JP7132059B2 - Olefin polymerization catalyst and method for producing ethylene polymer using said olefin polymerization catalyst - Google Patents

Description

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

It is well known that ethylene-based polymers obtained with Ziegler catalysts or 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 an ethylene polymer obtained using a Ziegler catalyst or a metallocene catalyst (for example, Patent Document 1), or a long chain branched type using a specific metallocene catalyst A method for producing an ethylene-based polymer has been disclosed (for example, Patent Document 2).

In addition, it has been reported that by using two specific crosslinked metallocene compounds, a large number of long chain branches are introduced, and an ethylene-based polymer with excellent moldability can be produced (for example, Patent Documents 3 and 4). Furthermore, production methods capable of reducing the occurrence of fouling and the like during polymerization, including such ethylene-based polymers, have also been disclosed (Patent Documents 5 to 7).

Patent Documents 8 to 11 also report on methods for producing long-chain branched ethylene-based polymers using two kinds of metallocene compounds.

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

The aforementioned Patent Documents 1 to 4 and 8 to 11 do not disclose problems such as occurrence of fouling during the polymerization reaction. Further, as a result of investigation by the present inventors, even with the techniques of Patent Documents 5 to 7, the solution after slurry polymerization becomes cloudy, and when the polymer concentration during polymerization is increased, fouling occurs, making it difficult to continue operation. A problem was found that it may become

As a result of further investigation by the present inventors, the reason for this is presumed to be that the amount of free polymer that precipitates in the solution after slurry polymerization increases, making the solution cloudy and causing fouling in the polymerization tank. reached.

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

As a result of intensive research in view of the above situation, the present inventors have found that by using two types of crosslinked metallocene compounds having a specific structure in the same polymerization system, there are many long chain branches, and molding processability and mechanical properties are improved. While maintaining the characteristics of giving an ethylene polymer having excellent physical strength, the amount of free polymer that precipitates in the solution after slurry polymerization is reduced, and it is possible to suppress fouling in the polymerization tank. Completed.

That is, the olefin polymerization catalyst of the present invention comprises the following component (A), the following component (B), the following component (C) and a solid carrier (S).
Component (A): 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 from 1 to 4 that satisfies the valence of M,
X is a hydrogen atom, a halogen atom, a hydrocarbon group, an anionic ligand, or a neutral ligand capable of coordinating with a lone pair; 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 derivative group; when n is 2 or more, a plurality of Xs may be the same or different. may be combined with each other to form a ring,
Q ¹ is a Group 14 transition atom of the periodic table,
R ¹ to R ⁴ and R ⁷ to R ¹² are each independently 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 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 at least one atom selected from nitrogen, oxygen and sulfur; A heterocyclic aromatic group which may have a substituent and has a five-membered ring as a base skeleton containing one,
R ⁶ is a saturated hydrocarbon group having a linear portion of 3 to 10 carbon atoms or a terminal unsaturated hydrocarbon group having a linear portion of 3 to 10 carbon atoms,
R ¹ and R ² and R ³ and R ⁴ may combine with each other to form an optionally substituted saturated ring,
R ² and R ³ and adjacent substituents of R ⁷ to R ¹⁰ may be bonded to each other to form a ring optionally having a substituent,
R ¹¹ and R ¹² may combine with each other to form a ring containing Q ¹ , and the ring may have a substituent. ]
Component (B): a 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,
each X is an atom or 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 a tin Two adjacent groups selected from the containing groups may combine to form a ring. ]
Component (C): an organometallic compound (c-1) represented by the following general formulas (3) to (5), an organoaluminum oxy compound (c-2), and components (A) and (B) at least one compound selected from the group consisting of compounds (c-3) that react to form an ion pair;
R ^a _m Al (OR ^b ) _n H _p X _q (3)
[In the 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 satisfying 0≤q<3, and m+n+p+q=3. ]
M ^a AlR ^a ₄ (4)
[In Formula (4), M ^a represents Li, Na or K, and R ^a represents a hydrocarbon group having 1 to 15 carbon atoms. ]
R ^a _r M ^b R ^b _s X _t (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 represents a halogen atom; , r is 0<r≦2, s is 0≦s≦1, t is 0≦t≦1, and r+s+t=2. ]

The method for producing an ethylene-based polymer of the present invention comprises polymerizing ethylene alone or copolymerizing ethylene with an olefin having 3 to 20 carbon atoms in the presence of the olefin polymerization catalyst of the present invention. 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) Melt flow rate (MFR) at 190° C. with a load of 2.16 kg is 0.1 g/10 min or more and 30 g/10 min or less;
(2) Density is 875 kg/m ³ or more and 970 kg/m ³ or less;
( ₃ ) The ratio ( ^η ₀ /Mw ^6.8 ) is 0.03×10 ⁻³⁰ or more and 7.5×10 ⁻³⁰ or less;
(4) Intrinsic viscosity [[η] (dl/g)] measured in decalin at 135°C and the weight average molecular weight measured by the GPC-viscosity detector method (GPC-VISCO) to the power of 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 olefin polymerization catalyst of the present invention, the amount of free polymer that precipitates in the solution after slurry polymerization is reduced, and fouling in the polymerization tank can be suppressed. And an ethylene polymer excellent in mechanical strength can be stably produced.

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

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

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

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. is.

In the above formula (1), n is an integer of 1 to 4 satisfying the valence of M, preferably 2.
In the above formula (1), X is a hydrogen atom, a halogen atom, a hydrocarbon group, an anion ligand, or a neutral ligand capable of coordinating with a lone electron pair; the anion ligand contains a halogen group, silicon-containing group, oxygen-containing group, sulfur-containing group, nitrogen-containing group, phosphorus-containing group, boron-containing group, aluminum-containing group or conjugated diene derivative group; , may be the same or different, and may be combined 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, more preferably a halogen atom or a hydrocarbon group having 1 to 10 carbon atoms.

The halogen atom includes fluorine, chlorine, bromine and iodine, with chlorine being particularly preferred.
Examples of the hydrocarbon group include
methyl group, ethyl group, 1-propyl group, 1-butyl group, 1-pentyl group, 1-hexyl group, 1-heptyl group, 1-octyl group, iso-propyl group, sec-butyl group (butane-2- yl 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), siamyl group (1,2-dimethylpropyl group), iso-hexyl group (4-methylpentyl group), 2,2-dimethylbutyl group, 2 ,3-dimethylbutyl group, 3,3-dimethylbutyl group, thexyl group (2,3-dimethylbut-2-yl group), linear or branched alkyl groups such as 4,4-dimethylpentyl 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) , but-1,3-dienyl group, pent-4-en-1-yl group, pent-3-en-1-yl group, pent-2-en-1-yl group, iso-pentenyl group (3- methylbut-3-en-1-yl group), 2-methylbut-3-en-1-yl group, pent-4-en-2-yl group, prenyl group (3-methylbut-2-en-1-yl a linear or branched alkenyl group or an unsaturated double bond-containing group such as
linear or branched alkynyl groups or unsaturated triple bond-containing groups such as ethynyl group, prop-2-yn-1-yl group, propargyl group (prop-1-yn-1-yl group);
benzyl group, 2-methylbenzyl group, 4-methylbenzyl group, 2,4,6-trimethylbenzyl group, 3,5-dimethylbenzyl group, cuminyl group (4-iso-propylbenzyl group), 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 a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cycloheptatrienyl group, a norbornyl group, a norbornenyl group, a 1-adamantyl group, and a 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), juryl group (2,3, 5,6-tetramethylphenyl group), 2,6-di-iso-propylphenyl group, 2,4,6-tri-iso-propylphenyl group, 4-tert-butylphenyl group, 3,5-di- Aromatic substituents such as tert-butylphenyl group, naphthyl group, biphenyl group, ter-phenyl group, binaphthyl group, acenaphthalenyl group, phenanthryl group, anthracenyl group, pyrenyl group and ferrocenyl group can be mentioned.

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

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. , a tetrafluorophenyl group, a pentafluorophenyl group, a trifluoromethylphenyl group, a bistrifluoromethylphenyl group, and a hexachloroantimonate anion.

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

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

Among the oxygen-containing groups, a methoxy group, an ethoxy group, an iso-propoxy group, and a tert-butoxy group are preferred.
Examples of the sulfur-containing group include a mesyl group (methanesulfonyl group), a phenylsulfonyl group, a tosyl group (p-toluenesulfonyl group), a triflyl group (trifluoromethanesulfonyl group), a nonafryl group (nonafluorobutanesulfonyl group), Mesylate group (methanesulfonate group), tosylate group (p-toluenesulfonate group), triflate group (trifluoromethanesulfonate group), nonaflate group (nonafluorobutanesulfonate group).

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

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

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 (each R independently represents a hydrogen atom, an alkyl group, an aryl group which may have a substituent, a halogen atom, or the like. shown.).
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 optionally substituted aryl group or represents a halogen atom, etc.).

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

Examples of neutral ligands capable of coordinating with a lone pair include ethers such as diethyl ether, tetrahydrofuran, dioxane, 1,2-dimethoxyethane, amines such as triethylamine and diethylamine, pyridine, picoline, lutidine, Heterocyclic compounds such as oxazoline, oxazole, thiazole, imidazole and thiophene, and organophosphorus compounds such as triphenylphosphine, tricyclohexylphosphine and tri-tert-butylphosphine are included.

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 the above 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, a nitrogen-containing group. or a sulfur-containing group, and 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 an optionally substituted heterocyclic aromatic group having a 5-membered ring as a base skeleton containing at least one atom selected from sulfur.

The hydrocarbon groups having 1 to 40 carbon atoms as R ¹ to R ⁵ and R ⁷ to R ¹² are preferably hydrocarbon groups having 1 to 20 carbon atoms (excluding aromatic hydrocarbon groups) or carbon It is an aromatic hydrocarbon group of numbers 6 to 40. The 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.

Examples of the hydrocarbon group having 1 to 40 carbon atoms include:
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), siamyl 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-dimethylbutyl group, 3,3 -dimethylbutyl group, thexyl group, 3-methylpentan-3-yl group, 3,3-dimethylbut-2-yl group, hexan-3-yl group, 2-methylpentan-3-yl group, heptane-4 -yl group, 2,4-dimethylpentan-2-yl group, 3-ethylpentan-3-yl group, 4,4-dimethylpentyl group, 4-methylheptan-4-yl group, 4-propylheptane-4 -yl group, 2,3,3-trimethylbutan-2-yl group, 2,4,4-trimethylpentan-2-yl group and other linear or branched alkyl groups having 1 to 40 carbon atoms ;
vinyl group, allyl group, propenyl group, iso-propenyl group, allenyl group, but-3-en-1-yl group, crotyl group, but-3-en-2-yl group, methallyl group, pent-4-ene -1-yl group, pent-3-en-1-yl group, pent-2-en-1-yl group, iso-pentenyl group, 2-methylbut-3-en-1-yl group, pent-4- en-2-yl group, prenyl group, 2-methyl-but-2-en-1-yl group, pent-3-en-2-yl group, 2-methyl-but-3-en-2-yl group , pent-1-en-3-yl group, penta-2,4-dien-1-yl group, pent-1,3-dien-1-yl group, penta-1,4-dien-3-yl group , iso-prenyl group (2-methyl-but-1,3-dien-1-yl group), penta-2,4-dien-2-yl group, hex-5-en-1-yl group, hexa- 4-en-1-yl group, hex-3-en-1-yl group, hex-2-en-1-yl group, 4-methyl-pent-4-en-1-yl group, 3-methyl- pent-4-en-1-yl group, 2-methyl-pent-4-en-1-yl group, hex-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-en-1-yl group, 2-methylpent-4-en-2-yl group, 3-ethylpenta -1-en-3-yl group, hex-3,5-dien-1-yl group, hex-2,4-dien-1-yl group, 4-methylpent-1,3-dien-1-yl group , 2,3-dimethyl-but-1,3-dien-1-yl group, hexa-1,3,5-trien-1-yl group, 2-(cyclopentadienyl)propan-2-yl group, A linear or branched alkenyl group or an unsaturated double bond-containing group having 2 to 40 carbon atoms such as a 2-(cyclopentadienyl)ethyl group;
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, pent-1-yn-1-yl group, pent-2-yn-1-yl group, pent-3-yn-1-yl group, pent-4-yn-1-yl group, 3-methyl-buta- 1-yn-1-yl group, pent-3-yn-2-yl group, 2-methyl-but-3-yn-1-yl group, pent-4-yn-2-yl group, hex-1- yn-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 -1-yl group, hex-4-yn-1-yl group, hex-5-yn-1-yl group, a linear or branched alkynyl group having 2 to 40 carbon atoms, or an unsaturated triple a 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-di -tert-butylphenyl)propan-2-yl group, 3-phenylpentan-3-yl group, 4-phenylhepta-1,6-dien-4-yl group, 1,2,3-triphenylpropane-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-phenylpropy group, cinnamyl group (3-phenylallyl group), neophyll 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-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 groups having 7 to 40 carbon atoms such as (1-azulenyl)ethyl groups and unsaturated double bond-containing groups;
cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclopentenyl group, cyclopentadienyl group, dimethylcyclopentadienyl group, n-butylcyclopentadienyl group, n-butyl-methylcyclopentadienyl group, tetramethylcyclo 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, cyclooctadienyl group, cyclooctatrienyl group, 1-methylcyclooctyl group, 1-allylcyclooctyl group, 1-benzylcyclooctyl group, 4-cyclohexyl-tert-butyl group, norbornyl group, norbornenyl group, norbornadienyl group, 2- methylbicyclo[2.2.1]heptan-2-yl group, 7-methylbicyclo[2.2.1]heptan-7-yl group, bicyclo[2.2.2]octan-1-yl 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, indacenyl group, tetrahydroindacenyl group, benzoindenyl group, azulenyl group, etc. having 3 to 40 carbon atoms cyclic saturated and unsaturated hydrocarbon groups of;
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 aromatic substituents having 6 to 40 carbon atoms.

