JP2019172603A - Transition metal compound, catalyst for olefin polymerization and method for producing olefin polymer - Google Patents

Abstract

To provide a transition metal compound useful for the production of an olefin polymer with a high molecular weight.SOLUTION: The present invention provides a transition metal compound [A] represented by formula [I]. [R-Rare H, a hydrocarbon group or the like; M is a group 4 transition metal atom; j is an integer of 1-4; Q is halogen or the like; A and B are S, O, N=CRor CR(Ris H, a hydrocarbon group or the like); if A is S, O or N=CR, then B is CR, and if B is S, O or N=CR, then A is CR; a ring containing A and B has a double bond].SELECTED DRAWING: None

Description

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

  In recent years, metallocene compounds are well known as homogeneous catalysts for olefin polymerization. A method for polymerizing olefins using a metallocene compound, particularly a method for stereoregularly polymerizing α-olefins, has been a lot of research since isotactic polymerization was reported by W. Kaminsky et al. Has been made.

  In the polymerization of α-olefin using a metallocene compound, it can be obtained by introducing a substituent into the cyclopentadienyl ring of the ligand of the metallocene compound or by crosslinking two cyclopentadienyl rings. It is known that the stereoregularity and molecular weight of α-olefin polymers change greatly. Various properties such as mechanical strength and heat resistance of the α-olefin polymer are improved by increasing the stereoregularity of the α-olefin polymer or increasing the molecular weight.

  For example, when a metallocene compound having a ligand in which a cyclopentadienyl ring and a fluorenyl ring are bridged is used as a polymerization catalyst for propylene, from the viewpoint of stereoregularity of the polymer, dimethylmethylene (cyclopentadienyl) ) (Fluorenyl) zirconium dichloride is syndiotactic polypropylene (Non-Patent Document 2), and dimethylmethylene (3-methylcyclopentadienyl) (fluorenyl) zirconium dichloride in which a methyl group is introduced at the 3-position of the cyclopentadienyl ring is Hemiisotactic polypropylene (Patent Document 1) is similarly used in dimethylmethylene (3-tert-butylcyclopentadienyl) (fluorenyl) zirconium dichloride in which a tert-butyl group is introduced at the 3-position of the cyclopentadienyl ring. Isotact Click polypropylene is obtained (Patent Document 2).

  Further, Patent Document 3 discloses a metallocene compound represented by the following formula. By performing olefin polymerization in the presence of this metallocene compound, particularly propylene polymerization, the molecular weight decreased with a narrow molecular weight distribution. It is described that polymers with crystallinity can be produced.

LGZMXp
[L is a divalent group that bridges molecules G and Z;
Z is represented by the following formula;

（Ｒ³およびＲ⁴は、水素、アルキル基等であり、
ＡおよびＢは、硫黄（Ｓ）、酸素（Ｏ）またはＣＲ⁵（Ｒ⁵は、水素、アルキル基等である。）、ＡがＳ又はＯであるならばＢはＣＲ⁵であるか、又はＢがＳ又はＯであるならばＡはＣＲ⁵であり、ＡとＢを含む環は可能な位置で二重結合を有する）であり；
Ｇは下式で表され；

(R ³ and R ⁴ are hydrogen, an alkyl group, etc.,
A and B are sulfur (S), oxygen (O) or CR ⁵ (R ⁵ is hydrogen, an alkyl group, etc.), if A is S or O, B is CR ⁵ , or If B is S or O, then A is CR ⁵ and the ring containing A and B has a double bond at a possible position);
G is represented by the following formula;

（Ｒ⁶〜Ｒ⁹は、水素、アルキル基等である。）
Ｍは、所定の遷移金属原子であり；
Ｘは、ハロゲン原子等であり；
ｐは１〜３の整数である。〕

(R ^{6 to} R ⁹ are hydrogen, an alkyl group, etc.)
M is a predetermined transition metal atom;
X is a halogen atom or the like;
p is an integer of 1 to 3. ]

Japanese Patent Laid-Open No. 3-19396 JP-A-6-122718 Special table 2003-519156 gazette

Angew. Chem. Int. Ed. Engl., 24, 507 (1985) J. Am. Chem. Soc., 110, 6225 (1988)

However, ethylene polymerization using a conventional metallocene compound has room for further improvement in terms of increasing the molecular weight.
An object of this invention is to provide the manufacturing method of an olefin polymer with a high molecular weight, a metallocene compound useful for manufacture of such an olefin polymer, and the catalyst for olefin polymerization.

