀ (P)] at 200 ° C. of the ethylene-based polymer is 20 × 10 ⁻¹³ × Mw ^6.8 or less, the occurrence of takeover surge in the ethylene-based polymer is suppressed.

Furthermore, when η ₀ / Mw ^6.8 is in the above range, there is an effect that the blocking resistance of the film obtained from the ethylene-based polymer is extremely excellent. The reason why such an effect appears is presumed as follows.

  It is known that the blocking resistance is remarkably improved by forming minute unevenness on the film surface. When the molten resin flows into the die, extensional flow generates tensile stress. When this tensile stress exceeds a critical value, fracture occurs in a brittle manner, causing unstable flow at the die exit called melt fracture, and micro unevenness is formed on the surface of the molded body (FN Cogswell, Polymer Melt Rheology, Wiley, 1981).

When η ₀ / Mw ^6.8 is in the claim range, the tensile stress becomes large at the strain rate in general forming process, and melt fracture occurs. Since minute unevenness is formed on the film surface by this melt fracture, the blocking resistance of the obtained film is extremely excellent.

It is known that the tensile stress is strongly influenced by the number and length of long chain branches, and the larger the number, the longer the length, the larger the tensile stress. When η ₀ / Mw ^6.8 exceeds the upper limit value, the number of long chain branches tends to be insufficient, and when it is below the lower limit value, the length of long chain branches tends to be insufficient.

The relationship between the zero shear viscosity [η ₀ (P)] and the weight average molecular weight (Mw) is considered to depend on the content and length of long chain branching in the ethylene-based polymer, and the long chain branching content is The higher the number and the shorter the length of the long chain branch, the closer to the lower limit of the range the zero shear viscosity [η ₀ (P)], and the smaller the long chain branch content, the longer the length of the long chain branch The zero shear viscosity [η ₀ (P)] is considered to exhibit a value close to the upper limit of the claim range.

  Here, long-chain branching is defined as a branched structure having a length equal to or greater than the molecular weight (Me) between entanglement points contained in the ethylene-based polymer, and the melt physical properties of the ethylene-based polymer and molding by introducing long-chain branching. Processability is known to change significantly (for example, Kazuo Matsuura et al., "Polyethylene Technology Reader", Industrial Research Association, 2001, p. 32, 36).

  In the mechanism by which the ethylene-based polymer is formed, the inventors of the present invention have ethylene and 4 carbon atoms in the presence of a catalyst component for olefin polymerization including the component (A), the component (C) and the solid support (S). A “macromonomer”, which is a polymer having terminal vinyl with a number average molecular weight of 4000 or more and 20000 or less, preferably 4000 or more and 15000 or less, is produced by copolymerizing with an α-olefin of 10 or less and then component (B ), The component (C) and the solid support (S), and by copolymerizing the macromonomer in a competitive manner with the polymerization of ethylene and an α-olefin having 4 to 10 carbon atoms, by the catalyst component for olefin polymerization, It is estimated that long chain branching is generated in the ethylene-based polymer.

  The higher the compositional ratio of the macromonomer to ethylene in the polymerization system ([macromonomer] / [ethylene]), the longer the long chain branching content. By increasing the molar ratio ([A] / [A + B]) of the component (A) to the ratio of the component (A) in the olefin polymerization catalyst, that is, the total of the component (A) and the component (B) [ Since the macromonomer] / [ethylene] can be increased, the long chain branch content is increased by increasing ([A] / [A + B]). In addition, when the composition ratio of hydrogen and ethylene (hydrogen / ethylene) in the polymerization system is increased, the molecular weight of the macromonomer is decreased, and hence the length of the long chain branch introduced into the ethylene-based polymer is shortened.

From this, by adjusting [A] / [A + B] and hydrogen / ethylene, it is possible to produce an ethylene-based polymer having η ₀ / Mw ^6.8 within the above range.
Besides these, polymerization conditions for controlling the amount of long chain branching are disclosed, for example, in WO 2007/034920.

(4) Intrinsic viscosity [[η] (dl / g)] measured in 135 ° C. decalin and weight-average molecular weight measured by GPC-viscosity detector method (GPC-VISCO): 0.776 (Mw ^0.776) The ratio of [η] / Mw ^0.776 is 0.90 × 10 ⁻⁴ or more and 1.65 × 10 ⁻⁴ or less. That is, in the ethylene polymer used in the present invention, [[] and Mw have the following formula (Eq-2)
^{0.90 × 10 -4 ≦ [η]} / Mw 0.776 ≦ 1.65 × 10 -4 --- (Eq-2)
Meet. Here, the lower limit is preferably 0.95 × 10 ⁻⁴ , more preferably 1.00 × 10 ⁻⁴ , and the upper limit is preferably 1.55 × 10 ⁻⁴ , more preferably 1.45 × 10 ^-4 .

[Eta] / Mw ^0.776 is it is 0.90 × 10 ^-4 or more 1.65 × 10 ^-4 or less, upon log-log plot of Mw and [eta], and log ([η])) It is synonymous with that log (Mw) exists in the area | region prescribed by a following formula (Eq-2 ').
0.776 Log (Mw)-4.046 Log Log ([]]) 0.7 0.776 Log (Mw)-3.783--(Eq-2 ')

It is known that when long-chain branching is introduced into an ethylene-based polymer, the intrinsic viscosity [η] (dl / g) decreases relative to the molecular weight as compared to a linear ethylene-based polymer without long-chain branching. For example, Walther Burchard, ADVANCES IN POLYMER SCIENCE, 143, Branched Polymer II, p. 137 (1999). Therefore, when [η] / Mw ^0.776 of the present ethylene polymer is not more than the above upper limit value, particularly 1.65 × 10 ^-4 or less, it has a large number of long chain branches, and Fluidity is excellent.

  As described above, by increasing the ratio ([A] / [A + B]) of the component (A) in the olefin polymerization catalyst, the long chain branch content is increased, so [A] / [A + B] is increased or decreased. Thus, an ethylene-based polymer (α) having an intrinsic viscosity [η] of the claimed range can be produced. The ethylene-based polymer particles obtained by the polymerization reaction and other components optionally added may be melted, kneaded, and granulated by any method for the purpose of suppressing variation in physical property values.

The ethylene-based polymer obtained in the present invention may be pelletized by the following method.
(I) A method of mechanically blending an ethylene-based polymer and other components optionally added, using an extruder, a kneader or the like, and cutting into a predetermined size.