Among the linear or branched alkyl groups having 1 to 40 carbon atoms, methyl group, ethyl group, 1-propyl group, 1-butyl group, 1-pentyl group, 1-hexyl group and 1-heptyl group, 1-octyl group, iso-propyl group, sec-butyl group (butan-2-yl group), tert-butyl group, iso-butyl group, iso-pentyl group, neopentyl group, tert-pentyl group, pentane- 3-yl group, iso-hexyl group, 1,1-dimethylbutyl group, 3,3-dimethylbutyl group, thexyl group, 3-methylpentan-3-yl group, heptane-4-yl group, 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. are preferred, methyl group, ethyl group, 1-propyl group, 1-butyl group, 1-pentyl group, 1-hexyl group, iso-propyl group, tert-butyl group, A neopentyl group, a 2,4-dimethylpentan-2-yl group, and a 2,4,4-trimethylpentan-2-yl group are more preferred.

Among the linear or branched alkenyl groups or unsaturated double bond-containing groups having 2 to 40 carbon atoms, vinyl group, allyl group, but-3-en-1-yl group, crotyl group, methallyl group, pent-4-en-1-yl group, prenyl group, pent-1,4-dien-3-yl group, hex-5-en-1-yl group, 2-methylpent-4-en-2- yl group, 2-(cyclopentadienyl)propan-2-yl group, 2-(cyclopentadienyl)ethyl group and the like are preferred, and vinyl group, allyl group, but-3-en-1-yl group, penta -4-en-1-yl group, prenyl group and hex-5-en-1-yl group are more preferred.

Among the linear or branched alkynyl groups or unsaturated triple bond-containing groups having 2 to 40 carbon atoms, ethynyl group, prop-2-yn-1-yl group, propargyl group, but-2-yne -1-yl group, but-3-yn-1-yl group, pent-3-yn-1-yl group, pent-4-yn-1-yl group, 3-methyl-but-1-yn-1 -yl group, 3,3-dimethyl-but-1-yn-1-yl group, hex-4-yn-1-yl group, hex-5-yn-1-yl group and the like are preferable, and prop-2- In-1-yl group, propargyl group, but-2-yn-1-yl group and but-3-yn-1-yl group are more preferred.

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

Among the cyclic saturated and unsaturated hydrocarbon groups having 3 to 40 carbon atoms, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclopentenyl group, cyclopentadienyl group, 1-methylcyclopentyl group, 1-allylcyclopentyl group, 1-benzylcyclopentyl group, cyclohexyl group, cyclohexenyl group, 1-methylcyclohexyl group, 1-allylcyclohexyl group, 1-benzylcyclohexyl group, cycloheptyl group, cycloheptenyl group, cycloheptatrienyl group, 1-methylcyclo heptyl group, 1-allylcycloheptyl group, 1-benzylcycloheptyl group, cyclooctyl group, cyclooctenyl group, cyclooctadienyl group, 4-cyclohexyl-tert-butyl group, norbornyl group, 2-methylbicyclo[2.2 .1]heptan-2-yl group, bicyclo[2.2.2]octan-1-yl group, 1-adamantyl group, 2-adamantyl group, pentalenyl group, indenyl group, fluorenyl group and the like are preferred, cyclopentyl group, A cyclopentenyl group, a 1-methylcyclopentyl group, a cyclohexyl group, a cyclohexenyl group, a 1-methylcyclohexyl group and a 1-adamantyl group are more preferred.

Among the 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 A phenyl group, a tolyl group, a xylyl group, a mesityl group, a cumenyl group, a 2,6-di-iso-propylphenyl group, a 2,4,6- tri-iso-propylphenyl group, 4-tert-butylphenyl group, 3,5-di-tert-butylphenyl group, allylphenyl group, 4-adamantylphenyl group, naphthyl group, biphenyl group, phenanthryl group, anthracenyl group more preferred.

Examples of the halogen-containing groups as R ¹ to R ⁵ and R ⁷ to R ¹² include fluoromethyl group, trifluoromethyl group, trichloromethyl group, pentafluoroethyl group and 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, bistrifluoromethoxyphenyl group, trifluoromethylthiophenyl group, bistrifluoromethylthiophenyl group, fluorobiphenyl group, difluorobiphenyl group, trifluorobiphenyl group, tetrafluorobiphenyl group, pentafluorobiphenyl group, di-tert-butyl- fluorobiphenyl group, trifluoromethylbiphenyl group, bistrifluoromethylbiphenyl group, trifluoromethoxybiphenyl group, bistrifluoromethoxybiphenyl group, trifluoromethyldimethylsilyl group, trifluoromethoxy group, pentafluoroethoxy group, fluorophenoxy group, difluoro phenoxy group, trifluorophenoxy group, pentafluorophenoxy group, di-tert-butyl-fluorophenoxy group, trifluoromethylphenoxy group, bistrifluoromethylphenoxy group, trifluoromethoxyphenoxy group, bistrifluoromethoxyphenoxy group, difluoromethylenedi oxyphenyl group, bistrifluoromethylphenyliminomethyl group, trifluoromethylthio group, and the like.

Among the halogen-containing groups, fluoromethyl group, trifluoromethyl group, pentafluoroethyl group, 2,2,2-trifluoroethyl group, 3,3,3-trifluoropropyl group, 4,4,4-trifluoromethyl group, fluorobutyl group, fluorophenyl group, difluorophenyl group, trifluorophenyl group, tetrafluorophenyl group, pentafluorophenyl group, trifluoromethylphenyl group, bistrifluoromethylphenyl group, trifluoromethoxyphenyl group, pentafluorobiphenyl group, A trifluoromethylbiphenyl group, a bistrifluoromethylbiphenyl group, a trifluoromethoxy group, a pentafluorophenoxy group, a bistrifluoromethylphenoxy group, a bistrifluoromethylphenoxy group, a difluoromethylenedioxyphenyl group and a trifluoromethylthio group are preferred, and trifluoro A methyl group, a fluorophenyl group, a pentafluorophenyl group, a trifluoromethylphenyl group, a bistrifluoromethylphenyl group, a pentafluorobiphenyl group, a trifluoromethoxy group, and a pentafluorophenoxy group are more preferred.

Examples of the silicon-containing groups as R ¹ to R ⁵ and R ⁷ to R ¹² include trimethylsilyl group, triethylsilyl group, tri-iso-propylsilyl group, diphenylmethylsilyl group, tert-butyldimethylsilyl group, tert-butyldimethylsilyl group, and tert-butyldimethylsilyl group. -butyldiphenylsilyl group, triphenylsilyl group, tris(trimethylsilyl)silyl group, cyclopentadienyldimethylsilyl group, di-n-butyl(cyclopentadienyl)silyl group, cyclopentadienyldiphenylsilyl group, indenyl dimethylsilyl group, di-n-butyl(indenyl)silyl group, indenyldiphenylsilyl group, fluorenyldimethylsilyl group, di-n-butyl(fluorenyl)silyl group, fluorenyldiphenylsilyl group, 4-trimethylsilylphenyl group, 4-triethylsilylphenyl group, 4-tri-iso-propylsilylphenyl group, 4-tert-butyldiphenylsilylphenyl group, 4-triphenylsilylphenyl group, 4-tris(trimethylsilyl)silylphenyl group, 3, 5-bis(trimethylsilyl)phenyl group and the like.

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

Examples of the oxygen-containing groups for R ¹ to R ⁵ and R ⁷ to R ¹² include methoxy, ethoxy, n-propoxy, iso-propoxy, allyloxy, n-butoxy and sec-butoxy groups. , iso-butoxy group, tert-butoxy group, methallyloxy group, prenyloxy group, benzyloxy group, methoxymethoxy group, methoxyethoxy group, phenoxy group, naphthoxy group, toluyloxy group, iso-propylphenoxy group, allylphenoxy group, tert-butylphenoxy group, methoxyphenoxy group, iso-propoxyphenoxy group, allyloxyphenoxy group, biphenyloxy group, binaphthyloxy group, methoxymethyl group, allyloxymethyl group, benzyloxymethyl group, phenoxymethyl group, methoxyethyl group , allyloxyethyl group, benzyloxyethyl group, phenoxyethyl group, methoxypropyl group, allyloxypropyl group, benzyloxypropyl group, phenoxypropyl group, methoxyvinyl group, allyloxyvinyl group, benzyloxyvinyl group, phenoxyvinyl group , methoxyallyl group, allyloxyallyl group, benzyloxyallyl group, phenoxyallyl group, dimethoxymethyl group, di-iso-propoxymethyl group, dioxolanyl group, tetramethyldioxolanyl group, dioxanyl group, methoxyphenyl group, iso- propoxyphenyl group, allyloxyphenyl group, phenoxyphenyl group, methylenedioxyphenyl group, 3,5-dimethyl-4-methoxyphenyl group, 3,5-di-tert-butyl-4-methoxyphenyl group, furyl group, methylfuryl, tetrahydrofuryl, pyranyl, tetrahydropyranyl, furfuryl, benzofuryl, dibenzofuryl and the like.

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

Examples of the nitrogen-containing groups for R ¹ to R ⁵ and R ⁷ to R ¹² include amino group, dimethylamino group, diethylamino group, allylamino group, diallylamino group, didecylamino group, benzylamino group and dibenzylamino group. , pyrrolidinyl group, piperidinyl group, morpholyl group, azepinyl group, dimethylaminomethyl group, dibenzylaminomethyl group, pyrrolidinylmethyl group, dimethylaminoethyl group, benzylaminomethyl group, benzylaminoethyl group, pyrrolidinylethyl group , dimethylaminovinyl group, benzylaminovinyl group, pyrrolidinylvinyl group, dimethylaminopropyl group, benzylaminopropyl group, pyrrolidinylpropyl group, dimethylaminoallyl group, benzylaminoallyl group, pyrrolidinylallyl group, amino phenyl group, dimethylaminophenyl group, 3,5-dimethyl-4-dimethylaminophenyl group, 3,5-di-iso-propyl-4-dimethylaminophenyl group, julolidinyl group, tetramethyljulolidinyl group, pyrrolidinyl lphenyl 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-butylcarba zolyl group, imidazolyl group, dimethylimidazolidinyl group, benzimidazolyl group, oxazolyl group, oxazolidinyl group, benzoxazolyl group and the like.

Among the nitrogen-containing groups, amino group, dimethylamino group, diethylamino group, allylamino group, benzylamino group, dibenzylamino group, pyrrolidinyl group, piperidinyl group, morpholyl group, dimethylaminomethyl group, benzylaminomethyl group, pyrrolidinyl methyl group, dimethylaminoethyl group, pyrrolidinylethyl group, dimethylaminopropyl group, pyrrolidinylpropyl group, dimethylaminoallyl group, pyrrolidinylallyl group, aminophenyl group, dimethylaminophenyl group, 3,5- dimethyl-4-dimethylaminophenyl group, 3,5-di-iso-propyl-4-dimethylaminophenyl group, julolidinyl group, tetramethyljulolidinyl group, pyrrolidinylphenyl group, pyrrolylphenyl group, carbazolyl phenyl group, di-tert-butylcarbazolylphenyl group, pyrrolyl group, pyridyl group, quinolyl group, tetrahydroquinolyl group, iso-quinolyl group, tetrahydro-iso-quinolyl group, indolyl group, indolinyl group, carbazolyl group, di -tert-butylcarbazolyl group, imidazolyl group, dimethylimidazolidinyl group, benzimidazolyl group, oxazolyl group, oxazolidinyl group, benzoxazolyl group, etc. are preferred, amino group, dimethylamino group, diethylamino group, pyrrolidinyl group, dimethylaminophenyl group, 3,5-dimethyl-4-dimethylaminophenyl group, 3,5-di-iso-propyl-4-dimethylaminophenyl group, julolidinyl group, tetramethyljulolidinyl group, pyrrolidinyl Phenyl group, pyrrolyl group, pyridyl group, carbazolyl group and imidazolyl group are more preferred.

Examples of sulfur-containing groups for R ¹ to R ⁵ and R ⁷ to R ¹² include methylthio, ethylthio, benzylthio, phenylthio, naphthylthio, methylthiomethyl, benzylthiomethyl and phenylthiomethyl groups. , naphthylthiomethyl group, methylthioethyl group, benzylthioethyl group, phenylthioethyl group, naphthylthioethyl group, methylthiovinyl group, benzylthiovinyl group, phenylthiovinyl group, naphthylthiovinyl group, methylthiopropyl group, benzylthio propyl, phenylthiopropyl, naphthylthiopropyl, methylthioallyl, benzylthioallyl, phenylthioallyl, naphthylthioallyl, mercaptophenyl, methylthiophenyl, thienylphenyl, methylthienylphenyl, benzo thienylphenyl group, dibenzothienylphenyl group, benzodithienylphenyl group, thienyl group, tetrahydrothienyl group, methylthienyl group, thienofuryl group, thienotienyl group, benzothienyl group, dibenzothienyl group, thienobenzofuryl group, benzodithienyl group, A dithiolanyl group, a dithianyl group, an oxathiolanyl group, an oxathianyl group, a thiazolyl group, a benzothiazolyl group, a thiazolidinyl group and the like can be mentioned.