As a result of intensive studies, the present inventors have found that the above problems can be solved by using a novel metallocene compound, and have completed the present invention.
The gist of the present invention is as follows.

[1]
Transition metal compound [A] represented by the following general formula [I].

［式［Ｉ］中、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶、Ｒ⁷およびＲ⁸は、それぞれ独立に、水素原子、炭化水素基、ケイ素含有基、ハロゲン原子またはハロゲン含有炭化水素基であり、
Ｒ¹〜Ｒ⁸のうちの隣接した置換基同士は、互いに結合して環を形成していてもよく、
Ｒ⁹およびＲ¹⁰は、それぞれ独立に、水素原子、炭素数１から２０の炭化水素基、アリール基、置換アリール基、ケイ素含有基、窒素含有基、酸素含有基、ハロゲン原子およびハロゲン含有基からなる群から選ばれる原子または置換基であり、
ＡおよびＢは、硫黄原子、酸素原子、Ｎ＝ＣＲ¹¹またはＣＲ¹¹であり、複数個あるＲ¹¹は、それぞれ独立に、水素原子、炭素数１から２０の炭化水素基、アリール基、置換アリール基、ケイ素含有基、窒素含有基、酸素含有基、ハロゲン原子およびハロゲン含有基からなる群から選ばれる原子または置換基であり、Ａが硫黄原子、酸素原子またはＮ＝ＣＲ¹¹である場合、ＢはＣＲ¹¹であり、Ｂが硫黄原子、酸素原子またはＮ＝ＣＲ¹¹である場合、ＡはＣＲ¹¹であり、ＡおよびＢを含む環は二重結合を形成可能な位置に二重結合を有し、
Ｍは周期表第４族遷移金属原子であり、
ｊは１〜４の整数であり、
Ｑはハロゲン原子、炭化水素基、炭素原子数１０以下の中性の共役もしくは非共役ジエン、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、ｊが２以上の場合、複数個あるＱはそれぞれ同一であっても異なっていてもよい。］

[In the formula [I], R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently a hydrogen atom, a hydrocarbon group, a silicon-containing group, a halogen atom or A halogen-containing hydrocarbon group,
The adjacent substituents of R ^{1 to} R ⁸ may be bonded to each other to form a ring,
R ⁹ and R ¹⁰ are each independently a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an aryl group, a substituted aryl group, a silicon-containing group, a nitrogen-containing group, an oxygen-containing group, a halogen atom or a halogen-containing group. An atom or substituent selected from the group consisting of
A and B are a sulfur atom, an oxygen atom, N = CR ¹¹ or CR ¹¹ , and a plurality of R ¹¹ are each independently a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an aryl group, or a substituted aryl. An atom or a substituent selected from the group consisting of a group, a silicon-containing group, a nitrogen-containing group, an oxygen-containing group, a halogen atom and a halogen-containing group, and when A is a sulfur atom, an oxygen atom or N = CR ¹¹ , B Is CR ¹¹ and when B is a sulfur atom, oxygen atom or N = CR ¹¹ , A is CR ¹¹ and the ring containing A and B has a double bond at a position where a double bond can be formed. And
M is a group 4 transition metal atom in the periodic table,
j is an integer of 1 to 4,
Q is a halogen atom, a hydrocarbon group, a neutral conjugated or non-conjugated diene having 10 or less carbon atoms, an anionic ligand, or a neutral ligand that can coordinate with a lone electron pair, and j is 2 or more. In this case, a plurality of Qs may be the same or different. ]

[2]
The transition metal compound [A] of the above [1], wherein in the general formula [I], R ¹ is a tert-butyl group or a 1-adamantyl group.
[3]
The catalyst for olefin polymerization containing the transition metal compound [A] of [1] or [2].
[4]
[B] [B-1] organometallic compound,
[B-2] The above-mentioned [3] further containing at least one compound selected from the group consisting of an organoaluminum oxy compound and [B-3] a compound that reacts with a transition metal compound [A] to form an ion pair. ] Olefin polymerization catalyst.