  (Ii) Dissolve the ethylene polymer and optionally added other components in a suitable good solvent (for example, hydrocarbon solvents such as hexane, heptane, decane, cyclohexane, benzene, toluene and xylene), and then add the solvent A method of mechanical blending and cutting to a predetermined size using an extruder, a kneader, etc. after removal.

  The ethylene polymer obtained by the present invention is a weather resistant stabilizer, a heat resistant stabilizer, an antistatic agent, an antislip agent, an antiblocking agent, an antifogging agent, a lubricant, a pigment, as long as the object of the present invention is not impaired. Additives such as dyes, nucleating agents, plasticizers, anti-aging agents, hydrochloric acid absorbents, antioxidants and the like may be blended as required.

  The ethylene-based polymer obtained in the present invention and, if necessary, a resin composition containing a thermoplastic resin and an additive, are processed by general film forming, blow molding, injection molding and extrusion molding. Film forming is obtained by extrusion laminate forming, T-die film forming, inflation forming (air cooling, water cooling, multistage cooling, high speed processing) or the like. The film obtained by using the ethylene-based polymer can be used as a single layer, but can be further imparted with various functions by forming it into a multilayer. In that case, the co-extrusion method in each said shaping | molding method is mentioned. On the other hand, lamination with paper and barrier films (aluminum foil, vapor deposition film, coating film, etc.) which coextrusion is difficult is mentioned by bonding lamination molding methods like extrusion lamination molding or dry lamination method. The production of high-performance products in multilayering by coextrusion by blow molding, injection molding, and extrusion molding is possible as well as film molding.

  Examples of molded articles obtained by processing the ethylene-based polymer obtained by the present invention and, if necessary, a resin composition containing a thermoplastic resin and additives, include films, blow infusion bags, blow bottles, gasoline tanks, Injection molded products such as extrusion molded tubes, pipes, tear caps, household sundries, etc., fibers, large molded products manufactured by rotational molding, and the like.

  Furthermore, a film obtained by processing the ethylene-based polymer obtained by the present invention, and, if necessary, a resin composition containing a thermoplastic resin and an additive, can be obtained as a water package bag, a liquid soup package, a liquid paper container , Lami original fabric, special shape liquid packaging bags (standing pouches etc.), standard bags, heavy bags, wrap films, sugar bags, oily packaging bags, various packaging films for food packaging etc, protective films, infusion bags, agriculture It is suitable for materials etc. Moreover, it can also bond with base materials, such as nylon and polyester, and can also use it as a multilayer film.

  Hereinafter, the present invention will be more specifically described based on examples, but the present invention is not limited to these examples. In the following Examples and Comparative Examples, the measurement of the amount of free polymer in the production of the ethylene-based polymer and the physical properties of the obtained ethylene-based polymer were performed as follows.

<Amount of free polymer>
The amount (wt%) of the free polymer is obtained by fractionating the supernatant (solvent) after slurry polymerization and drying this to obtain the amount of polymer X (g) and the total yield Y of the polymer obtained (g) And was determined by the following equation.
Amount of free polymer (wt%) = X / (X + Y) × 100

<Melt flow rate (MFR)>
It measured on the conditions of 190 degreeC and 2.16 kg load (kgf).

<Density (D)>
The strand obtained at the time of MFR measurement was heat-treated at 100 ° C. for 30 minutes, and after standing at room temperature for 1 hour, it was measured by density gradient tube method.

Melt tension (MT)
The melt tension (MT) at 190 ° C. (in g) was determined by measuring the stress when stretched at a constant rate. A capillary rheometer: Capirograph 1D manufactured by Toyo Seiki Seisaku-sho, Ltd. was used for measurement. The conditions are: resin temperature 190 ° C, melting time 6 minutes, barrel diameter 9.55 mmφ, extrusion speed 15 mm / min, winding speed 24 m / min (If the melting filament breaks, the winding speed is decreased by 5 m / min each) The nozzle diameter was 2.095 mm and the nozzle length was 8 mm.

<Shear viscosity (η ^* )>
The shear viscosity [η ^* (1.0)] (P) at an angular velocity of 1.0 rad / sec at 200 ° C. was measured by the following method.
Shear viscosity (eta ^*) measures the angular velocity [omega (rad / sec)] variance of a shear viscosity at a measurement temperature of 200 ° C. (eta ^*) in the range of 0.01 ≦ ω ≦ 100. For measurement, a viscoelasticity measuring apparatus Physica MCR 301 manufactured by Anton Paar Co., Ltd. was used, a parallel plate of 25 mmφ was used as a sample holder, and a sample thickness was about 2.0 mm. The measurement points were 5 points per single digit of ω. The amount of distortion was appropriately selected in the range of 3 to 10% so that torque in the measurement range could be detected and torque over would not occur.

The sample used for shear viscosity measurement is a press molding machine manufactured by Kamitoko Kogyo Co., Ltd., preheating temperature 190 ° C., preheating time 5 minutes, heating temperature 190 ° C., heating time 2 minutes, heating pressure 100 kgf / cm ² , cooling temperature 20 The measurement sample was produced by press-molding to a thickness of 2 mm under the conditions of ° C., a cooling time of 5 minutes, and a cooling pressure of 100 kgf / cm ² .

<Zero shear viscosity (η ₀ )>
The zero shear viscosity (η ₀ ) (P) at 200 ° C. was determined by the following method.
The angular velocity ω (rad / second) dispersion of the shear viscosity ( ^** ) is measured in the range of 0.01 ≦ ω ≦ 100 at a measurement temperature of 200 ° C. For measurement, a viscoelasticity measuring apparatus Physica MCR 301 manufactured by Anton Paar Co., Ltd. was used, a parallel plate of 25 mmφ was used as a sample holder, and a sample thickness was about 2.0 mm. The measurement points were 5 points per single digit of ω. The amount of distortion was appropriately selected in the range of 3 to 10% so that torque in the measurement range could be detected and torque over would not occur.

The sample used for shear viscosity measurement is a press molding machine manufactured by Kamitoko Kogyo Co., Ltd., preheating temperature 190 ° C., preheating time 5 minutes, heating temperature 190 ° C., heating time 2 minutes, heating pressure 100 kgf / cm ² , cooling temperature 20 The measurement sample was produced by press-molding to a thickness of 2 mm under the conditions of ° C., a cooling time of 5 minutes, and a cooling pressure of 100 kgf / cm ² .

The zero shear viscosity ( _{0 0} ) was calculated by fitting a Carreau model of the following formula (Eq-3) to the measured rheological curve [angular velocity (ω) dispersion of shear viscosity (η ^* )] by nonlinear least squares method .
Η ^* = η ₀ [1+ (λω) ^a ] ^{(n-1) / a} ---(Eq-3)

  Here, λ is a parameter having a dimension of time, and n is a power law index of the material. In addition, the fitting by the non-linear least squares method was performed so that d in a following formula (Eq-4) might become the minimum.