Among the above sulfur-containing groups, thienyl, methylthienyl, thienofuryl, thienotienyl, benzothienyl, dibenzothienyl, thienobenzofuryl, benzodithienyl, thiazolyl, and benzothiazolyl groups are preferred.

An optionally substituted heterocyclic aromatic 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 the options for R ⁵ Examples of the group include groups represented by the following general formulas [5a] to [5h].

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 each R ^d is independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, which may be the same or different. good. The wavy lines in the formulas [5a] to [5h] indicate the bonding sites with the benzene ring.

Examples of the hydrocarbon group having 1 to 20 carbon atoms include 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. is 1 to 20, preferably 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, 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-adamantyl 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, 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, cyclopentyl 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 an optionally substituted 5- to 8-membered saturated or unsaturated hydrocarbon group in which adjacent R ^d' s are bonded to each other and independently condensed to form a heterocyclic 5-membered ring moiety. is not particularly limited as long as the effect of the present invention is exhibited, but is preferably a 5- or 6-membered ring. thiophene ring, indole ring, carbazole ring, benzoxazole ring, benzothiazole ring, benzimidazole ring, benzopyrazole ring and the like.

Among the heterocyclic aromatic groups represented by the above formulas [5a] to [5h], the heterocyclic aromatic groups represented by the above formula [5a] are preferred.
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 preferred.

In the above formula (1), R ¹ and R ² and R ³ and R ⁴ may combine with 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 optionally having a substituent group condensed to the cyclopentadienyl ring portion. In addition, when a plurality of rings are present, they may be the same or different. Although it is not particularly limited as long as the effect of the present invention is exhibited, it is preferably a 6- or 7-membered ring. Examples include an octahydrofluorene ring and a substituted tetrahydroazulene ring, preferably a substituted tetrahydro-1-indene ring.

In the above formula (1), the adjacent substituents of R ² and R ³ may combine with 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 optionally having a substituent group condensed to the cyclopentadienyl ring portion. In addition, when a plurality of rings are present, they may be the same or different. Although it is not particularly limited as long as the effect of the present invention is exhibited, it is preferably a 6- or 7-membered ring. A 2-indene ring is included, preferably a substituted 2-indene ring.

In the above formula (1), adjacent substituents of R ⁷ to R ¹⁰ may be combined 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 group condensed to the aromatic ring portion. In addition, when a plurality of rings exist, they may be the same or different. Although it is not particularly limited as long as the effect of the present invention is exhibited, it is preferably a 5- or 6-membered ring. , substituted tetrahydroindacene ring and substituted cyclopentatetrahydronaphthalene, preferably substituted benzoindenyl ring and substituted tetrahydroindacene ring.

In formula (1) above, R ¹¹ and R ¹² may combine with each other to form a ring containing Q ¹ , and these rings may have a substituent. The ring formed in this case preferably forms an optionally substituted 3- to 8-membered saturated or unsaturated ring. Although it is not particularly limited as long as the effects of the present invention are exhibited, it is preferably ^a 4- to 6-membered ring. cyclobutane (silentane) ring, substituted silacyclopentane (silolane) ring, substituted silacyclohexane (silinane) and substituted silafluorene ring, preferably substituted cyclopentane ring, substituted silacyclobutane ring and substituted silacyclopentane ring .

In the above formula (1), R ⁶ is a saturated hydrocarbon group having a linear portion of 3 to 10 carbon atoms or a terminal unsaturated hydrocarbon group having a linear portion of 3 to 10 carbon atoms.
Examples of the saturated hydrocarbon group having 3 to 10 carbon atoms in the linear portion include n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group and n-octyl. group, n-nonyl group, n-decyl group, sec-butyl group, tert-pentyl group, 2-methylpentan-2-yl group, 1-ethylcyclopentyl group, 1-(n-propyl)cyclopentyl group, 1- Ethylcyclohexyl group, 1-(n-propyl)cyclohexyl group and the like, preferably n-propyl group, n-butyl group, n-pentyl group and n-hexyl group.

Examples of the terminal unsaturated hydrocarbon group having 3 to 10 carbon atoms in the linear portion include allyl group, but-3-en-1-yl group, methallyl group, crotyl group, pent-4-ene- 1-yl group, prenyl group, hex-5-en-1-yl group, hept-6-en-1-yl group, octa-7-en-1-yl group, non-8-en-1-yl group, dec-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 , 1-vinylcyclohexyl group, 1-allylcyclohexyl group and the like, allyl group, but-3-en-1-yl group, pent-4-en-1-yl group, hex-5-en-1- It is preferably an yl group.

In a preferred embodiment of the transition metal compound (1), Q ¹ is a silicon atom, R ¹ to R ⁴ and R ⁷ to R ¹² are each independently 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, wherein 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, 1 to 20 nitrogen-containing groups, substituted furan rings or substituted thiophene rings (1-a),
As a more preferred embodiment, in the above embodiment (1-a), R ¹ to R ⁴ are all hydrogen atoms, and R ⁵ and R ⁸ to R ¹² are each independently a hydrogen atom or a carbon atom having 1 to 10 carbon atoms. Embodiment (1-b) in which it 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. be
A more preferred embodiment is the embodiment (1-c) in which all of R ⁷ to R ¹⁰ are hydrogen atoms in the above embodiment (1-b).

Specific examples of the transition metal compound (1) are shown below, but the scope of the present invention is not particularly limited by these.
For convenience, the ligand structure of transition metal compound (1) excluding MXn (metal moiety) is replaced with cyclopentadienyl ring moieties, indenyl ring moieties, and cyclopentadienyl ring moieties R ¹ , R ² , R ³ and R ⁴ . Groups and indenyl ring moieties ^R5 substituents, indenyl ring moieties ^R6 substituents, indenyl ring moieties ^R7 and ^R10 substituents, ^indenyl ring moieties R8 and ^R9 substituents, bridging moieties. The abbreviation for the cyclopentadienyl ring portion is α, the abbreviation for the indenyl ring portion is β, the abbreviation for the cyclopentadienyl ring portion R ¹ , R ² , R ³ , R ⁴ substituents and the indenyl ring portion R ⁵ substituent is γ. , the abbreviation for the R6 substituent in the indenyl ring portion is δ, the abbreviation for the ^R7 and ^R10 substituents ⁱⁿ the ^indenyl ring portion is ε, the abbreviation for the R8 and ^R9 substituents in the indenyl ring portion is ζ, and the abbreviation for the structure of the bridging portion is η, and the abbreviations of each substituent are 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。

The wavy lines in [Table 1] to [Table 2] indicate the bonding sites with the crosslinked portions.

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 [Table 3] may be the same or different in 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 [Table 5] may be the same or different in 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 [Table 6] may be the same or different in combination.

Specific examples of the metal portion 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(OMe) ₂ , Ti(OiPr) ₂ , Ti(NMe2) ₂ , Ti(OMs) ₂ , Ti(OTs) ₂ , Ti ₍ OTf) ₂ , _ZrF2 , _ZrCl2 , _ZrBr2 , 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(OMe) ₂ , Zr(OiPr) ₂ , Zr( NMe2) ₂ , Zr(OMs) ₂ , Zr(OTs) ₂ , Zr(OTf) ₂ , _HfF2 , _HfCl2 , _HfBr2 , _{HfI2, 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( _CH2 -Si(Me) ₃ ) ₂ , Hf(OMe) ₂ , Hf(OiPr) ₂ , Hf(NMe2) ₂ , Hf( _OMs ) ₂ , Hf(OTs) ₂ , Hf( OTf) ₂ and the like. Me is a methyl group, Bn is a benzyl group, tBu is a tert-butyl group, Si(Me) ₃ is a trimethylsilyl group, OMe is a methoxy group, OiPr is an iso-propoxy group, _NMe2 is a dimethylamino group, and OMs is methanesulfonate. OTs is the p-toluenesulfonate group and OTf is the trifluoromethanesulfonate group.

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

Further, the cyclopentadienyl ring moiety is α-2 in [Table 1], the indenyl ring moiety is β-2 in [Table 2], and the cyclopentadienyl ring moiety R ³ and R ⁴ substituents are both [ γ-1 in Table 3], the indenyl ring moiety R ⁵ substituent is γ-1 in [Table 3], the indenyl ring moiety R ⁶ substituent is δ-18 in [Table 4], the bridging moiety is 7], and when the metal moiety MXn is Zr(NMe ₂ ) ₂ , the following compound [7] is exemplified.

Further, 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 both [ γ-1 in Table 3], the indenyl ring moiety R ⁵ substituent is γ-2 in [Table 3], the indenyl ring moiety R ⁶ substituent is δ-1 in [Table 4], the indenyl ring moiety R ⁷ and R ¹⁰ substituents are both ε-2 in [Table 5], indenyl ring moieties R ⁸ and R ⁹ substituents are both ζ-1 in [Table 6], and the bridging moiety is ε-1 in [Table 7] When it is composed of a combination of η-31 and the metal moiety MXn is HfMe ₂ , the following compound [8] is exemplified.

Further, 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 both [ γ-1 in Table 3], the indenyl ring moiety R ⁵ substituent is γ-5 in [Table 3], the indenyl ring moiety R ⁶ substituent is δ-2 in [Table 4], the indenyl ring moiety R ⁷ and R ¹⁰ substituents are both ε-1 in [Table 5], the bridging portion is a combination of η-29 in [Table 7], and the metal moiety MXn is Ti (1,3-pentadienyl) , 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 typical synthesis routes are shown below, but the production method is not particularly limited.

A substituted cyclopentadiene compound as a starting material can be produced by a known method, and the production method is not particularly limited. 1989, 30, 3513.", "J. Org. Chem. 1990, 55, 3395.", "Inorg. Chem. 1991, 30, 853." Chem. 1999, 577, 211.”, “J. Organomet. Chem. 1999, 590, 169.” Chem. 2003, 677, 133.", "J. Organomet. Chem. 2005, 690, 952.", "Org. Lett. 2008, 10, 2545."

The starting substituted indene compound can be produced by a known method, and the production method is not particularly limited. As known production methods, for example, "Organometallics 1994, 13, 954.", "Eur. J. Org. Chem. 2005, 1058.", "Organometallics 2006, 25, 1217." "Bioorg. Med. Chem. 2008, 16, 7399.", WO2009/080216, "Organometallics 2011, 30, 5744." Chem. Eur. J. 2012, 18, 4174.”, JP 2012-012307, JP 2012-121882, JP 2014-196319, JP 2014-513735, JP 2015- 063495, JP 2016-501952, and the like.

Among the substituted indene compounds described above, the substituted indene compound in which a branched alkyl substituent is introduced at the 1- or 3-position can be produced, for example, by a known method as represented by the following reaction formula [1]. is not limited. Examples of known production methods include "J. Organomet. Chem. 2002, 650, 114." and "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 above reaction formula [1], base is a basic substance capable of producing an indenyl anion, such as sodium hydride, n-butyllithium, organometallic compounds 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 alkyl lithium reagent, an aromatic lithium reagent, an alkyl Grignard reagent, or 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 organometallic compound. It may be used for synthesizing a precursor compound (ligand) of compound (1).

Of the above-described substituted indene compounds, those unsubstituted at the 2-position can be brominated at the 2-position by a known method such as that 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 its monohydrate. An indene compound has 5-membered ring partial double bond positional isomers, and a mixture of these isomers may be used. Examples of known production methods include JP-A-2012-121882 and JP-A-2015-063495, as well as JP-A-2014-111568.

The 2-brominated indene compound and the 4-brominated indene compound are subjected to the corresponding coupling by a known method such as Suzuki-Miyaura coupling reaction with a palladium catalyst, as shown in the following reaction formula [3]. The product can be manufactured, and the manufacturing 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。

As mentioned above, there are 5-membered ring partial double bond positional isomers of indene compounds, and mixtures of these isomers may also be used.

Instead of the boronic acid, other boron compounds such as various boronic esters and boroxines may be used, and the reaction mixture of the halogenated compound and the metal reagent and then the boron compound may be used without isolation and purification, A nickel or iron catalyst may be used instead of the palladium catalyst. Examples of known production methods include those disclosed in JP-A-2014-196274 in addition to those described above.

Also, instead of Suzuki-Miyaura coupling with boron compounds, Negishi coupling with organozinc reagents, Mizoroki-Heck reaction with alkene compounds, Hiyama coupling with organosilicon compounds, Sonogashira-Hagiwara coupling with terminal alkyne compounds, Migita-Kosugi-Stille coupling with organotin compounds, Kumada-Tamao-Corriu coupling with organomagnesium compounds, Buchwald-Hartwig coupling, Goldberg amination reaction or Ullmann ether synthesis reactions may also be used. Examples of known production methods include those disclosed in JP-A-8-183814, JP-A-2005-529865, JP-A-2006-509046, and the like, in addition to those described above.

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

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 the reaction formula [4], Ar represents an aromatic substituent, and a mixture of 5-membered ring partial double bond positional isomers of the indene compound may be used. Known production methods include, for example, 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 produced by the above-described methods and the like. When Q ¹ is a silicon atom, a germanium atom or a tin atom, it can be produced by, for example, the method shown in the following reaction formula [5], and the production method is not particularly limited.