[5]
The catalyst for olefin polymerization of [3] or [4], further comprising a support [C], wherein the transition metal compound [A] is supported on the support [C].
[6]
The manufacturing method of the olefin polymer including process [P] which superposes | polymerizes ethylene in presence of the catalyst for olefin polymerization in any one of said [3]-[5].

[7]
The method for producing an olefin polymer according to [6], wherein the step [P] is a step of polymerizing ethylene at a temperature of 40 ° C. or higher and 200 ° C. or lower.
[8]
The method for producing an olefin polymer according to [6] or [7], wherein the step [P] is a step of homopolymerizing ethylene.
[9]
The step [P] is an α-olefin having 3 to 20 carbon atoms together with ethylene, and the proportion of structural units derived from the α-olefin in the olefin polymer is less than 50 mol% with respect to the total structural units. The method for producing an olefin polymer according to the above [6] or [7], which is a step of copolymerizing to a proportion.

  According to the present invention, an olefin polymer having a high molecular weight can be produced.

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

<R ⁸ from R ^1>
In the formula [I], R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently a hydrogen atom, a hydrocarbon group, a silicon-containing group, a halogen atom or a halogen atom. It is a contained hydrocarbon group.

Examples of the hydrocarbon group in R ¹ to R ⁸ include one or more of a linear hydrocarbon group, a branched hydrocarbon group, a cyclic saturated hydrocarbon group, a cyclic unsaturated hydrocarbon group, and a saturated hydrocarbon group. And a group formed by substituting a hydrogen atom of a cyclic unsaturated hydrocarbon group. Carbon number of a hydrocarbon group is 1-20 normally, Preferably it is 1-15, More preferably, it is 1-10.

  Examples of the linear hydrocarbon group include methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, and n-nonyl. And linear alkyl groups such as n-decanyl group; linear alkenyl groups such as allyl group.

  Examples of the branched hydrocarbon group include isopropyl group, tert-butyl group, tert-amyl group, 3-methylpentyl group, 1,1-diethylpropyl group, 1,1-dimethylbutyl group, 1-methyl-1 Examples thereof include branched alkyl groups such as -propylbutyl group, 1,1-propylbutyl group, 1,1-dimethyl-2-methylpropyl group, and 1-methyl-1-isopropyl-2-methylpropyl group.

  Examples of the cyclic saturated hydrocarbon group include cycloalkyl groups such as cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, and methylcyclohexyl group; and polycyclic groups such as norbornyl group, adamantyl group, and methyladamantyl group. It is done.

  Examples of the cyclic unsaturated hydrocarbon group include an aryl group such as a phenyl group, a tolyl group, a naphthyl group, a biphenyl group, a phenanthryl group, and an anthracenyl group; a cycloalkenyl group such as a cyclohexenyl group; and 5-bicyclo [2.2. 1] Polycyclic unsaturated alicyclic groups such as a hepta-2-enyl group.

  Examples of the group formed by substituting one or more hydrogen atoms of a saturated hydrocarbon group with a cyclic unsaturated hydrocarbon group include a benzyl group, a cumyl group, a 1,1-diphenylethyl group, and a triphenylmethyl group. And a group formed by substituting one or two or more hydrogen atoms of the alkyl group with an aryl group.

Examples of the silicon-containing group in R ¹ to R ⁸ include a formula —SiR ₃ such as a trimethylsilyl group, a triethylsilyl group, a dimethylphenylsilyl group, a diphenylmethylsilyl group, a triphenylsilyl group, and the like. Independently an alkyl group having 1 to 15 carbon atoms or a phenyl group).