上記式（Ｅｑ−４）中、η_exp（ω）は実測のせん断粘度を表し、η_calc（ω）はＣａｒｒｅａｕモデルより算出したせん断粘度を表す。

In said Formula (Eq-4), (eta) _exp ((omega)) represents the shear viscosity of measurement, and (eta) _calc ((omega)) represents the shear viscosity calculated from the Carreau model.

<Number average molecular weight (Mn), weight average molecular weight (Mw), Z average molecular weight (Mz), molecular weight distribution (Mw / Mn, Mz / Mw)>
It measured as follows using GPC- viscosity detector (GPC-VISCO) GPC / V2000 by Waters company.

  The guard column uses Shodex AT-G, the analysis column uses two AT-806, the detector uses a differential refractometer and a 3-capillary viscometer, the column temperature is 145 ° C, and the mobile phase is An o-dichlorobenzene containing 0.3% by weight of BHT was used as an antioxidant, the flow rate was 1.0 ml / min, and the sample concentration was 0.1% by weight. As the standard polystyrene, one manufactured by Tosoh Corporation was used. Molecular weight calculation calculates actual measurement viscosity from viscometer and refractometer, number average molecular weight (Mn), weight average molecular weight (Mw), Z average molecular weight (Mz), molecular weight distribution (Mw / Mn, Mz) from measurement universal calibration / Mw was determined.

<Intrinsic viscosity [η]>
About 20 mg of a measurement sample was dissolved in 15 ml of decalin, and the specific viscosity _{sp sp} was measured in an oil bath at 135 ° C. After diluting 5 ml of decalin solvent to the decalin solution to dilute, the specific viscosity _{sp sp} was measured in the same manner. This dilution operation is further repeated twice, and the value of _{sp sp} / C when the concentration (C) is extrapolated to 0 as shown in the following formula (Eq-5) is the limiting viscosity [η] (unit; dl / g Asked as).
[Η] = lim (η _sp / C) (C → 0)---(Eq-5)

[Synthesis of Component (A) and Component (B)]
Synthesis Example 1
(1) 5.01 mL (43.0 mmol) of indene and 50 mL of tetrahydrofuran are charged into a 300 mL reactor sufficiently dried and purged with argon, and 28.0 mL of n-butyllithium solution (hexane solution, 1.62 M, 45.4 mmol) ) Was added under ice-cooling and stirred at room temperature for 2 hours. To this solution was added dropwise 5.20 mL (45.4 mmol) of butyl iodide under ice-cooling, and stirring was continued for 15 hours while gradually returning to room temperature. Saturated aqueous ammonium chloride solution was added, the solubles were extracted with n-hexane, and the obtained fraction was washed with saturated brine and dried over anhydrous magnesium sulfate. After magnesium sulfate is filtered, the filtrate is evaporated and the residue thus obtained is purified by silica gel column chromatography to obtain the desired product (hereinafter referred to as compound (A-1a)) represented by the following formula (A-1a) Obtained as a mixture of 6.50 g (yield 88%) of isomers.

¹ H NMR (270 MHz, CDCl ₃ ) δ 7.44 (1 H, d, J = 7.3 Hz, Ar-H), 7.41-7.24 (2 H, m, Ar-H), 7.24- 7.13 (1 H, m, Ar-H), 6.18 (1 H, t, J = 1.5 Hz, C = CH-C), 3.31 (2 H, d, J = 2.0 Hz, C- _{CH 2 -CH), 2.62-2.47 (2H} , m, C-CH 2 -CH 2 -), 1.75-1.57 (2H, m, -CH 2 -CH 2 -), 1 _{.53-1.30 (2H, m, -CH 2} -CH 2 -), 0.95 (3H, t, J = 7.3Hz, -CH 2 -CH 3) ppm

（２）充分に乾燥、アルゴン置換した１００ｍＬの反応器に、前記（１）で得られた化合物（Ａ−１ａ）１．５７ｇ（９．１３ｍｍｏｌ）とテトラヒドロフラン２０ｍＬを仕込み、ｎ−ブチルリチウム溶液５．６０ｍＬ（ヘキサン溶液、１．６４Ｍ、９．１８ｍｍｏｌ）を氷冷下で加え、室温で２時間攪拌した。この反応液を、ジメチルシリルジクロリド５．５０ｍＬ（４６．０ｍｍｏｌ）のｎ−ヘキサン１０ｍＬ希釈溶液に、−７８℃冷却下でゆっくりと加え、室温まで戻しながら２０時間攪拌を続けた。反応液の溶媒および未反応のジメチルシリルジクロリドを留去した後、残渣にテトラヒドロフラン１０ｍＬ、１，３−ジメチル−２−イミダゾリジノン０．９０ｍＬ（９．５８ｍｍｏｌ）を加えた。充分に乾燥、アルゴン置換した１００ｍＬの反応器に、ナトリウムシクロペンタジエニド溶液４．６０ｍＬ（テトラヒドロフラン溶液、２．０Ｍ、９．２０ｍｍｏｌ）、テトラヒドロフラン１０ｍＬを仕込んだ。この溶液を、−７８℃に冷却した先程の反応残渣希釈溶液に滴下し、ゆっくりと室温まで戻しながら１９時間攪拌を続けた。飽和塩化アンモニウム水溶液を加え、ｎ−ヘキサンで可溶分を抽出し、得られた分画を飽和食塩水で洗浄し、無水硫酸マグネシウムで乾燥した。硫酸マグネシウムをろ過した後、ろ液を留去して得られた残渣をシリカゲルカラムクロマトグラフィーで精製すると、下記式（Ａ−１Ｌ）で示した目的物（以下「化合物（Ａ−１Ｌ）」ともいう。）が２．２０ｇ（収率８２％）の異性体混合物として得られた。