In the reaction formula [5], in the precursor compound (ligand) synthesis, the organolithium reagent prepared from the substituted cyclopentadienyl compound and the organolithium reagent prepared from the substituted indene compound are Q It is preferred to react with chlorides containing ¹ , in any order. After the reaction with the organometallic reagent in the first step, the by-product inorganic compound may be removed under an inert atmosphere, and the reaction product is isolated by distillation, crystallization or washing before use. good too. During the reaction with the organometallic reagent in the second stage, DMI (1,3-dimethyl-2-imidazolidinone), DMPU (N,N'-dimethylpropylene urea) or HMPA (hexamethylphosphoric acid triamide), etc. , preferably 0.1 to 5.0 equivalents, more preferably 1.0 equivalents of DMI, relative to the organometallic reagent. The substituted cyclopentadienyl compound, the substituted indene compound and the precursor compound (ligand) include 5-membered ring partial double bond positional isomers, and a mixture of these isomers may be used. Further, when the substituted cyclopentadienyl compound is the 2-brominated 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 shown above, "Macromolecules 1995, 28, 3771.", JP-A-11-315089, JP-A-2001-302687, JP-A-2001-220404, "Polymer Papers 2002, 59, 243.", JP-A-2003-522194, "Macromolecules 2004, 37, 2342." -320935, JP-A-2011-126813, and the like.

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 Reaction Formula [6] above, base is a basic substance capable of producing a cyclopentadienyl anion, and examples thereof include those shown in Reaction Formula [1] above, but are not particularly limited. A fulvene compound can be synthesized by a known method from a substituted cyclopentadienyl compound and a carbonyl compound in the presence of a basic substance. It is possible to manufacture The substituted cyclopentadienyl compound, the substituted indene compound and the precursor compound (ligand) include 5-membered ring partial double bond positional isomers, and a mixture of these isomers may be used. Further, when the substituted cyclopentadienyl compound is the 2-brominated indene compound, it can be produced, for example, by the method shown in the following reaction formula [7], and the production method is not particularly limited. do not have.

In the above reaction formula [7], base is a basic substance capable of producing an indenyl anion, examples of which include those shown in the above reaction formula [1], but are not particularly limited. A fulvene compound can be synthesized by a known method from a substituted 1-indene compound and a carbonyl compound in the presence of a basic substance. ) can be manufactured. The substituted indene compound and the precursor compound (ligand) include 5-membered ring partial double bond positional isomers, and a mixture of these isomers may be used.

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

Further, in the transition metal compound (1) of the present invention, the cyclopentadienyl ring portion that bonds to the central metal across the bridging portion has two planes (front side and back side). Therefore, when the cyclopentadienyl ring portion does not have a plane of symmetry, there are two structural isomers represented by the following general formula [10a] or [10b].

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, even when the substituents R ¹¹ and R ¹² of the crosslinked portion are not the same, there are two types of structural isomers represented by the following general formulas [11a] and [11b].

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

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

<Component (B)>
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 Group 4 transition metal atom in the periodic table, specifically 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; is an atom or group selected from, preferably a halogen atom or a hydrocarbon group. Specific examples of the halogen atom, hydrocarbon group, halogen-containing hydrocarbon group, silicon-containing group, oxygen-containing group, sulfur-containing group, nitrogen-containing group and phosphorus-containing group are the same as those exemplified in formula (1) above. are listed.

Q ² is a divalent group that bonds 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; , 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 an alkylene group, a substituted alkylene group and an alkylidene group having 1 to 1 carbon atoms. 10 hydrocarbon groups.

Examples of the hydrocarbon group having 1 to 20 carbon atoms (divalent hydrocarbon group having 1 to 20 carbon atoms) include alkylene groups such as methylene, ethylene, propylene and butylene; isopropylidene, dimethylmethylene, diethylmethylene and 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; cyclopropylidene, cyclobutylidene, cyclopentylidene, cyclohexylidene, cycloheptylidene, bicyclo [3.3.1] cycloalkylene groups such as nonylidene, norbornylidene, adamantylidene, tetrahydronaphthylidene and dihydroindanilidene; and alkylidene groups such as ethylidene, propylidene and butylidene.

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

Examples of the germanium-containing group (divalent germanium-containing group) or the tin-containing group (tin-containing group) include groups in which silicon is converted to germanium or tin in the above silicon-containing group.

As the halogen-containing group (divalent halogen-containing group), one or more of the hydrogen atoms in the alkylene group, substituted alkylene group, cycloalkylene group, alkylidene group or silicon-containing group is substituted with a suitable halogen atom. groups (halogen-containing silicon-containing groups) such as bis(trifluoromethyl)methylene, 4,4,4-trifluorobutylmethylmethylene, bis(trifluoromethyl)silylene, 4,4,4-trifluoromethyl A fluorobutylmethylsilylene group and the like can be mentioned.

R ¹³ to R ²⁴ are monovalent atoms or groups, each independently hydrogen atom, hydrocarbon group, halogen-containing group, oxygen-containing group, nitrogen-containing group, boron-containing group, sulfur-containing group, phosphorus-containing group, Two adjacent groups selected from silicon-containing groups, germanium-containing groups and tin-containing groups may be linked to form a ring. Specific examples of the hydrocarbon group, halogen-containing group, oxygen-containing group, nitrogen-containing group, boron-containing group, sulfur-containing group, phosphorus-containing group, and silicon-containing group are the same as those exemplified in formula (1) above. things are mentioned. Further, examples of the germanium-containing group and the tin-containing group include groups obtained by converting silicon to germanium or tin in the silicon-containing group.

Specific examples of the transition metal compound (2) include isopropylidene(cyclopentadienyl)(fluorenyl)zirconium dichloride and isopropylidene(cyclopentadienyl)(2,7-di-t-butyl-9-fluorenyl). zirconium dichloride, isopropylidene(cyclopentadienyl)(3,6-di-t-butylfluorenyl)zirconium dichloride, isopropylidene(cyclopentadienyl)(octamethyloctahydride dibenzfluorenyl)zirconium dichloride, dibutylmethylene(cyclopentadienyl)(fluorenyl)zirconium dichloride, dibutylmethylene(cyclopentadienyl)(2,7-di-t-butylfluorenyl)zirconium dichloride, dibutylmethylene(cyclopentadienyl) (3, 6-di-t-butylfluorenyl)zirconium dichloride, dibutylmethylene(cyclopentadienyl)(octamethyloctahydride dibenzfluorenyl)zirconium dichloride, cyclohexylidene(cyclopentadienyl)(fluorenyl)zirconium dichloride , cyclohexylidene(cyclopentadienyl)(2,7-di-t-butylfluorenyl)zirconium dichloride, cyclohexylidene(cyclopentadienyl)(3,6-di-t-butylfluorenyl) Zirconium dichloride, cyclohexylidene (cyclopentadienyl) (octamethyloctahydrido dibenzfluorenyl) zirconium dichloride, dimethylsilyl (cyclopentadienyl) (fluorenyl) zirconium dichloride, dimethylsilyl (cyclopentadienyl) (2 ,7-di-t-butylfluorenyl)zirconium dichloride, dimethylsilyl(cyclopentadienyl)(3,6-di-t-butylfluorenyl)zirconium dichloride and dimethylsilyl(cyclopentadienyl)(octa methyloctahydridodibenzfluorenyl)zirconium dichloride, and more preferred specific examples include isopropylidene(cyclopentadienyl)(2,7-di-t-butyl-9-fluorenyl)zirconium dichloride. However, it is not limited to these.

The transition metal compound (2) and its production method are not particularly limited as long as the effects of the present invention are achieved, and specific examples thereof include those exemplified in JP-A-2006-233208.

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

<Component (C)>
Component (C) is an organometallic compound (c-1) represented by the following general formulas (3) to (5), an organoaluminum oxy compound (c-2), and component (A) and component (B). is at least one compound selected from the group consisting of compounds (c-3) that form an ion pair by reacting with
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 0≤q<3, and m+n+p+q=3.
M ^a AlR ^a ₄ (4)
In formula (4), M ^a represents Li, Na or K, and R ^a represents a hydrocarbon group having 1 to 15 carbon atoms.
R ^a _r M ^b R ^b _s X _t (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, X represents a halogen atom, r is 0<r≦2, s is 0≦s≦1, t is 0≦t≦1, and r+s+t=2.

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

Examples of the formula (4) include lithium aluminum hydride, and examples of the formula (5) include dialkylzinc compounds described in JP-A-2003-171412. It can also be used in combination with a compound or the like.

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

As the compound (c-3) that forms an ion pair by reacting with the component (A) and the component (B), JP-A-1-501950, JP-A-1-502036, JP-A-3-179005 Publications, JP-A-3-179006, JP-A-3-207703, JP-A-3-207704 and US5321106 Lewis acids, ionic compounds, borane compounds and carborane compounds, and further heteropoly compounds and isopoly compounds can be used.

In the olefin polymerization catalyst according to the present invention, when an organoaluminumoxy compound such as methylaluminoxane is used as a cocatalyst component, not only does it exhibit extremely high polymerization activity for olefin compounds, but it also reacts with active hydrogen in the solid support. The component (C) preferably contains at least the organoaluminum oxy compound (c-2), since the solid carrier component containing the co-catalyst component can be easily prepared by reaction.

<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 inorganic compounds 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 , or compounds or mixtures containing these, specifically includes natural or synthetic zeolites such as SiO2-MgO, _SiO2 - _Al2O3 , _SiO2 - _TiO2 , _{SiO2 - V2O5 , SiO2 - Cr2O3} and _{SiO2 - TiO2} -MgO. is used. Among these, those containing SiO ₂ as a main component are preferred.

The above porous oxides may contain a small amount of _Na2CO3 , _K2CO3 , _CaCO3 , _MgCO3 , _Na2SO4 , Al2 _{( SO4} ) _{3 , BaSO4 , KNO3} , Mg ₍ NO ₃ ) Carbonates such as ₂ , Al(NO ₃ ) ₃ , Na ₂ O, K ₂ O and Li ₂ O, sulfates, nitrates and oxide components may be contained.

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

Examples of the solid aluminoxane compound include an aluminoxane having a structure represented by the following general formula (Sa), an aluminoxane having a structure represented by the following general formula (Sb), and a general formula (Sc) below. and a repeating unit represented by the following general formula (Sd) as a structure.

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

In the above formulas (Sa) and (Sb), r represents an integer of 2-500, preferably 6-300, particularly preferably 10-100. In formulas (Sc) and (Sd), s and t each represent an integer of 1 or more. r, s and t are selected such that the aluminoxane remains substantially solid under the reaction environment employed.

The solid aluminoxane compound, unlike conventionally known carriers for olefin polymerization catalysts, does not contain inorganic solid components such as silica and alumina, and organic polymer components such as polyethylene and polystyrene. It has become. By "solid state" is meant that the aluminoxane component remains substantially solid under the reaction environment in which it is used. More specifically, when preparing an olefin polymerization catalyst (e.g., an ethylene polymerization catalyst) by contacting the transition metal compound [A] with an aluminoxane component as described later, and the prepared olefin polymerization catalyst is to maintain the aluminoxane component in a substantially solid state during the polymerization (for example, suspension polymerization) of olefin (eg, ethylene) using .

Visual confirmation is the simplest method for determining whether the aluminoxane component is in a solid state or not. However, visual confirmation is often difficult, for example, during polymerization. In that case, it is possible to determine, for example, from the properties of the polymer powder obtained after polymerization, the state of adhesion to the reactor, and the like. Conversely, if the polymer powder has good properties and little adhesion to the reactor, even if some of the aluminoxane component is eluted under the polymerization environment, it does not depart from the gist of the present invention. Indices for judging the properties of the polymer powder include bulk density, particle shape, surface shape, and the degree of presence of amorphous polymer. Polymer bulk density is preferable from the viewpoint of quantification. The bulk density is generally 0.01 to 0.9, preferably 0.05 to 0.6, more preferably 0.1 to 0.5.

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

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

As the solid aluminoxane compound, known solid aluminoxane can be used without limitation, and for example, the solid polyaluminoxane composition described in International Publication No. 2014/123212 can also be used. Known production methods include, for example, JP-B-7-42301, JP-A-6-220126, JP-A-6-220128, JP-A-11-140113, JP-A-11-310607, Examples include the production methods described in JP-A-2000-38410, JP-A-2000-95810, and International Publication No. 2010/55652.

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

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

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

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

Clay is usually composed mainly of clay minerals. An ion-exchangeable layered compound is a compound having a crystal structure in which planes formed by ionic bonds or the like are stacked in parallel with weak bonding force, and the ions contained therein 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.

Clays, clay minerals, and ionic crystalline compounds having a layered crystal structure such as hexagonal close-packing type, antimony type, _CdCl2 type, _CdI2 type, etc. are used as clays, clay minerals, or ion-exchangeable layered compounds. can be exemplified.

Such clays and clay minerals include kaolin, bentonite, kibushi clay, gyrome clay, allophane, hisingerite, pyrophyllite, ummo group, montmorillonite group, vermiculite, ryokudite group, palygorskite, kaolinite, nacrite, and dickite. _{and halloysite . _ _ _ _ _} α-Ti(HPO4) ₂ , α _- Ti( _HAsO4 ) _2.H2O , α _- Sn(HPO4) _2.H2O , γ _- Zr ₍ HPO4) ₂ , γ _- Ti ₍ HPO4 ) ₂ and crystalline acid salts of polyvalent metals such as γ-Ti(NH ₄ PO ₄ ) ₂ ·H ₂ O and the like.