Of the substituents from R ¹ to R ⁸ , two adjacent substituents (eg, R ⁸ and R ¹ , R ¹ and R ² , R ³ and R ⁵ , R ³ and R ⁶ , R ⁴ and R ⁵⁾ R ⁴ and R ⁶ , R ⁵ and R ⁷ , R ⁶ and R ⁷ ; R ³ and R ⁴ , R ⁵ and R ⁶ ; R ² and R ³ , R ² and R ⁴ ; R ⁷ and R ⁸ ) They may be bonded to each other to form a ring, or may not be bonded to each other. Two or more ring formations may exist in the molecule.

  In this specification, examples of the ring (additional ring) formed by bonding two substituents to each other include an alicyclic ring, an aromatic ring, and a heterocyclic ring. Specifically, a cyclohexane ring, a benzene ring, a hydrogenated benzene ring, and a cyclopentene ring are mentioned, Preferably a cyclohexane ring, a benzene ring, and a hydrogenated benzene ring are mentioned. Such a ring structure may further have a substituent such as an alkyl group on the ring.

Examples of halogen atoms include group 17 elements such as fluorine, chlorine, bromine and iodine.
Examples of the halogen-containing group include a trifluoromethyl group, a tribromomethyl group, a pentafluoroethyl group, and a pentafluorophenyl group, which are groups in which the hydrogen atom is substituted with a halogen atom in the above-described hydrocarbon group or silicon-containing group. Illustrated.

R ² and R ⁸ are preferably a hydrogen atom.
R ¹ is preferably a hydrocarbon group or a silicon-containing group, more preferably a hydrocarbon group, more preferably a hydrocarbon group having 1 to 20 carbon atoms, and not an aryl group. More preferably, it is a straight chain hydrocarbon group, a branched hydrocarbon group or a cyclic saturated hydrocarbon group, and the carbon having a free valence (carbon bonded to the cyclopentadienyl ring) is a tertiary carbon. Particularly preferred is a certain substituent.

Specific examples of R ¹ include a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, a tert-pentyl group, a tert-amyl group, a 1-methylcyclohexyl group, and a 1-adamantyl group. Is a substituent in which the carbon having a free valence is a tertiary carbon, such as a tert-butyl group, a tert-pentyl group, a 1-methylcyclohexyl group, or a 1-adamantyl group, particularly preferably a 1-adamantyl group, tert- It is a butyl group.

R ^{3 to} R ⁶ are preferably each independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. As a hydrocarbon group, the C1-C20 alkyl group enumerated above is preferable. R ⁴ and R ⁵ may be bonded to each other to form the ring described above, and examples of the ring include an alicyclic ring such as a cyclohexane ring.
R ⁷ is preferably a hydrocarbon group, and particularly preferably an alkyl group such as a methyl group.

<R ^9, R ^10, A and B>
R ⁹ and R ¹⁰ are each independently a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an aryl group, a substituted aryl group, a silicon-containing group, a nitrogen-containing group, an oxygen-containing group, a halogen atom or a halogen-containing group. The atom or substituent selected.

A and B are a sulfur atom, an oxygen atom, N = CR ¹¹ or CR ¹¹ , and a plurality of R ¹¹ are each independently a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an aryl group, or a substituted aryl. An atom or a substituent selected from the group consisting of a group, a silicon-containing group, a nitrogen-containing group, an oxygen-containing group, a halogen atom and a halogen-containing group, and when A is a sulfur atom, an oxygen atom or N = CR ¹¹ , B Is CR ¹¹ and when B is a sulfur atom, oxygen atom or N = CR ¹¹ , A is CR ¹¹ , and in a preferred embodiment, A or B is a sulfur atom and the other is CH. Can be mentioned. The ring containing A and B has a double bond at a position where a double bond can be formed.

  In general formula [I]

で表される構造の例としては、以下の構造が挙げられる。

The following structures are mentioned as an example of the structure represented by these.

炭素数１から２０の炭化水素基としては、炭素数１〜２０のアルキル基、炭素数３〜２０の環状飽和炭化水素基、炭素数２〜２０の鎖状不飽和炭化水素基、炭素数３〜２０の環状不飽和炭化水素基が例示される。

Examples of the hydrocarbon group having 1 to 20 carbon atoms include an alkyl group having 1 to 20 carbon atoms, a cyclic saturated hydrocarbon group having 3 to 20 carbon atoms, a chain unsaturated hydrocarbon group having 2 to 20 carbon atoms, and 3 carbon atoms. Illustrative are -20 cyclic unsaturated hydrocarbon groups.