(2) 1.57 g (9.13 mmol) of the compound (A-1a) obtained in the above (1) and 20 mL of tetrahydrofuran are charged in a sufficiently dried and argon-substituted 100 mL reactor, and n-butyllithium solution 5 .60 mL (hexane solution, 1.64 M, 9.18 mmol) was added under ice-cooling and stirred at room temperature for 2 hours. The reaction solution was slowly added to a dilute solution of 5.50 mL (46.0 mmol) of dimethylsilyl dichloride in 10 mL of n-hexane under cooling with cooling, and stirring was continued for 20 hours while returning to room temperature. After the solvent of the reaction solution and unreacted dimethylsilyl dichloride were distilled off, 10 mL of tetrahydrofuran and 0.90 mL (9.58 mmol) of 1,3-dimethyl-2-imidazolidinone were added to the residue. A sufficiently dried, argon-replaced 100 mL reactor was charged with 4.60 mL of a sodium cyclopentadienide solution (tetrahydrofuran solution, 2.0 M, 9.20 mmol) and 10 mL of tetrahydrofuran. This solution was added dropwise to the previously diluted reaction residue diluted solution cooled to −78 ° C., and stirring was continued for 19 hours while gradually returning to room temperature. Saturated aqueous ammonium chloride solution was added, the solubles were extracted with n-hexane, and the obtained fraction was washed with saturated brine and dried over anhydrous magnesium sulfate. After magnesium sulfate is filtered, the filtrate is evaporated and the obtained residue is purified by silica gel column chromatography to obtain the desired product (hereinafter referred to as "compound (A-1L)") represented by the following formula (A-1L) Was obtained as an isomer mixture of 2.20 g (yield 82%).

¹ H NMR (270 MHz, CDCl ₃ ) δ 7.62-7.15 (5 H, m, Ar-H & C = CH-C), 6.90-6.08 (4 H, m, C = CH-C), 3.78-2.80 (2H, m, Si- CH), 2.76-2.52 (2H, m, C-CH 2 -CH 2 -), 1.84-1.60 (2H, m , -CH ₂ -CH _2- ), 1.60-1.38 (2H, m, -CH ₂ -CH _2- ), 1.03 (3H, t, J = 7.3 Hz, -CH ₂ -CH _{3), 0.30 - -0.50 (6H} , m, Si-CH 3) ppm

  (3) 0.59 g (2.01 mmol) of the compound (A-1 L) obtained in the above (2), 20 mL of toluene and 0.4 mL of tetrahydrofuran were charged into a sufficiently dried and argon-substituted 100 mL reactor. . After adding 2.50 mL (hexane solution, 1.64 M, 4.10 mmol) of n-butyllithium solution to this solution at room temperature, stirring was continued in a 40 ° C. oil bath for 3 hours. After the solvent of the reaction solution was distilled off, 20 mL of diethyl ether was added to the obtained solid. The solution was cooled to 0 ° C., 0.46 g (1.95 mmol) of zirconium tetrachloride was added, and stirring was continued at room temperature for 19 hours. After distilling off the solvent of the reaction solution, dichloromethane was added to the obtained solid to prepare a suspension, and the insoluble matter was removed with Celite on a glass filter. The resulting solution was concentrated under reduced pressure, and then a suspension was prepared by adding n-hexane, and the insoluble matter was separated by filtration using a glass filter. By drying the residue under reduced pressure, the compound dimethylsilylene (3-n-butyl-1-indenyl) (cyclopentadienyl) zirconium dichloride represented by the following formula (A-1) is obtained as a yellow powder (hereinafter referred to as “component (A) -1) ") was obtained (yield 54%).

¹ H NMR (270 MHz, CDCl ₃ ) δ 7.60 (1 H, dt, J = 8.5 and 1.0 Hz, Ar-H), 7.47-7.36 (2 H, m, Ar-H), 7. 13-7.03 (1 H, m, Ar-H), 6.84-6. 73 (2 H, m, Cp-H), 5.89-5. 84 (1 H, m, Cp-H), 5 .82 (1H, s, Ind- H), 5.80-5.75 (1H, m, Cp-H), 2.90 (2H, t, J = 7.7Hz, C-CH 2 -CH 2 -), 1.70-1.50 (2H, m , -CH 2 -CH 2 -), 1.50-1.25 (2H, m, -CH 2 -CH 2 -), 1.03 (3H _{, s, Si-CH 3)} , 0.92 (3H, t, J = 7.3Hz, -CH 2 -CH 3), 0.81 (3H, s, Si-CH 3) ppm
FD-mass spectrometry (M ⁺ ): 454

Synthesis Example 2
(1) 3.91 g (30.0 mmol) of 2-methylindene and 30 mL of tetrahydrofuran are charged into a sufficiently dried, argon-substituted 300 mL reactor, and 19.2 mL of n-butyllithium solution (hexane solution, 1.64 M, 31.5 mmol) was added under ice-cooling and stirred at room temperature for 3 hours. To this solution, 3.61 mL (31.5 mmol) of butyl iodide was added dropwise under ice-cooling, and stirring was continued for 2 hours while gradually returning to room temperature. Saturated aqueous ammonium chloride solution was added, the solubles were extracted with n-hexane, and the obtained fraction was washed with saturated brine and dried over anhydrous magnesium sulfate. After magnesium sulfate is filtered, the filtrate is evaporated and the obtained residue is purified by silica gel column chromatography to obtain the desired product (hereinafter referred to as "compound (A-2a)") represented by the following formula (A-2a) Is obtained as an isomer mixture of 5.40 g (yield 97%).

¹ H NMR (270 MHz, CDCl ₃ ) δ 7.34 (1 H, d, J = 7.4 Hz, Ar-H), 7.24-7.14 (2 H, m, Ar-H), 7.14 7.02 (1 H, m, Ar-H), 6.44 (1 H, s, C = CH-C), 3.33 (1 H, t, J = 5.0 Hz, C-CH-C), 2 .05 (3H, d, J = 0.8Hz, -CH 3), 2.03-1.08 (1H, m, CH-CH 2 -CH 2 -), 1.83-1.63 (1H, _{m, CH-CH 2 -CH 2} -), 1.31-1.17 (2H, m, -CH 2 -CH 2 -), 1.16-0.86 (2H, m, -CH 2 -CH _{2 -), 0.82 (3H,} t, J = 7.3Hz, -CH 2 -CH 3) ppm

  (2) 3.73 g (20.0 mmol) of the compound (A-2a) obtained in the above (1) and 30 mL of tetrahydrofuran are charged in a sufficiently dried and argon-substituted 100 mL reactor, and n-butyllithium solution 12 .2 mL (hexane solution, 1.64 M, 20.0 mmol) was added under ice-cooling and stirred at room temperature for 2 hours. This reaction solution was slowly added to a solution of 12.0 mL (100 mmol) of dimethylsilyl dichloride in 10 mL of n-hexane under cooling with cooling, and stirring was continued for 19 hours while returning to room temperature. After distilling off the solvent of the reaction solution and unreacted dimethylsilyl dichloride, 20 mL of tetrahydrofuran and 1.90 mL (20.2 mmol) of 1,3-dimethyl-2-imidazolidinone were added to the residue. In a sufficiently dried, argon-replaced 100 mL reactor, 10.0 mL of a sodium cyclopentadienide solution (tetrahydrofuran solution, 2.0 M, 20.0 mmol) and 20 mL of tetrahydrofuran were charged. This solution was added dropwise to the previously diluted reaction residue diluted solution cooled to −78 ° C., and stirring was continued for 19 hours while gradually returning to room temperature. Saturated aqueous ammonium chloride solution was added, the solubles were extracted with n-hexane, and the obtained fraction was washed with saturated brine and dried over anhydrous magnesium sulfate. After magnesium sulfate is filtered, the filtrate is evaporated and the obtained residue is purified by silica gel column chromatography to obtain the desired product (hereinafter referred to as "compound (A-2L)" represented by the following formula (A-2L) Was obtained as an isomer mixture of 5.41 g (yield 88%).