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

Clays and clay minerals are also preferably chemically treated. Any chemical treatment can be used, such as surface treatment for removing impurities adhering to the surface, treatment for affecting the crystal structure of clay, and the like. Specific examples of chemical treatment include acid treatment, alkali treatment, salt treatment, organic substance treatment, and the like. The acid treatment removes surface impurities and also elutes cations such as Al, Fe and Mg in the crystal structure to increase the surface area. Alkaline treatment destroys the crystalline structure of the clay, resulting in changes in the clay structure. Also, in salt treatment and organic matter treatment, ionic complexes, molecular complexes, organic derivatives, etc. are formed, and the surface area and interlayer distance can be changed.

The ion-exchangeable layered compound may be a layered compound in which the interlayer spacing is expanded by exchanging the exchangeable ions between the layers with other large bulky ions by utilizing the ion-exchangeability. Such bulky ions play a pillar-like role supporting the layered structure and are usually called pillars. Also, the introduction of another substance between the layers of a layered compound is called intercalation. Guest compounds for intercalation include cationic inorganic compounds such as TiCl ₄ and ZrCl ₄ , metal alkoxides such as Ti(OR) ₄ , Zr(OR) ₄ , PO(OR) ₃ and B(OR) ₃ ( R is a hydrocarbon group, etc.), metal hydroxide ions such as [Al ₁₃ O ₄ (OH) ₂₄ ] ⁷⁺ , [Zr ₄ (OH) ₁₄ ] ²⁺ , [Fe ₃ O(OCOCH ₃ ) ₆ ] ⁺ etc. These compounds are used alone or in combination of two or more. Polymerization obtained by hydrolyzing metal alkoxides (R is a hydrocarbon group, etc.) such as Si(OR) ₄ , Al(OR) ₃ and Ge(OR) ₄ when intercalating these compounds. Colloidal inorganic compounds such as SiO ₂ and the like can coexist. Examples of pillars include oxides produced by intercalating the above metal hydroxide ions between layers and then dehydrating them by heating.

Clays, clay minerals, and ion-exchangeable layered compounds may be used as they are, or may be used after being subjected to treatments such as ball milling and sieving. Alternatively, water may be newly added and adsorbed, or may be used after heat dehydration treatment. Furthermore, it may be used alone or in combination of two or more.

Examples of the organic compound used as the solid carrier (S) include granular or particulate solids having a particle size in the range of 10 to 300 μm. Specific examples of the organic compound include polymers produced mainly from olefins having 2 to 14 carbon atoms such as ethylene, propylene, 1-butene, and 4-methyl-1-pentene, or vinylcyclohexane, Granular or particulate solids composed of polymers and reactants mainly composed of styrene and divinylbenzene, and modified products thereof can be mentioned.
As the solid carrier (S), a porous oxide is preferable from the viewpoint of foreign matter prevention during molding.

<Method for preparing olefin polymerization catalyst>
In the olefin polymerization catalyst according to the present invention, component (A), component (B), component (C) and solid support (S) are added to an inert hydrocarbon or to a polymerization system using an inert hydrocarbon. A preferred embodiment is the solid catalyst component (X) prepared by

Examples of the solid catalyst component (X) include the solid catalyst component (XA) formed from the solid support (S), the component (C) and the component (A), the solid support (S), the component ( C) and a solid catalyst component (XB) formed from component (B); and a solid support (S), component (A), component (B) and component (C). and an olefin polymerization catalyst comprising a solid catalyst component (XC) formed from Among these, an olefin polymerization catalyst comprising a solid catalyst component (XC) is more preferred.

The order of contacting each component is arbitrary, but preferred methods for preparing an olefin polymerization catalyst include, for example:
(i) Component (C) and solid support (S) are contacted, then component (A) is contacted to prepare a solid catalyst component (XA), and component (C) and solid support (S) are ) followed by contacting component (B) to prepare a solid catalyst component (XB);
(ii) component (A) and component (C) are mixed and contacted, then contacted with a solid support (S) to prepare a solid catalyst component (XA), and component (B) and component (C) are a method of mixing and contacting and then contacting a solid support (S) to prepare a solid catalyst component (XB),
(iii) contacting the component (C) with the solid support (S), then contacting the contact product of the component (A) and the component (C) to prepare the solid catalyst component (XA), and a method of contacting C) with a solid support (S) and then contacting the contact product of component (B) with component (C) to prepare a solid catalyst component (XB);
(iv) contacting the component (C) with the solid support (S), then contacting the component (A), and then contacting the component (C) to prepare a solid catalyst component (XA); , a method of contacting the component (C) with the solid support (S), then contacting the component (B), and then contacting the component (C) to prepare the solid catalyst component (XB);
(v) a method of contacting the solid support (S) with the component (C), then contacting the component (A) and then contacting the component (B) to prepare the solid catalyst component (XC);
(vi) contacting the solid support (S) with the component (C), then contacting the component (B), and then contacting the component (A) to prepare the solid catalyst component (XC);
(vii) contacting the solid support (S) with component (C) and then contacting the contact mixture of component (A) and component (B) to prepare a solid catalyst component (XC);
(viii) A method of contacting component (A) with component (B), followed by contacting component (C), followed by contacting with solid support (S) to prepare solid catalyst component (XC);
(ix) After contacting the solid support (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 the solid catalyst component ( XC),
(x) After contacting the solid support (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 ( XC),
(xi) After contacting the solid support (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 brought into contact with the solid catalyst component ( XC),
(xii) contacting the solid support (S) with the component (C) and then contacting the contact mixture of the component (A), the component (B) and the component (C) to prepare a solid catalyst component (XC); how to,
(xiii) contacting the solid support (S) with the component (C), then contacting the contact mixture of the component (A) and the component (C), and then contacting the component (B) to obtain the solid catalyst component (X); - a method of preparing C),
(xiv) contacting the solid support (S) with the component (C), then contacting the contact mixture of the component (B) and the component (C), and then contacting the component (A) to obtain the solid catalyst component (X); - a method of preparing C),
(xv) After contacting the solid support (S) with the component (C), further contacting the component (C), then the contact mixture of the component (A) and the component (C) and the component (B) and the component ( a method of contacting the contact mixture of C) in this order to prepare a solid catalyst component (XC);
(xvi) After contacting the solid support (S) with the component (C), further contacting the component (C), then the contact mixture of the component (B) and the component (C) and the component (A) and the component ( a method of contacting the contact mixture of C) in this order to prepare a solid catalyst component (XC);
(xvii) After contacting the solid carrier (S) with the component (C), further contacting the component (C), and then contacting the contact mixture of the component (A), the component (B) and the component (C) a method of preparing a solid catalyst component (XC) by
(xviii) A mixture of components (A) and (C) and a mixture of components (B) and (C) are mixed in advance, and then brought into contact with the contact product of the solid carrier (S) and component (C). a method of preparing a solid catalyst component (XC) by
(xix) After premixing the mixture of component (A) and component (C) with the mixture of component (B) and component (C), the solid carrier (S) and component (C) are brought into contact, and further component A method of preparing a solid catalyst component (XC) by contacting a contact mixture in which (C) is contacted, and the like.

When multiple components (C) are used, the components (C) may be the same or different. Among them, a particularly preferable contact order is (xi), (xiii), (xv
), (xvi), (xvii), (xxii), (xxiii) and (xxiv).

By contacting the component (C) and the solid carrier (S), the reaction sites in the component (C) react with the reaction sites in the solid carrier (S) to form the component (C) and the solid carrier (S). They are chemically combined to form a contact between component (C) and solid carrier (S). The contact time between the component (C) and 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. is. If the component (C) and the solid support (S) are brought into rapid initial contact, the solid support (S) will collapse due to the reaction heat and reaction energy, and the morphology of the resulting solid catalyst component (X) will deteriorate. However, when this is used for polymerization, continuous operation is often difficult due to poor polymer morphology. Therefore, at the initial stage of contact between the component (C) and the solid carrier (S), contact is made at a low temperature of -20 to 30 ° C. for the purpose of suppressing the reaction heat generation, or the reaction heat generation is controlled and the initial contact temperature is It is preferred to react at a sustainable rate. The same applies when the component (C) is brought into contact with the solid carrier (S) and then the component (C) is brought into contact with the solid carrier (S). The molar ratio of contact between the component (C) and the solid support (S) (component (C)/solid support (S)) can be arbitrarily selected, but the higher the molar ratio, the better the contact between the component (A) and the solid support (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 component (C) and solid support (S) [=molar amount of component (C)/molar amount of solid support (S)] is preferably 0.2 to 2.0. , particularly preferably 0.4 to 2.0.

Regarding the contact of the component (C) and the solid carrier (S) with the component (A) and the component (B), the contact time is usually 0 to 5 hours, preferably 0 to 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 component (c-1), the molar ratio [(c-1)/M] of component (c-1) to all transition metal atoms (M) in components (A) and (B) is It is usually used in an amount of 0.01 to 100,000, preferably 0.05 to 50,000. In the case of component (c-2), the molar ratio of aluminum atoms in component (c-2) to all transition metal atoms (M) in components (A) and (B) [(c-2)/ M] is generally used in an amount of 10 to 500,000, preferably 20 to 100,000. In the case of component (c-3), the molar ratio [(c-3)/M] of component (c-3) to all transition metal atoms (M) in components (A) and (B) is , usually 1 to 10, preferably 1 to 5. The molar ratio of component (C) to all transition metal atoms (M) in components (A) and (B) can be determined by inductively coupled plasma atomic emission spectrometry (ICP analysis).

Solvents used for the preparation of the solid catalyst component (X) include inert hydrocarbon solvents. 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; be done.

In each method showing the contact order 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 step comprising contacting the solid support (S) with the component (A), ) and component (B) in contact, and in the step of contacting solid support (S) with component (A) and component (B), (g-1) polyalkylene oxide block as component (G) , (g-2) higher aliphatic amides, (g-3) polyalkylene oxides, (g-4) polyalkylene oxide alkyl ethers, (g-5) alkyldiethanolamines, and (g-6) polyoxyalkylenealkylamines At least one compound selected from may coexist. By coexisting such a component (G), fouling during the polymerization reaction can be suppressed, and the particle properties of the produced polymer are improved. Among components (G), (g-1), (g-2), (g-3) and (g-4) are preferred.

The use ratio of component (A) and component (B) can be appropriately determined according to the molecular weight and molecular weight distribution of the polymer to be produced.
In the polymerization of olefin, the solid catalyst component (X) as described above can be used as it is, but the solid catalyst component (X) is prepolymerized with olefin to form the prepolymerized catalyst component (XP) before use. can also

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

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

The prepolymerization temperature is usually -20 to 80°C, preferably 0 to 60°C. Further, the preliminary polymerization time is usually 0.5 to 100 hours, preferably 1 to 50 hours.
As the form of the solid catalyst component (X) used for prepolymerization, those already described can be used without limitation. In addition, component (C) is used as necessary, and the organoaluminum compound represented by the above formula (3) in (c-1) is particularly preferably used. When the organoaluminum compound of formula (3) is used as component (C), the molar ratio (component ( C)/transition metal compound), which is usually used in an amount of 0.1 to 10,000, preferably 0.5 to 5,000.

The concentration of the solid catalyst component (X) in the prepolymerization system is preferably 1 to 1000 g/liter, preferably 10 to 500 g/liter, in terms of solid catalyst component (X)/1 liter polymerization volume. At the time of prepolymerization, the component (G) can coexist for the purpose of suppressing fouling or improving particle properties.

In addition, component (G) is added to the preliminary polymerization catalyst component (XP) once generated by preliminary polymerization for the purpose of improving the fluidity of the preliminary polymerization catalyst component (XP) and suppressing the occurrence of heat spots, sheeting and polymer lumps during polymerization. may be brought into contact. In this case, as the component (G) to be used, the above (g-1), (g-2), (g-3) and (g-4) are preferable.

The temperature at which 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 mixing and contacting the solid catalyst component (X) and the component (G), the component (G) is usually added in an amount of 0.1 to 20 parts by weight, preferably 0.1 to 20 parts by weight, per 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.

The mixed contact of the solid catalyst component (X) and the component (G) can be carried out in an inert hydrocarbon solvent. are listed.

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

Drying of the preliminary polymerization catalyst component (XP) is carried out by keeping the preliminary polymerization catalyst component (XP) at a temperature of 70° C. or less, preferably in the range of 20 to 50° C. under inert gas flow. The amount of volatile components in the obtained dry prepolymerized catalyst is desirably 2.0% by weight or less, preferably 1.0% by weight or less. The lower the amount of volatile components in the dried prepolymerized catalyst, the better. Although there is no particular lower limit, it is practically 0.001% by weight. The drying time is usually 3 to 8 hours depending on the drying temperature. When the amount of volatile components in the dried prepolymerized catalyst exceeds 2.0% by weight, the fluidity of the dried prepolymerized catalyst is lowered, and it may not be possible to stably supply the catalyst to the polymerization reactor.

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

In the method using gas chromatography, volatile components such as hydrocarbons are extracted from the dried prepolymerized catalyst, a calibration curve is drawn according to the internal standard method, and weight percent is calculated from the GC area.