  Examples of the alkyl group having 1 to 20 carbon atoms include methyl, ethyl, n-propyl, allyl, n-butyl, n-pentyl, and n-hexyl which are linear saturated hydrocarbon groups. Group, n-heptyl group, n-octyl group, n-nonyl group, n-decanyl group, etc., branched saturated hydrocarbon groups such as isopropyl group, isobutyl group, s-butyl group, t-butyl group, t-amyl group Group, neopentyl group, 3-methylpentyl group, 1,1-diethylpropyl group, 1,1-dimethylbutyl group, 1-methyl-1-propylbutyl group, 1,1-dipropylbutyl group, 1,1- Examples include dimethyl-2-methylpropyl group, 1-methyl-1-isopropyl-2-methylpropyl group, cyclopropylmethyl group and the like. Preferably carbon number of an alkyl group is 1-6.

  Examples of the cyclic saturated hydrocarbon group having 3 to 20 carbon atoms include cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, norbornenyl group, 1-adamantyl group, which are cyclic saturated hydrocarbon groups, 3-methylcyclopentyl group, 3-methylcyclohexyl group, 4-methylcyclohexyl group, which is a group in which a hydrogen atom of a cyclic saturated hydrocarbon group such as 2-adamantyl group is replaced with a hydrocarbon group having 1 to 17 carbon atoms, 4 Examples include -cyclohexylcyclohexyl group and 4-phenylcyclohexyl group. The number of carbon atoms of the cyclic saturated hydrocarbon group is preferably 5-11.

  Examples of chain unsaturated hydrocarbon groups having 2 to 20 carbon atoms include ethenyl groups (vinyl groups), 1-propenyl groups, 2-propenyl groups (allyl groups), and 1-methylethenyl groups (isopropenyl groups) which are alkenyl groups. Examples thereof include ethynyl group, 1-propynyl group, 2-propynyl group (propargyl group), which are alkynyl groups. The chain unsaturated hydrocarbon group preferably has 2 to 4 carbon atoms.

  Examples of the cyclic unsaturated hydrocarbon group having 3 to 20 carbon atoms include cyclopentadienyl group, norbornyl group, phenyl group, naphthyl group, indenyl group, azulenyl group, phenanthryl group, anthracenyl group and the like, which are cyclic unsaturated hydrocarbon groups 3-methylphenyl group (m-tolyl group), 4-methylphenyl group (p-tolyl group), which is a group in which a hydrogen atom of a cyclic unsaturated hydrocarbon group is replaced with a hydrocarbon group having 1 to 15 carbon atoms 4-ethylphenyl group, 4-t-butylphenyl group, 4-cyclohexylphenyl group, biphenylyl group, 3,4-dimethylphenyl group, 3,5-dimethylphenyl group, 2,4,6-trimethylphenyl group ( A group in which a hydrogen atom of a linear hydrocarbon group or a branched saturated hydrocarbon group is replaced by a cyclic saturated hydrocarbon group or a cyclic unsaturated hydrocarbon group having 3 to 19 carbon atoms, such as a mesityl group) Njiru group, such as cumyl group and the like. The number of carbon atoms of the cyclic unsaturated hydrocarbon group is preferably 6-10.

  Examples of the alkylene group having 1 to 20 carbon atoms include methylene group, ethylene group, dimethylmethylene group (isopropylidene group), ethylmethylene group, 1-methylethylene group, 2-methylethylene group, 1,1-dimethylethylene group, Examples include 1,2-dimethylethylene group and n-propylene group. Preferably carbon number of an alkylene group is 1-6.

  Examples of the arylene group having 6 to 20 carbon atoms include o-phenylene group, m-phenylene group, p-phenylene group, and 4,4′-biphenylylene group. The carbon number of the arylene group is preferably 6 to 12.