¹ H NMR (270 MHz, CDCl ₃ ) δ 7.61 to 7.01 (4 H, m, Ar-H), 6.92 to 5.96 (4 H, m, C = CH-C), 3.80 2.75 (2H, m, Si- CH), 2.74-2.48 (2H, m, C-CH 2 -CH 2 -), 2.30-2.00 (3H, m, -CH 3 ), 1.70 to 1.36 (4H, m, -CH ₂ -CH _2- ), 1.02 (3H, t, J = 7.2 Hz, -CH ₂ -CH ₃ ), 0.30-- 0.40 (6H, m, Si-CH ₃ ) ppm

  (3) 0.62 g (2.01 mmol) of the compound (A-2L) obtained in the above (2), 20 mL of toluene, and 0.4 mL of tetrahydrofuran were charged into a sufficiently dried and argon-substituted 100 mL reactor. . After 2.60 mL (hexane solution, 1.55 M, 4.03 mmol) of n-butyllithium solution was added to this solution at room temperature, stirring was continued in a 40 ° C. oil bath for 3 hours. After the solvent of the reaction solution was distilled off, 20 mL of diethyl ether was added to the obtained solid. The solution was cooled to 0 ° C., 0.46 g (1.99 mmol) of zirconium tetrachloride was added, and stirring was continued at room temperature for 18 hours. After distilling off the solvent of the reaction solution, dichloromethane was added to the obtained solid to prepare a suspension, and the insoluble matter was removed with Celite on a glass filter. The resulting solution was concentrated under reduced pressure, and then a suspension was prepared by adding n-hexane, and the insoluble matter was separated by filtration using a glass filter. By drying the residue under reduced pressure, the compound dimethylsilylene (3-n-butyl-2-methyl-1-indenyl) (cyclopentadienyl) zirconium dichloride represented by the following formula (A-2) is obtained as a yellow powder: 0.22 g (yield 24%) of “component (A-2)” was obtained.

¹ H NMR (270 MHz, CDCl ₃ ) δ 7.59 (1 H, dt, J = 8.6 and 1.0 Hz, Ar-H), 7. 50 (1 H, dt, J = 8.6 and 1.0 Hz, Ar-H ), 7.45 to 7.35 (1 H, m, Ar-H), 7.07 to 6.97 (1 H, m, Ar-H), 6.84 to 6.76 (1 H, m, Cp-). H), 6.74-6.67 (1H, m, Cp-H), 5.81 (2H, t, J = 2.4 Hz, Cp-H), 2.95-2.75 (2H, m) , C-CH ₂ -CH _2- ), 2.09 (3 H, s, -CH ₃ ), 1.60 -1. 26 (4 H, m, -CH ₂ -CH _2- ), 1.07 (3 H) _{, s, Si-CH 3)} , 0.96 (3H, s, Si-CH 3), 0.92 (3H, t, J = 7.2Hz, -CH 2 -CH 3) ppm
FD-mass spectrometry (M ⁺ ): 468

Synthesis Example 3
(1) A sufficiently dried, argon-replaced 200 mL reactor was charged with 1.44 g (59.4 mmol) of magnesium pieces and vigorously stirred for 30 minutes while heating under reduced pressure. After cooling to room temperature, a reflux condenser was attached, and a piece of iodine and 15 mL of tetrahydrofuran were charged and stirred. A 10 mL diluted solution of 2.93 g (15.0 mmol) of 2-bromoindene is added dropwise (1.0 mL after addition, followed by heating to reflux until the color of iodine disappears with a drier, remaining after dropping of the reaction drop) It stirred at room temperature after completion | finish for 2 hours. This reaction solution was slowly added to a solution of 9.00 mL (75.3 mmol) of dimethylsilyl dichloride in 10 mL of n-hexane while cooling, and stirring was continued for 17 hours while returning to room temperature. After the solvent of the reaction solution and unreacted dimethylsilyl dichloride were distilled off, 10 mL of tetrahydrofuran and 1.50 mL (16.0 mmol) of 1,3-dimethyl-2-imidazolidinone were added to the residue. 2.80 g (15.0 mmol) of the compound (A-2a) obtained in the above Synthesis Example 2 (1) and 15 mL of tetrahydrofuran were charged in a sufficiently dried and argon-substituted 100 mL reactor, and n-butyllithium solution 9 .70 mL (hexane solution, 1.55 M, 15.0 mmol) was added and stirred at room temperature for 2 hours. This solution was added dropwise to the previously diluted reaction residue diluted solution cooled to −78 ° C., and stirring was continued for 16 hours while slowly returning to room temperature. Saturated aqueous ammonium chloride solution was added, the solubles were extracted with n-hexane, and the obtained fraction was washed with saturated brine and dried over anhydrous magnesium sulfate. After magnesium sulfate is filtered, the filtrate is evaporated and the obtained residue is purified by silica gel column chromatography to obtain the desired product (hereinafter referred to as "compound (A-3L)") represented by the following formula (A-3L) Is obtained as an isomer mixture of 3.15 g (yield 58%).