As for the method for measuring the amount of volatile components in the dried prepolymerized catalyst, when the amount of volatile components in the dried prepolymerized catalyst is about 1% by weight or more, the weight loss method is adopted, and the amount of volatile components in the dried prepolymerized catalyst is about 1% by weight. If it is less than % by weight, a method using gas chromatography is adopted.

Nitrogen gas, argon gas, neon gas, and the like are examples of the inert gas used for drying the prepolymerized catalyst component (XP). Such an inert gas has an oxygen concentration of 20 ppm or less, preferably 10 ppm or less, more preferably 5 ppm or less (by volume), and a water content of 20 ppm or less, preferably 10 ppm or less, more preferably 5 ppm or less (by weight). ) is desirable. If the oxygen concentration and water content in the inert gas exceed the above ranges, the olefin polymerization activity of the dried prepolymerized catalyst may be greatly reduced.

Since the dried prepolymerized catalyst has excellent fluidity, it can be stably supplied to the polymerization reactor. Moreover, since the solvent used for suspension does not need to be entrained in the gas phase polymerization system, the polymerization can be stably carried out.

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

In the present invention, polymerization can be carried out by either a liquid phase polymerization method such as solution polymerization or suspension polymerization, or a gas phase polymerization method. It is preferable to use

Specific examples of inert hydrocarbon media used in liquid phase polymerization include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; 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. Moreover, in the liquid phase polymerization method, the olefin itself can be used as a solvent.

When ethylene is polymerized using the above olefin polymerization catalyst, component (A) and component (B) are usually added in an amount of 10 ⁻¹² to 10 ⁻¹ mol, preferably 10 ⁻⁸ to 10 mol, per liter of reaction volume. It is used in such an amount that it becomes ^-2 moles. In addition, component (C) is used, and the organoaluminum compound represented by formula (3) in (c-1) is particularly preferably used.

The temperature for ethylene polymerization using the solid catalyst component (X) described above is generally -50 to +200°C, preferably 0 to 170°C, and particularly preferably 60 to 170°C. The polymerization pressure is usually normal pressure to 100 kg/cm ² , preferably normal pressure to 50 kg/cm ² , and the polymerization reaction can be carried out in any of batch, semi-continuous and continuous processes. can be done. Furthermore, it is also possible to carry out the polymerization in two or more stages with different reaction conditions.

The molecular weight of the resulting polymer can be adjusted by the presence of hydrogen in the polymerization system or by varying the polymerization temperature. In general, the more the low-molecular-weight component, the more it adheres to the walls of the polymerization reactor and the stirring blades, which may increase the load on the cleaning process and lead to a decrease in productivity. During polymerization, the component (G) can coexist for the purpose of suppressing fouling or improving particle properties.

Moreover, the olefin supplied to the copolymerization reaction in the present invention is one or more monomers selected from olefins having 3 to 20 carbon atoms. Specific examples of olefins having 3 to 20 carbon atoms include propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, and 1-dodecene. , 1-tetradecene, 1-hexadecene, 1-octadecene and 1-eicosene; Cyclic olefins such as 8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene and the like are included. Examples of the olefins include styrene, vinylcyclohexane, dienes, acrylic acid, methacrylic acid, fumaric acid, maleic anhydride, etc.; methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, polar Also included are monomers and the like.

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 olefin polymerization catalyst of the present invention, which is a preferred embodiment of the present invention. The ethylene polymer preferably satisfies the following requirements (1) to (4). The methods for measuring these requirements are as described in Examples.

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

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

(2) 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 within the above range, the film formed from the ethylene polymer has less stickiness on the surface 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. Good.

In general, the density depends on the α-olefin content of the ethylene-based polymer; the lower the α-olefin content, the higher the density, and the higher the α-olefin content, the lower the density. Further, it is known that the α-olefin content in the ethylene-based polymer is determined by the compositional ratio (α-olefin/ethylene) of the α-olefin and ethylene in the polymerization system (for example, Walter Kaminsky, Makromol.Chem.193, p.606 (1992)). Therefore, by increasing or decreasing α-olefin/ethylene, it is possible to produce an ethylene-based polymer having a density within the above range.

( ₃ ) The ratio ( ^η ₀ /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 are expressed by 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 .

η ₀ /Mw ^6.8 is 0.03×10 ⁻³⁰ or more and 7.5×10 ⁻³⁰ or less because when η ₀ and Mw are double-logarithm plotted, log(η ₀ ) and logMw are expressed by the following formula It is synonymous with existing in the region defined by (Eq-1').
6.8 Log (Mw) - 31.523 < Log (η ₀ ) < 6.8 Log (Mw) - 29.125 --- (Eq-1')

When plotting the zero-shear viscosity [η ₀ (P)] against the weight-average molecular weight (Mw) in a log-logarithm, an ethylene polymer that has no long-chain branching, is linear, and does not show strain hardening in extensional viscosity is , the slope follows the power law of 3.4. On the other hand, an ethylene-based polymer that has many relatively short long-chain branches and whose elongational viscosity exhibits strain rate hardening exhibits a zero shear viscosity [η ₀ (P)] lower than the power law, and the slope is It is known to be a value greater 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)), a slope of 6.8 can be chosen empirically. Japanese Patent Application Laid-Open No. 2011-1545 also discloses the ratio of η ₀ and Mw ^6.8 .

When the ethylene polymer has a zero shear viscosity [η ₀ (P)] at 200° C. of 20×10 ⁻¹³ ×Mw ^6.8 or less, take-up surging is suppressed in the ethylene polymer.

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

It is known that the anti-blocking property is remarkably improved by forming fine irregularities on the film surface. When molten resin flows into the die, extensional stress is generated by the extensional flow. When this tensile stress exceeds a critical value, brittle fracture occurs, and unstable flow called melt fracture occurs at the exit of the die, forming minute irregularities on the surface of the compact (FN Cogswell, Polymer Melt Rheology, Wiley, 1981).

If η ₀ /Mw ^6.8 is within the claimed range, the tensile stress becomes large at the strain rate in general molding, and melt fracture occurs. Since this melt fracture forms fine irregularities on the film surface, the blocking resistance of the resulting film is extremely excellent.

It is known that extensional stress is strongly affected by the number and length of long chain branches, and the greater the number and the longer the length, the greater the extensional stress. If η ₀ /Mw ^6.8 exceeds the upper limit, the number of long-chain branches tends to be insufficient, and if it is below the lower limit, the length of the 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 thought to depend on the content and length of long chain branches in the ethylene polymer. The zero shear viscosity [η ₀ (P)] shows a value closer to the lower limit of the claimed range as the content of long chain branching increases and the length of long chain branching decreases. It is considered that the zero shear viscosity [η ₀ (P)] shows a value closer to the upper limit of the claimed range as the value increases.

Here, long-chain branching is defined as a branched structure having a length equal to or greater than the molecular weight between entanglement points (Me) contained in the ethylene-based polymer. It is known that processability changes remarkably (for example, edited by Kazuo Matsuura et al., "Polyethylene Technical Readers", Industrial Research Institute, 2001, pp. 32, 36).

In the mechanism by which the ethylene-based polymer is produced, the present inventors discovered that ethylene and C4 A "macromonomer" which is a polymer having a 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 an α-olefin of 10 or more and then component (B ), component (C) and solid support (S), by copolymerizing the macromonomer competitively with the polymerization of ethylene and an α-olefin having 4 to 10 carbon atoms, It is presumed that long-chain branches are formed in the ethylene-based polymer.

The higher the composition ratio of the macromonomer and ethylene ([macromonomer]/[ethylene]) in the polymerization system, the higher the long-chain branch content. [ Macromonomer]/[ethylene] can be increased, so increasing ([A]/[A+B]) increases the long chain branching content. Further, when the composition ratio of hydrogen and ethylene (hydrogen/ethylene) in the polymerization system is increased, the molecular weight of the macromonomer is decreased, so that the length of the long chain branch introduced into the ethylene polymer is shortened.

Accordingly, by increasing or decreasing [A]/[A+B] and hydrogen/ethylene, an ethylene polymer having η ₀ /Mw ^6.8 within the above range can be produced.
In addition to these, polymerization conditions for controlling the amount of long chain branching are disclosed, for example, in International Publication No. 2007/034920 pamphlet.

(4) Intrinsic viscosity [[η] (dl/g)] measured in decalin at 135°C and the weight average molecular weight measured by the GPC-viscosity detector method (GPC-VISCO) to the power of 0.776 (Mw ^0.776 ), [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, [η] and Mw are represented by 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 .

[η]/Mw ^0.776 is 0.90 × 10 ^-4 or more and 1.65 × 10 ^-4 or less is log ([η])) and It is synonymous with log(Mw) existing in the region defined by the following formula (Eq-2′).
0.776 Log (Mw) - 4.046 ≤ Log ([η])) ≤ 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) becomes smaller relative to the molecular weight compared to a straight-chain ethylene-based polymer having no long-chain branching. (eg 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, especially not more than 1.65×10 ⁻⁴ , the ethylene polymer has a large number of long chain branches, and the ethylene polymer has moldability and Excellent liquidity.

As described above, increasing the ratio ([A]/[A+B]) of component (A) in the olefin polymerization catalyst increases the content of long chain branches, so [A]/[A+B] is increased or decreased. Thus, an ethylene-based polymer (α) having a limiting viscosity [η] in the scope of claims can be produced. For the purpose of suppressing variations in physical properties, the ethylene-based polymer particles obtained by the polymerization reaction and other optional components may be melted, kneaded, and granulated by any method.

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

(ii) The ethylene-based polymer and other optional components are dissolved in a suitable good solvent (e.g., hydrocarbon solvents such as hexane, heptane, decane, cyclohexane, benzene, toluene and xylene), and then the solvent is A method of removing, then mechanically blending using an extruder, kneader, etc., and cutting into a predetermined size.

The ethylene-based polymer obtained in the present invention contains a weather stabilizer, a heat stabilizer, an antistatic agent, an antislip agent, an antiblocking agent, an antifogging agent, a lubricant, a pigment, a Additives such as dyes, nucleating agents, plasticizers, anti-aging agents, hydrochloric acid absorbers, and antioxidants may be added as necessary.

The ethylene-based polymer obtained in the present invention and, if necessary, a resin composition containing a thermoplastic resin and additives are processed by general film molding, blow molding, injection molding and extrusion molding. In film molding, it can be obtained by extrusion lamination molding, T-die film molding, inflation molding (air cooling, water cooling, multi-stage cooling, high-speed processing), or the like. A film obtained using the ethylene-based polymer can be used even in a single layer, but can be provided with various functions by making it into a multilayer. In that case, the co-extrusion method in each of the molding methods described above may be used. On the other hand, lamination with paper or barrier films (aluminum foil, vapor-deposited film, coating film, etc.), which are difficult to co-extrude, can be achieved by a pasting lamination molding method such as extrusion lamination molding or dry lamination. Blow molding, injection molding, and extrusion molding can be used to produce multi-layered high-performance products by co-extrusion in the same manner as film molding.

Molded articles obtained by processing the resin composition containing the ethylene-based polymer obtained in the present invention and, if necessary, thermoplastic resins and additives include films, blow infusion bags, blow bottles, gasoline tanks, Extrusion-molded tubes, pipes, tear-off caps, injection-molded products such as daily necessities, fibers, large-sized rotational molding products, and the like.

Furthermore, the film obtained by processing the ethylene-based polymer obtained in the present invention and, if necessary, a resin composition containing a thermoplastic resin and additives, can be used as a water product packaging bag, a liquid soup packet, a liquid paper container , laminated raw fabric, special shape liquid packaging bags (standing pouches, etc.), standard bags, heavy duty bags, wrap film, sugar bags, oil packaging bags, various packaging films such as food packaging, protective films, infusion bags, agriculture It is suitable for use as a raw material. It can also be used as a multi-layer film by laminating it with a base material such as nylon or polyester.

EXAMPLES The present invention will be described in more detail below based on examples, but the present invention is not limited to these examples. In the following examples and comparative examples, the amount of free polymer in the production of the ethylene-based polymer and the physical properties of the obtained ethylene-based polymer were measured as follows.

<Amount of free polymer>
The amount of free polymer (wt%) is the amount X (g) of the polymer obtained by drying the supernatant (solvent) after slurry polymerization, and the total yield Y (g ) was measured and obtained by the following formula.
Amount of free polymer (wt%) = X/(X + Y) x 100

<Melt flow rate (MFR)>
Measured under the conditions of 190° C. and 2.16 kg load (kgf).

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

<Melt tension (MT)>
The melt tension (MT) (unit: g) at 190° C. was determined by measuring the stress when drawing at a constant speed. For the measurement, a capillary rheometer: Capilograph 1D manufactured by Toyo Seiki Seisakusho Co., Ltd. was used. 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 molten filament breaks, reduce the winding speed by 5 m/min) ), a nozzle diameter of 2.095 mm, and a nozzle length of 8 mm.

<Shear viscosity (η ^* )>
The shear viscosity [η ^* (1.0)] (P) at 200°C and an angular velocity of 1.0 rad/sec was measured by the following method.
The shear viscosity (η ^* ) is measured by angular velocity [ω (rad/sec)] dispersion of the shear viscosity (η ^* ) at a measurement temperature of 200°C within the range of 0.01≤ω≤100. For the measurement, a viscoelasticity measuring device Physica MCR301 manufactured by Anton Paar was used, a parallel plate of 25 mmφ was used as a sample holder, and the thickness of the sample was set to about 2.0 mm. The measurement points were five points per one digit of ω. The amount of strain was appropriately selected in the range of 3 to 10% so that the torque in the measurement range could be detected and torque over would not occur.