¹ H NMR (270 MHz, CDCl ₃ ) δ 7.43 (1 H, d, J = 7.3 Hz, Ar-H), 7.38 (1 H, d, J = 7.4 Hz, Ar-H), 7. 33-7.12 (5H, m, Ar-H), 7.10-6.98 (2H, m, Ar-H & C = CH-C), 3.45 (1 H, s, Si-CH), 3 .22 (2H, dd, J = 47.7and22.4Hz, C-CH 2 -C -), 2.49 (2H, t, J = 7.3Hz, -CH 2 -CH 3), 2.01 ( _{3H, s, -CH 3),} 1.49-1.18 (4H, m, -CH 2 -CH 2 -), 0.82 (3H, t, J = 7.1Hz, -CH 2 -CH 3 ), 0.21 (3H, s, Si-CH 3), 0.15 (3H, s, Si-CH 3) ppm

  (2) 0.72 g (2.00 mmol) of the compound (A-3 L) obtained in the above (1), 20 mL of toluene, and 0.4 mL of tetrahydrofuran were charged into a sufficiently dried and argon-substituted 100 mL reactor. . After 2.60 mL (hexane solution, 1.55 M, 4.03 mmol) of n-butyllithium solution was added to this solution at room temperature, stirring was continued in a 40 ° C. oil bath for 3 hours. After the solvent of the reaction solution was distilled off, 20 mL of diethyl ether was added to the obtained solid. The solution was cooled to 0 ° C., 0.47 g (2.00 mmol) of zirconium tetrachloride was added, and stirring was continued at room temperature for 19 hours. After distilling off the solvent of the reaction solution, dichloromethane was added to the obtained solid to prepare a suspension, and the insoluble matter was removed with Celite on a glass filter. The resulting solution was concentrated under reduced pressure, and then a suspension was prepared by adding n-hexane, and the insoluble matter was separated by filtration using a glass filter. By drying the residue under reduced pressure, the compound dimethylsilylene (3-n-butyl-1-indenyl) (2-indenyl) zirconium dichloride represented by the following formula (A-3) is obtained as a yellow powder (hereinafter referred to as “component (A- 3) ") was obtained (yield: 39%).

¹ H NMR (270 MHz, CDCl ₃ ) δ 7.73-7.63 (2H, m, Ar-H), 7.50 (1 H, dt, J = 8.6 and 1.0 Hz, Ar-H), 7. 39-7.25 (2H, m, Ar-H), 7.25-7. 16 (2H, m, Ar-H), 7.16-7.07 (1 H, m, Ar-H), 6 .09-6.03 (1H, m, Ind- H), 2.95-2.60 (2H, m, C-CH 2 -CH 2 -), 2.17 (3H, s, Ind-CH 3 ), 1.60-1.20 (4H, m, -CH 2 -CH 2 -), 1.13 (3H, s, Si-CH 3), 1.00 (3H, s, Si-CH 3) , 0.89 (3H, t, J = 7.1Hz, -CH 2 -CH 3) ppm
FD-mass spectrometry (M ⁺ ): 518

Synthesis Example 4
The dimethylsilylene (3-n-propylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride (hereinafter also referred to as “component (A-4)”) represented by the following formula (A-4) is disclosed in Japanese Patent No. 5455354 It synthesize | combined by the method of a statement.

Synthesis Example 5
The dimethylsilylene (cyclopentadienyl) (1-indenyl) zirconium dichloride (hereinafter also referred to as “compound (A-5)”) represented by the following formula (A-5) is a Macromolecules 1995, 28, 3771. It synthesize | combined by the method of a statement.

Synthesis Example 6
The isopropylidene (cyclopentadienyl) (2,7-di-tert-butylfluorenyl) zirconium dichloride (hereinafter also referred to as “component (B-1)”) represented by the following formula (B-1) is It synthesize | combined based on the method as described in Unexamined-Japanese-Patent No. 4-69394.

Example 1
<Preparation of Solid Catalyst Component (X)>
Silica with an average particle diameter of 70 μm, a specific surface area of 340 m ² / g, and a pore volume of 1.3 cm ³ / g as a solid carrier (S) in a nitrogen atmosphere in a 270 l internal volume reactor with a stirrer g, 250 ° C. calcination) 10 kg was suspended in 77 liters of toluene and then cooled to 0 to 5 ° C. To this suspension, 20.4 liters of a toluene solution of methylaluminoxane (3.5 mol / L in terms of Al atom) as component (C) was added dropwise over 30 minutes. At this time, the temperature in the system was maintained at 0 to 5 ° C. Subsequently, the mixture was allowed to react at 0 to 5 ° C. for 30 minutes, heated to 95 to 100 ° C. over about 1.5 hours, and then allowed to react at 95 to 100 ° C. for 4 hours. Thereafter, the temperature was lowered to normal temperature, the supernatant was removed by decantation, and after washing twice with toluene, a total of 59.0 liters of toluene slurry was prepared. A part of the obtained slurry component was collected and the concentration was examined. The slurry concentration was 232.0 g / L and the Al concentration was 1.19 mol / L.

  Among them, 8.6 ml (solid content mass: 2.0 g) was charged into a stirred reactor with an internal volume of 200 ml under a nitrogen atmosphere, and a total of 65.7 ml of toluene was added. Next, 35.0 μmol of a toluene solution of the component (A-1) obtained in Synthesis Example 1 was added as Zr, and 15.0 μmol of a toluene solution of the component (B-1) obtained in Synthesis Example 5 was added as Zr ( Component (A) / component (B) molar ratio = 70/30). After contacting them at a system temperature of 73 to 77 ° C. for 2 hours, the supernatant is removed by decantation, and after washing twice with 100 ml of hexane, the solid catalyst component (X- The hexane slurry of 1) was prepared.

<Production of ethylene-based polymer>
After adding 500 ml of heptane under an atmosphere of nitrogen to a 1-liter SUS autoclave with an internal volume sufficiently purged with nitrogen, ethylene was allowed to flow to saturate the liquid phase and the gas phase with ethylene. Next, after charging 10 mL of 1-hexene, 0.375 mmol of triisobutylaluminum and 40 mg of the solid catalyst component (X-1) as a solid component, the temperature is raised to 80 ° C. and 0.8 MPaG with ethylene. The pressure was increased and polymerization was performed for 90 minutes. The obtained polymer was filtered and vacuum dried at 80 ° C. for 10 hours to obtain 58.4 g of an ethylene-based polymer. At this time, the amount of free polymer measured by the above method was 1.5 wt%. The polymerization activity per solid catalyst is 1,460 g / g-cat. Met. No deposits were observed on the wall of the autoclave after the polymerization of the slurry and on the stirring blade.

0.1% by mass of Irgano X 1076 (trade name, manufactured by Ciba Specialty Chemicals, Inc.) and 0.1% by mass of Irgafos 168 (trade name, manufactured by Ciba Specialty Chemicals, Inc.) as a heat resistant stabilizer are added to the obtained ethylene-based polymer Using a laboplast mill (manufactured by Toyo Seiki Seisakusho Co., Ltd.), melt kneading was performed for 5 minutes at a resin temperature of 180 ° C. and a rotation number of 50 rpm. Furthermore, the molten polymer was cooled using a press molding machine (manufactured by Kamitoh Metal Works, Ltd.) at a cooling temperature of 20 ° C., a cooling time of 5 minutes, and a cooling pressure of 100 kg / cm ² . Physical properties were measured using the obtained sample as a measurement sample. The results are shown in Table 8.