The samples used for shear viscosity measurement were preheated at 190° C., preheated for 5 minutes, heated at 190° C., heated for 2 minutes, heated at a pressure of 100 kgf/cm ² , and cooled at a cooling temperature of 20 using a press molding machine manufactured by Shindo Kinzoku Kogyo Co., Ltd. C., a cooling time of 5 minutes, and a cooling pressure of 100 kgf/ ^cm.sup.2 .

<Zero shear viscosity (η ₀ )>
The zero shear viscosity (η ₀ ) (P) at 200°C was obtained by the following method.
At a measurement temperature of 200° C., the angular velocity ω (rad/sec) dispersion of shear viscosity (η ^* ) is measured in the range of 0.01≦ω≦100. For the measurement, a viscoelasticity measuring device Physica MCR301 manufactured by Anton Paar was used, a parallel plate of 25 mmφ was used as a sample holder, and the thickness of the sample was set to about 2.0 mm. The measurement points were five points per one digit of ω. The amount of strain was appropriately selected in the range of 3 to 10% so that the torque in the measurement range could be detected and torque over would not occur.

The samples used for shear viscosity measurement were preheated at 190°C, preheated for 5 minutes, heated at 190°C, heated for 2 minutes, heated at a pressure of 100 kgf/cm ² , and cooled at a cooling temperature of 20 using a press molding machine manufactured by Shindo Kinzoku Kogyo Co., Ltd. C., a cooling time of 5 minutes, and a cooling pressure of 100 kgf/ ^cm.sup.2 .

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

where λ is a time-dimensional parameter and n is the power law index of the material. The fitting by the nonlinear least squares method was performed so that d in the following formula (Eq-4) was minimized.

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 the above formula (Eq-4), η _exp (ω) represents the measured shear viscosity, and η _calc (ω) 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)>
Using a GPC-viscosity detector (GPC-VISCO) GPC/V2000 manufactured by Waters, measurements were made as follows.

Shodex AT-G is used for the guard column, two AT-806 are used for the analysis column, a differential refractometer and 3 capillary viscometers are used as the detector, the column temperature is 145 ° C., and the mobile phase is 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 standard polystyrene, one manufactured by Tosoh Corporation was used. For molecular weight calculation, the measured viscosity is calculated from the viscometer and refractometer, and the number average molecular weight (Mn), weight average molecular weight (Mw), Z average molecular weight (Mz), molecular weight distribution (Mw/Mn, Mz /Mw) was determined.

<Intrinsic viscosity [η]>
About 20 mg of the measurement sample was dissolved in 15 ml of decalin, and the specific viscosity η _sp was measured in an oil bath at 135°C. 5 ml of the decalin solvent was added to the decalin solution to dilute it, and then the specific viscosity η _sp was measured in the same manner. This dilution operation is repeated twice, and the intrinsic viscosity [η] (unit: _dl /g ).
[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 were charged into a 300 mL reactor that was sufficiently dried and replaced with argon, and 28.0 mL of n-butyllithium solution (hexane solution, 1.62 M, 45.4 mmol ) was added under ice-cooling, and the mixture was stirred at room temperature for 2 hours. To this solution, 5.20 mL (45.4 mmol) of butyl iodide was added dropwise under ice-cooling, and the mixture was slowly warmed to room temperature while stirring was continued for 15 hours. A saturated aqueous ammonium chloride solution was added, the soluble matter was extracted with n-hexane, the resulting fraction was washed with saturated brine and dried over anhydrous magnesium sulfate. After filtering magnesium sulfate, the residue obtained by evaporating the filtrate was purified by silica gel column chromatography to give the target compound represented by the following formula (A-1a) (hereinafter referred to as compound (A-1a)). Obtained as an isomeric mixture of 6.50 g (88% yield).

¹ H NMR (270 MHz, CDCl ₃ ) δ 7.44 (1H, d, J=7.3 Hz, Ar-H), 7.41-7.24 (2H, m, Ar-H), 7.24- 7.13 (1H, m, Ar-H), 6.18 (1H, t, J = 1.5 Hz, C = CH-C), 3.31 (2H, 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=7.3 Hz, --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 (1) and 20 mL of tetrahydrofuran were charged into a 100 mL reactor sufficiently dried and replaced with argon to obtain an n-butyllithium solution of 5 0.60 mL (hexane solution, 1.64 M, 9.18 mmol) was added under ice cooling and stirred at room temperature for 2 hours. This reaction solution was slowly added to a diluted solution of 5.50 mL (46.0 mmol) of dimethylsilyl dichloride in 10 mL of n-hexane under cooling at -78°C, and the mixture was allowed to warm to room temperature while stirring was continued for 20 hours. After distilling off the solvent of the reaction solution and unreacted dimethylsilyl dichloride, 10 mL of tetrahydrofuran and 0.90 mL (9.58 mmol) of 1,3-dimethyl-2-imidazolidinone were added to the residue. A 100 mL reactor sufficiently dried and purged with argon was charged with 4.60 mL of 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 solution of the reaction residue cooled to -78°C, and the mixture was allowed to warm slowly to room temperature while stirring was continued for 19 hours. A saturated aqueous ammonium chloride solution was added, the soluble matter was extracted with n-hexane, the resulting fraction was washed with saturated brine and dried over anhydrous magnesium sulfate. After filtering magnesium sulfate, the residue obtained by evaporating the filtrate was purified by silica gel column chromatography to obtain the target compound represented by the following formula (A-1L) (hereinafter also referred to as "compound (A-1L)" ) was obtained as an isomeric mixture of 2.20 g (82% yield).

¹ H NMR (270 MHz, CDCl ₃ ) δ 7.62-7.15 (5H, m, Ar-H&C=CH-C), 6.90-6.08 (4H, 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-1L) obtained in (2) above, 20 mL of toluene, and 0.4 mL of tetrahydrofuran were placed in a 100 mL reactor sufficiently dried and replaced with argon and stirred. . After adding 2.50 mL of n-butyllithium solution (hexane solution, 1.64 M, 4.10 mmol) to this solution at room temperature, stirring was continued for 3 hours in an oil bath at 40°C. After distilling off the solvent of the reaction solution, 20 mL of diethyl ether was added to the resulting solid. This 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 resulting solid to prepare a suspension, and insoluble matter was removed with celite on a glass filter. After concentrating the resulting solution under reduced pressure, n-hexane was added to prepare a suspension, and insoluble matter was filtered off through a glass filter. By drying the residue under reduced pressure, a yellow powdery compound dimethylsilylene(3-n-butyl-1-indenyl)(cyclopentadienyl)zirconium dichloride represented by the following formula (A-1) (hereinafter referred to as “component (A -1)”) was obtained (yield 54%).

¹ H NMR (270 MHz, CDCl ₃ ) δ 7.60 (1H, dt, J=8.5 and 1.0 Hz, Ar-H), 7.47-7.36 (2H, m, Ar-H), 7. 13-7.03 (1H, m, Ar-H), 6.84-6.73 (2H, m, Cp-H), 5.89-5.84 (1H, m, Cp-H), 5 .82 (1H, s, Ind-H), 5.80-5.75 (1H, m, Cp-H), 2.90 (2H, t, J = 7.7 Hz, C- _CH2 - _CH2 -), 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=7.3 Hz, —CH ₂ —CH ₃ ), 0.81 (3H, s, Si—CH ₃ ) ppm
FD-mass spectroscopy (M ⁺ ): 454

<Synthesis Example 2>
(1) 3.91 g (30.0 mmol) of 2-methylindene and 30 mL of tetrahydrofuran were charged into a 300 mL reactor that was sufficiently dried and replaced with argon, and 19.2 mL of n-butyllithium solution (hexane solution, 1.64 M, 31.5 mmol) was added under ice-cooling, and the mixture was 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 the mixture was slowly warmed to room temperature while stirring was continued for 2 hours. A saturated aqueous ammonium chloride solution was added, the soluble matter was extracted with n-hexane, the resulting fraction was washed with saturated brine and dried over anhydrous magnesium sulfate. After filtering magnesium sulfate, the residue obtained by evaporating the filtrate was purified by silica gel column chromatography to obtain the desired product represented by the following formula (A-2a) (hereinafter also referred to as "compound (A-2a)" ) was obtained as an isomeric mixture of 5.40 g (97% yield).

¹ H NMR (270 MHz, CDCl ₃ ) δ 7.34 (1H, d, J=7.4 Hz, Ar-H), 7.24-7.14 (2H, m, Ar-H), 7.14- 7.02 (1H, m, Ar—H), 6.44 (1H, s, C=CH—C), 3.33 (1H, t, J=5.0 Hz, C—CH—C), 2 .05 (3H, d, J = 0.8Hz, _-CH3 ), 2.03-1.08 (1H, m, CH- _{CH2 -} CH2-), 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 = 7.3 Hz, _-CH2 - _CH3 ) ppm

(2) 3.73 g (20.0 mmol) of the compound (A-2a) obtained in (1) and 30 mL of tetrahydrofuran were charged into a 100 mL reactor that had been sufficiently dried and replaced with argon, and an n-butyllithium solution of 12 .2 mL (hexane solution, 1.64 M, 20.0 mmol) was added under ice-cooling, and the mixture was stirred at room temperature for 2 hours. This reaction solution was slowly added to a diluted solution of 12.0 mL (100 mmol) of dimethylsilyl dichloride in 10 mL of n-hexane under cooling at −78° C., and the mixture was allowed to warm to room temperature while stirring was continued for 19 hours. 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. A 100 mL reactor sufficiently dried and purged with argon was charged with 10.0 mL of sodium cyclopentadienide solution (tetrahydrofuran solution, 2.0 M, 20.0 mmol) and 20 mL of tetrahydrofuran. This solution was added dropwise to the previously diluted solution of the reaction residue cooled to -78°C, and the mixture was allowed to warm slowly to room temperature while stirring was continued for 19 hours. A saturated aqueous ammonium chloride solution was added, the soluble matter was extracted with n-hexane, the resulting fraction was washed with saturated brine and dried over anhydrous magnesium sulfate. After filtering magnesium sulfate, the residue obtained by evaporating the filtrate was purified by silica gel column chromatography to give the target compound represented by the following formula (A-2L) (hereinafter also referred to as "compound (A-2L)" ) was obtained as an isomeric mixture of 5.41 g (88% yield).

¹ H NMR (270 MHz, CDCl ₃ ) δ 7.61-7.01 (4H, m, Ar—H), 6.92-5.96 (4H, 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 ), 1.70-1.36 (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 (2) above, 20 mL of toluene, and 0.4 mL of tetrahydrofuran were placed in a 100 mL reactor sufficiently dried and replaced with argon, and stirred. . After adding 2.60 mL of n-butyllithium solution (hexane solution, 1.55 M, 4.03 mmol) to this solution at room temperature, stirring was continued for 3 hours in an oil bath at 40°C. After distilling off the solvent of the reaction solution, 20 mL of diethyl ether was added to the resulting 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 resulting solid to prepare a suspension, and insoluble matter was removed with celite on a glass filter. After concentrating the resulting solution under reduced pressure, n-hexane was added to prepare a suspension, and insoluble matter was filtered off with a glass filter. By drying the residue under reduced pressure, a yellow powdery compound dimethylsilylene (3-n-butyl-2-methyl-1-indenyl)(cyclopentadienyl)zirconium dichloride (hereinafter referred to as Also referred to as "component (A-2)") was obtained 0.22 g (yield 24%).

¹ H NMR (270 MHz, CDCl ₃ ) δ 7.59 (1H, dt, J = 8.6 and 1.0 Hz, Ar-H), 7.50 (1H, dt, J = 8.6 and 1.0 Hz, Ar-H ), 7.45-7.35 (1H, m, Ar-H), 7.07-6.97 (1H, m, Ar-H), 6.84-6.76 (1H, 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 (3H, s, --CH ₃ ), 1.60-1.26 (4H, m, --CH ₂ --CH ₂ --), 1.07 (3H , s, Si—CH ₃ ), 0.96 (3H, s, Si—CH ₃ ), 0.92 (3H, t, J=7.2 Hz, —CH ₂ —CH ₃ ) ppm
FD-mass spectroscopy (M ⁺ ): 468

<Synthesis Example 3>
(1) 1.44 g (59.4 mmol) of magnesium pieces were placed in a 200 mL reactor that was sufficiently dried and replaced with argon, 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. 2-Bromoindene 2.93 g (15.0 mmol) diluted solution of 2.93 g (15.0 mmol) of tetrahydrofuran in 10 mL was added dropwise (after adding 1.0 mL, heated under reflux with a dryer until the color of iodine disappeared, and after the reaction was started, the remaining drops were added dropwise). After completion, the mixture was stirred at room temperature for 2 hours. This reaction solution was slowly added to a diluted solution of 9.00 mL (75.3 mmol) of dimethylsilyl dichloride in 10 mL of n-hexane under cooling at -78°C, and the mixture was allowed to warm to room temperature while stirring was continued for 17 hours. After distilling off the solvent of the reaction solution and unreacted dimethylsilyl dichloride, 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 Synthesis Example 2(1) and 15 mL of tetrahydrofuran were charged into a 100 mL reactor that was sufficiently dried and replaced with argon to give an 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 solution of the reaction residue cooled to -78°C, and the mixture was allowed to warm slowly to room temperature while stirring was continued for 16 hours. A saturated aqueous ammonium chloride solution was added, the soluble matter was extracted with n-hexane, the resulting fraction was washed with saturated brine and dried over anhydrous magnesium sulfate. After filtering magnesium sulfate, the residue obtained by evaporating the filtrate was purified by silica gel column chromatography to give the target compound represented by the following formula (A-3L) (hereinafter also referred to as "compound (A-3L)" ) was obtained as an isomeric mixture of 3.15 g (58% yield).