Example 2
<Preparation of Solid Catalyst Component (X)>
In Example 1, 40.0 μmol of the component (A-2) is used instead of 35.0 μmol of the component (A-1), and 15.0 μmol of the component (B-1) is changed to 10.0 μmol. A slurry of the solid catalyst component (X-2) was prepared in the same manner as in Example 1 except that the molar ratio of component / component (B) was changed to 80/20.

<Production of ethylene-based polymer>
After adding 500 ml of heptane under an atmosphere of nitrogen to a 1-liter SUS autoclave with an internal volume sufficiently purged with nitrogen, ethylene was allowed to flow to saturate the liquid phase and the gas phase with ethylene. Next, after charging 10 mL of 1-hexene, 0.375 mmol of triisobutylaluminum and 60 mg of the solid catalyst component (X-2) as a solid, ethylene / hydrogen mixed gas having a hydrogen concentration of 0.1 vol% The temperature was raised to 80 ° C. and 0.8 MPaG, and the pressure was raised, and the polymerization reaction was performed for 90 minutes. The obtained polymer was filtered and vacuum dried at 80 ° C. for 10 hours to obtain 143.2 g of an ethylene-based polymer. Under the present circumstances, the amount of free polymers measured by the said method was 0.7 wt%. The polymerization activity per solid catalyst was 2,390 g / g-cat. Met. No deposits were observed on the wall of the autoclave after the polymerization of the slurry and on the stirring blade. The obtained ethylene-based polymer was melt-kneaded and cooled in the same manner as in Example 1, and physical properties were measured using the obtained sample as a measurement sample. The results are shown in Table 8.

[Example 3]
<Preparation of Solid Catalyst Component (X)>
In Example 1, 20.5 μmol of the component (A-3) is used instead of 35.0 μmol of the component (A-1), and 15.0 μmol of the component (B-1) is changed to 13.7 μmol to obtain the component (A) A slurry of the solid catalyst component (X-3) was prepared in the same manner as in Example 1 except that the molar ratio of component / component (B) was changed to 60/40.

<Production of ethylene-based polymer>
After adding 500 ml of heptane under an atmosphere of nitrogen to a 1-liter SUS autoclave with an internal volume sufficiently purged with nitrogen, ethylene was allowed to flow to saturate the liquid phase and the gas phase with ethylene. Next, after charging 10 mL of 1-hexene, 0.375 mmol of triisobutylaluminum and 50 mg of the solid catalyst component (X-3) as a solid component, the temperature is raised to 80 ° C. and 0.8 MPaG with ethylene. The pressure was increased and polymerization was performed for 90 minutes. The obtained polymer was filtered and vacuum dried at 80 ° C. for 10 hours to obtain 96.9 g of an ethylene-based polymer. Under the present circumstances, the amount of free polymers measured by the said method was 2.4 wt%. The polymerization activity per solid catalyst is 1,930 g / g-cat. Met. No deposits were observed on the wall of the autoclave after the polymerization of the slurry and on the stirring blade. The obtained ethylene-based polymer was melt-kneaded and cooled in the same manner as in Example 1, and physical properties were measured using the obtained sample as a measurement sample. The results are shown in Table 8.

Comparative Example 1
<Preparation of Solid Catalyst Component (X)>
In Example 1, 20.0 μmol of the component (A-4) is used instead of 35.0 μmol of the component (A-1), and 15.0 μmol of the component (B-1) is changed to 30.0 μmol. A slurry of the solid catalyst component (X-4) was prepared in the same manner as in Example 1 except that the molar ratio of component / component (B) was changed to 40/60.

<Production of ethylene-based polymer>
In the same manner as in Example 1 except that 60 mg of solid catalyst component (X-4) was used instead of 40 mg of solid catalyst component (X-1) in Example 1, 87.0 g of ethylene-based polymer was obtained. The Under the present circumstances, the amount of free polymers measured by the said method was 10.0 wt%. The polymerization activity per solid catalyst is 1,450 g / g-cat. Met. Adherents were observed on the autoclave wall surface and the stirring blade after slurry polymerization. The obtained ethylene-based polymer was melt-kneaded and cooled in the same manner as in Example 1, and physical properties were measured using the obtained sample as a measurement sample. The results are shown in Table 8.

Comparative Example 2
<Preparation of Solid Catalyst Component (X)>
In Example 1, using 46.5 μmol of the component (A-5) instead of 35.0 μmol of the component (A-1), changing 15.0 μmol of the component (B-1) to 3.5 μmmol, the component (A) A slurry of the solid catalyst component (X-5) was prepared in the same manner as in Example 1 except that the molar ratio of component / component (B) was changed to 93/7.

<Production of ethylene-based polymer>
In the same manner as in Example 1 except that 100 mg of the solid catalyst component (X-5) was used instead of 40 mg of the solid catalyst component (X-1) in Example 1, 27.0 g of an ethylene-based polymer was obtained. The Under the present circumstances, the amount of free polymers measured by the said method was 8.5 wt%. The polymerization activity per solid catalyst is 270 g / g-cat. Met. Adherents were observed on the autoclave wall surface and the stirring blade after slurry polymerization. The obtained ethylene-based polymer was melt-kneaded and cooled in the same manner as in Example 1, and physical properties were measured using the obtained sample as a measurement sample. The results are shown in Table 8.

  Although the ethylene-based polymers obtained in Examples 1 to 3 have a low molecular weight as compared with the ethylene-based polymers obtained in Comparative Examples 1 and 2, the amount of free polymer was remarkably small. In addition, no deposits were found on the autoclave wall and the stirring blade, and fouling was also suppressed. That is, in Examples 1 to 3 of the present invention, it is clear that ethylene polymers having a large amount of long-chain branching and excellent moldability can be manufactured more stably than Comparative Examples 1 and 2.