¹ H NMR (270 MHz, CDCl ₃ ) δ 7.43 (1H, d, J=7.3 Hz, Ar-H), 7.38 (1H, 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 (1H, s, Si-CH), 3 .22 (2H, dd, J=47.7 and 22.4 Hz, C—CH ₂ —C—), 2.49 (2H, t, J=7.3 Hz, —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=7.1 Hz, —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-3L) obtained in (1) above, 20 mL of toluene, and 0.4 mL of tetrahydrofuran were placed in a 100 mL reactor sufficiently dried and replaced with argon, and stirred. . After adding 2.60 mL of n-butyllithium solution (hexane solution, 1.55 M, 4.03 mmol) to this solution at room temperature, stirring was continued for 3 hours in an oil bath at 40°C. After distilling off the solvent of the reaction liquid, 20 mL of diethyl ether was added to the obtained solid. This 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 resulting solid to prepare a suspension, and insoluble matter was removed with celite on a glass filter. After concentrating the resulting solution under reduced pressure, n-hexane was added to prepare a suspension, and insoluble matter was filtered off with a glass filter. By drying the residue under reduced pressure, a yellow powdery compound dimethylsilylene(3-n-butyl-1-indenyl)(2-indenyl)zirconium dichloride represented by the following formula (A-3) (hereinafter referred to as "component (A- 3)”) was obtained in an amount of 0.40 g (yield 39%).

¹ H NMR (270 MHz, CDCl ₃ ) δ 7.73-7.63 (2H, m, Ar-H), 7.50 (1H, 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 (1H, 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=7.1 Hz, —CH ₂ —CH ₃ ) ppm
FD-mass spectroscopy (M ⁺ ): 518

<Synthesis Example 4>
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 was synthesized by the method described in the publication.

<Synthesis Example 5>
Dimethylsilylene(cyclopentadienyl)(1-indenyl)zirconium dichloride represented by the following formula (A-5) (hereinafter also referred to as “compound (A-5)”) is prepared according to Macromolecules 1995, 28, 3771. Synthesized by the method described.

<Synthesis Example 6>
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 was synthesized based on the method described in JP-A-4-69394.

[Example 1]
<Preparation of solid catalyst component (X)>
Silica manufactured by Fuji Silysia Co., Ltd. (average particle diameter 70 μm, specific surface area 340 m ² /g, pore volume 1.3 cm ³ / g, calcined at 250°C) was suspended in 77 liters of toluene and then cooled to 0-5°C. To this suspension, 20.4 liters of a toluene solution of methylaluminoxane (3.5 mol/L in terms of Al atoms) was added dropwise over 30 minutes as component (C). At this time, the temperature in the system was kept at 0 to 5°C. After reacting at 0 to 5°C for 30 minutes, the temperature was raised to 95 to 100°C over about 1.5 hours, followed by reaction at 95 to 100°C for 4 hours. After that, the temperature was lowered to normal temperature, the supernatant liquid was removed by decantation, and after washing with toluene twice, a total amount of 59.0 liters of toluene slurry was prepared. A portion of the obtained slurry components was sampled and examined for concentration.

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

<Production of ethylene polymer>
After adding 500 ml of heptane in a nitrogen atmosphere to a 1 liter SUS autoclave equipped with a stirring blade that was sufficiently purged with nitrogen, ethylene was passed through to saturate the liquid phase and gas phase with ethylene. Next, 10 mL of 1-hexene, 0.375 mmol of triisobutylaluminum, and 40 mg of the solid catalyst component (X-1) as a solid content were added, and then heated to 80° C. and 0.8 MPaG with ethylene. , the pressure was increased, and the polymerization reaction was carried out for 90 minutes. After filtering the obtained polymer, it was 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 method described above was 1.5 wt %. The polymerization activity per solid catalyst was 1,460 g/g-cat. Met. No deposits were found on the walls of the autoclave or the stirring blades after the slurry polymerization.

To the obtained ethylene-based polymer, 0.1% by mass of IrganoX1076 (trade name, manufactured by Ciba Specialty Chemicals Co., Ltd.) and 0.1% by mass of Irgafos168 (trade name, manufactured by Ciba Specialty Chemicals Co., Ltd.) are added as heat stabilizers. , Labo Plastomill (manufactured by Toyo Seiki Seisakusho Co., Ltd.), and melt-kneaded for 5 minutes at a resin temperature of 180° C. and a rotation speed of 50 rpm. Further, this molten polymer was cooled using a press molding machine (manufactured by Shindo Kinzoku Kogyo Co., Ltd.) under conditions of a cooling temperature of 20° C., a cooling time of 5 minutes, and a cooling pressure of 100 kg/cm ² . Using the obtained sample as a measurement sample, physical properties were measured. Table 8 shows the results.

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

<Production of ethylene polymer>
After adding 500 ml of heptane in a nitrogen atmosphere to a 1 liter SUS autoclave equipped with a stirring blade that was sufficiently purged with nitrogen, ethylene was passed through to saturate the liquid phase and 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 content, an ethylene/hydrogen mixed gas having a hydrogen concentration of 0.1 vol% was added. was used to raise the temperature and pressure to 80° C. and 0.8 MPaG, and the polymerization reaction was carried out for 90 minutes. After filtering the obtained polymer, it was vacuum-dried at 80° C. for 10 hours to obtain 143.2 g of an ethylene-based polymer. At this time, the amount of free polymer measured by the above method was 0.7 wt%. The polymerization activity per solid catalyst was 2,390 g/g-cat. Met. No deposits were found on the walls of the autoclave or the stirring blades after the slurry polymerization. The obtained ethylene-based polymer was melt-kneaded and cooled in the same manner as in Example 1, and the physical properties were measured using the obtained sample as a measurement sample. Table 8 shows the results.

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

<Production of ethylene polymer>
After adding 500 ml of heptane in a nitrogen atmosphere to a 1 liter SUS autoclave equipped with a stirring blade that was sufficiently purged with nitrogen, ethylene was passed through to saturate the liquid phase and gas phase with ethylene. Next, 10 mL of 1-hexene, 0.375 mmol of triisobutylaluminum, and 50 mg of the solid catalyst component (X-3) as a solid content were charged, and then heated to 80° C. and 0.8 MPaG with ethylene. , the pressure was increased, and the polymerization reaction was carried out for 90 minutes. After filtering the obtained polymer, it was vacuum-dried at 80° C. for 10 hours to obtain 96.9 g of an ethylene-based polymer. At this time, the amount of free polymer measured by the above method was 2.4 wt %. The polymerization activity per solid catalyst was 1,930 g/g-cat. Met. No deposits were found on the walls of the autoclave or the stirring blades after the slurry polymerization. The obtained ethylene-based polymer was melt-kneaded and cooled in the same manner as in Example 1, and the physical properties were measured using the obtained sample as a measurement sample. Table 8 shows the results.

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

<Production of ethylene polymer>
87.0 g of an ethylene polymer was obtained in the same manner as in Example 1, except that 60 mg of the solid catalyst component (X-4) was used instead of 40 mg of the solid catalyst component (X-1). rice field. At this time, the amount of free polymer measured by the above method was 10.0 wt %. The polymerization activity per solid catalyst was 1,450 g/g-cat. Met. Deposits were found on the autoclave walls and stirring blades after slurry polymerization. The obtained ethylene-based polymer was melt-kneaded and cooled in the same manner as in Example 1, and the physical properties were measured using the obtained sample as a measurement sample. Table 8 shows the results.

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

<Production of ethylene polymer>
27.0 g of an ethylene polymer was obtained 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). rice field. At this time, the amount of free polymer measured by the above method was 8.5 wt %. The polymerization activity per solid catalyst was 270 g/g-cat. Met. Deposits were found on the autoclave walls and stirring blades after slurry polymerization. The obtained ethylene-based polymer was melt-kneaded and cooled in the same manner as in Example 1, and the physical properties were measured using the obtained sample as a measurement sample. Table 8 shows the results.

Although the ethylene polymers obtained in Examples 1 to 3 had lower molecular weights than the ethylene polymers obtained in Comparative Examples 1 and 2, the amount of free polymer was remarkably small. In addition, no deposits were observed on the autoclave wall surface or stirring blades, and fouling was suppressed. That is, it is clear that in Examples 1 to 3 of the present invention, it is possible to stably produce an ethylene polymer having a large amount of long-chain branching and excellent moldability as compared to Comparative Examples 1 and 2.

Claims (11)

An olefin polymerization catalyst comprising the following component (A), the following component (B), the following component (C) and a solid carrier (S).
Component (A): 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 from 1 to 4 that satisfies the valence of M,
X is a hydrogen atom, a halogen atom, a hydrocarbon group, an anionic ligand, or a neutral ligand capable of coordinating with a lone pair; 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 derivative group; when n is 2 or more, a plurality of Xs may be the same or different. may be combined with each other to form a ring,
Q ¹ is a Group 14 transition atom of the periodic table,
all of R ¹ to R ⁴ are hydrogen atoms, or R ¹ and R ⁴ are hydrogen atoms, and R ² and R ³ are bonded to each other to form a ring optionally having a substituent; and
R ⁷ to R ¹² are each independently a hydrogen atom or a hydrocarbon 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, a substituted furan ring or a substituted thiophene ring ;
R ⁶ is a saturated hydrocarbon group having a linear portion of 3 to 10 carbon atoms or a terminal unsaturated hydrocarbon group having a linear portion of 3 to 10 carbon atoms ,
Adjacent substituents of R ⁷ to R ¹⁰ may be combined to form an optionally substituted ring,
R ¹¹ and R ¹² may combine with each other to form a ring containing Q ¹ , and the ring may have a substituent. ]
Component (B): a 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,
each X is an atom or 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 a tin Two adjacent groups selected from the containing groups may combine to form a ring. ]
Component (C): an organometallic compound (c-1) represented by the following general formulas (3) to (5), an organoaluminum oxy compound (c-2), and components (A) and (B) at least one compound selected from the group consisting of compounds (c-3) that react to form an ion pair;
R ^a _m Al (OR ^b ) _n H _p X _q (3)
[In the 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 satisfying 0≤q<3, and m+n+p+q=3. ]
M ^a AlR ^a ₄ (4)
[In Formula (4), M ^a represents Li, Na or K, and R ^a represents a hydrocarbon group having 1 to 15 carbon atoms. ]
R ^a _r M ^b R ^b _s X _t (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 represents 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. or a silicon atom. 3. The olefin polymerization catalyst according to claim 2, wherein Q1 in the formula ( ¹ ) is a silicon atom. In the above formula (1), R ¹ to R ⁴ are all hydrogen atoms, and R ⁵ and R ⁸ to R ¹² are each independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms. The catalyst for olefin polymerization according to claim 3. In the above formula (1), R ¹ and R ⁴ are hydrogen atoms, and R ² and R ³ may have substituents that are bonded to each other and fused to the cyclopentadienyl ring portion. characterized in that it forms a ring as an unsaturated hydrocarbon group having up to 8 members, and R ⁵ and R ⁸ to R ¹² are each independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms. The catalyst for olefin polymerization according to claim 3 . 6. The olefin polymerization catalyst according to claim 4 , wherein R ⁷ to R ¹⁰ in the formula (1) are all hydrogen atoms. A solid catalyst component formed from the solid carrier (S), the component (C) and the component (A), and a solid catalyst component formed from the solid carrier (S), the component (C) and the component (B) The olefin polymerization catalyst according to any one of claims 1 to 6 , comprising: The olefin according to any one of claims 1 to 6 , characterized in that it consists of a solid catalyst component formed from a solid support (S), component (A), component (B) and component (C). Polymerization catalyst. 7. The olefin polymerization catalyst according to any one of claims 1 to 6 , wherein component (C) is an organoaluminumoxy compound and solid support (S) is a porous oxide. In the presence of the olefin polymerization catalyst according to any one of claims 1 to 9 , ethylene is polymerized alone, or ethylene and an olefin having 3 to 20 carbon atoms are copolymerized. A method for producing an ethylene-based polymer. According to claim 10 , the ethylene-based polymer is a copolymer of ethylene and an α-olefin having 4 to 20 carbon atoms and satisfies the following requirements (1) to (4). A method for producing the described ethylene-based polymer:
(1) Melt flow rate (MFR) at 190° C. with a load of 2.16 kg is 0.1 g/10 min or more and 30 g/10 min or less;
(2) Density is 875 kg/m ³ or more and 970 kg/m ³ or less;
( ₃ ) The ratio ( ^η ₀ /Mw ^6.8 ) is 0.03×10 ⁻³⁰ or more and 7.5×10 ⁻³⁰ or less;
(4) Intrinsic viscosity [[η] (dl/g)] measured in decalin at 135°C and the weight average molecular weight measured by the GPC-viscosity detector method (GPC-VISCO) to the power of 0.776 (Mw ^0.776 ) ratio ([η]/Mw ^0.776 ) is 0.90×10 ⁻⁴ or more and 1.65×10 ⁻⁴ or less.