Claims (10)

An olefin polymerization catalyst comprising the following component (A), the following component (B), the following component (C) and a solid carrier (S).
Component (A): transition metal compound represented by the following general formula (1);

[In the formula (1), M is a group 4 transition metal atom of the periodic table,
n is an integer of 1 to 4 satisfying the valence of M,
X is a hydrogen atom, a halogen atom, a hydrocarbon group, an anionic ligand, or a neutral ligand that can be coordinated with a lone electron pair; the anionic ligand is a halogen-containing group, a silicon-containing group, an oxygen-containing group A sulfur-containing group, a nitrogen-containing group, a phosphorus-containing group, a boron-containing group, an aluminum-containing group or a conjugated diene-based derivative group; and when n is 2 or more, plural Xs may be the same or different from each other Well, they may be combined with each other to form a ring,
Q ¹ is a group 14 transition atom in the periodic table,
R ^{1 to} R ⁴ and R ^{7 to} R ¹² each independently represent a hydrogen atom, a hydrocarbon group having 1 to 40 carbon atoms, a halogen-containing group, a silicon-containing group, an oxygen-containing group, a nitrogen-containing group or a sulfur-containing group ,
R ⁵ represents a hydrogen atom, a hydrocarbon group having 1 to 40 carbon atoms, a halogen-containing group, a silicon-containing group, an oxygen-containing group, a nitrogen-containing group, a sulfur-containing group, or at least one atom selected from nitrogen, oxygen and sulfur A heteroaromatic group which may have a substituent, which has a 5-membered ring as a mother skeleton containing
R ⁶ is a saturated hydrocarbon group having 3 to 10 carbon atoms in the linear portion or a terminal unsaturated hydrocarbon group having 3 to 10 carbon atoms in the linear portion,
R ¹ and R ² and R ³ and R ⁴ may be bonded to each other to form a saturated ring which may have a substituent,
Adjacent substituents of R ² and R ³ and R ^{7 to} R ¹⁰ may combine with each other to form a ring which may have a substituent,
R ¹¹ and R ¹² may be bonded to each other to form a ring containing Q ^1, and the ring may have a substituent. ]
Component (B): transition metal compound represented by the following general formula (2);

[In the formula (2), M is a group 4 transition metal atom of the periodic table,
X is an atom or a group independently selected from a hydrogen atom, a halogen atom, a hydrocarbon group, a halogen-containing hydrocarbon group, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group and a phosphorus-containing group
Q ² is a group selected from a hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing group, a silicon-containing group, a germanium-containing group and a tin-containing group,
R ^{13 to} R ²⁴ each independently represent a hydrogen atom, 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 and tin Two adjacent groups selected from the contained groups may be linked to form a ring. ]
Component (C): an organic metal compound (c-1) represented by the following general formulas (3) to (5), an organic aluminum oxy compound (c-2), and a component (A) and a component (B) At least one compound selected from the group consisting of compounds (c-3) which react to form an ion pair;
_{^{R a m Al (OR b)}} n H p X q ··· (3)
[In Formula (3), R ^a and R ^b each independently represent a hydrocarbon group having 1 to 15 carbon atoms, X represents a halogen atom, m is 0 <m ≦ 3, n is 0 ≦ n <3, p is 0 ≦ p <3, q is a number of 0 ≦ q <3, and m + n + p + q = 3. ]
M ^a Al R ^a ₄ (4)
Wherein (4), M ^a represents a Li, Na or K, R ^a represents a hydrocarbon group having 1 to 15 carbon atoms. ]
R ^a _r M ^b R ^b _s X _t (5)
[In Formula (5), R ^a and R ^b each independently represent a hydrocarbon group having 1 to 15 carbon atoms, M ^b is selected from Mg, Zn and Cd, and X is a halogen atom , R is 0 <r ≦ 2, s is 0 ≦ s ≦ 1, t is 0 ≦ t ≦ 1, and r + s + t = 2. ] In the above formula (1), M is a zirconium atom or a hafnium atom, X is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group or an oxygen-containing group, and Q ¹ is a carbon atom The catalyst for olefin polymerization according to claim 1, which is a silicon atom. In the above formula (1), Q ¹ is a silicon atom, and R ^{1 to} R ⁴ and R ^{7 to} R ¹² each independently represent a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or 1 to 20 carbon atoms. It is an oxygen-containing group or a nitrogen-containing group having 1 to 20 carbons, R ⁵ is a hydrogen atom, a hydrocarbon group having 1 to 20 carbons, an oxygen-containing group having 1 to 20 carbons, a nitrogen containing 1 to 20 carbons The catalyst for olefin polymerization according to claim 2, which is a group, a substituted furan ring or a substituted thiophene ring. In the formula (1), all of R ^{1 to} R ⁴ are hydrogen atoms, R ⁵ and R ^{8 to} R ¹² are each independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and R ⁷ is The catalyst for olefin polymerization according to claim 3, which is a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group having 1 to 20 carbon atoms, or a nitrogen-containing group having 1 to 20 carbon atoms. In the formula (1), the olefin polymerization catalyst according to claim 4, wherein R ⁷ to R ¹⁰ are all hydrogen atoms.   Solid catalyst component formed from solid carrier (S), component (C) and component (A), solid carrier (S), component (C) and component (B) The catalyst for olefin polymerization according to any one of claims 1 to 5, comprising:   The olefin according to any one of claims 1 to 5, comprising a solid support (S), a component (A), a component (B) and a solid catalyst component formed from the component (C). Polymerization catalyst.   The olefin polymerization catalyst according to any one of claims 1 to 5, wherein the component (C) is an organoaluminum oxy compound and the solid support (S) is a porous oxide.   An ethylene is polymerized alone in the presence of the catalyst for olefin polymerization according to any one of claims 1 to 8, or ethylene and an olefin having 3 to 20 carbon atoms are copolymerized. Method for producing ethylene-based polymer. The ethylene polymer is a copolymer of ethylene and an α-olefin having 4 to 20 carbon atoms, and the following requirements (1) to (4) are satisfied: Process for producing ethylene-based polymer as described:
(1) The melt flow rate (MFR) at a load of 2.16 kg at 190 ° C. is 0.1 g / 10 min or more and 30 g / 10 min or less;
(2) The density is 875 kg / m ³ or more and 970 kg / m ³ or less;
(3) zero shear viscosity at 200 ° C. and [eta ₀ (P)], GPC-ratio (eta ₀ of viscosity detector method 6.8 square of weight average molecular weight determined by (GPC-VISCO) (Mw ^6.8) / Mw ^6.8 ) is not less than 0.03 × 10 ^{-30 and not} more than 7.5 × 10 ^-30 ;
(4) Intrinsic viscosity [[η] (dl / g)] measured in 135 ° C. decalin and weight-average molecular weight measured by GPC-viscosity detector method (GPC-VISCO): 0.776 (Mw ^0.776) Ratio ([η] / Mw ^0.776 ) is 0.90 × 10 ⁻⁴ or more and 1.65 × 10 ⁻⁴ or less.