  The aryl group partially overlaps with the above-described examples of the cyclic unsaturated hydrocarbon group having 3 to 20 carbon atoms, but is a phenyl group, 1-naphthyl group, 2-naphthyl which is a substituent derived from an aromatic compound. Groups, anthracenyl group, phenanthrenyl group, tetracenyl group, chrysenyl group, pyrenyl group, indenyl group, azulenyl group, pyrrolyl group, pyridyl group, furanyl group, thiophenyl group and the like are exemplified. As the aryl group, a phenyl group or a 2-naphthyl group is preferable.

  Examples of the aromatic compounds include aromatic hydrocarbons and heterocyclic aromatic compounds such as benzene, naphthalene, anthracene, phenanthrene, tetracene, chrysene, pyrene, pyrene, indene, azulene, pyrrole, pyridine, furan, thiophene, etc. Is done.

  The substituted aryl group partially overlaps with the example of the cyclic unsaturated hydrocarbon group having 3 to 20 carbon atoms described above, but one or more hydrogen atoms of the aryl group are hydrocarbon groups having 1 to 20 carbon atoms, Examples include a group substituted with a substituent selected from an aryl group, a silicon-containing group, a nitrogen-containing group, an oxygen-containing group, a halogen atom and a halogen-containing group. Specifically, a 3-methylphenyl group (m-tolyl group) ), 4-methylphenyl group (p-tolyl group), 3-ethylphenyl group, 4-ethylphenyl group, 3,4-dimethylphenyl group, 3,5-dimethylphenyl group, biphenylyl group, 4- (trimethylsilyl) Phenyl group, 4-aminophenyl group, 4- (dimethylamino) phenyl group, 4- (diethylamino) phenyl group, 4-morpholinylphenyl group, 4-methoxyphenyl group, 4-ethoxyphenyl group, 4-phenoxy Enyl group, 3,4-dimethoxyphenyl group, 3,5-dimethoxyphenyl group, 3-methyl-4-methoxyphenyl group, 3,5-dimethyl-4-methoxyphenyl group, 3- (trifluoromethyl) phenyl group 4- (trifluoromethyl) phenyl group, 3-chlorophenyl group, 4-chlorophenyl group, 3-fluorophenyl group, 4-fluorophenyl group, 5-methylnaphthyl group, 2- (6-methyl) pyridyl group, etc. Illustrated. Examples of the substituted aryl group also include “electron-donating group-containing substituted aryl groups” described later.

  Examples of silicon-containing groups include alkyl groups such as trimethylsilyl groups, triethylsilyl groups, t-butyldimethylsilyl groups, triisopropylsilyl groups, etc., which are hydrocarbon groups having 1 to 20 carbon atoms in which carbon atoms are replaced by silicon atoms. Examples thereof include arylsilyl groups such as silyl group, dimethylphenylsilyl group, methyldiphenylsilyl group and t-butyldiphenylsilyl group, pentamethyldisiranyl group and trimethylsilylmethyl group. The alkylsilyl group preferably has 1 to 10 carbon atoms, and the arylsilyl group preferably has 6 to 18 carbon atoms.

Examples of the nitrogen-containing group include an amino group, a nitro group, an N-morpholinyl group, a group in which the above-described hydrocarbon group having 1 to 20 carbon atoms or a silicon-containing group is substituted with a nitrogen atom, A group in which the CH ₂ -structural unit is replaced by a nitrogen atom to which a hydrocarbon group having 1 to 20 carbon atoms is bonded, or a nitrogen atom or nitrile group in which a hydrocarbon group having a -CH ₃ structural unit is bonded to hydrocarbon groups having 1 to 20 carbon atoms And dimethylamino group, diethylamino group, dimethylaminomethyl group, cyano group, pyrrolidinyl group, piperidinyl group, pyridinyl group and the like, which are groups replaced by As the nitrogen-containing group, a dimethylamino group and an N-morpholinyl group are preferable.

Examples of the oxygen-containing group include a hydroxyl group, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, or a nitrogen-containing group in which the —CH ₂ — structural unit is replaced with an oxygen atom or a carbonyl group, or — A methoxy group, an ethoxy group, a t-butoxy group, a phenoxy group, a trimethylsiloxy group, a methoxyethoxy group, hydroxymethyl, which is a group in which the CH ₃ structural unit is replaced by an oxygen atom to which a hydrocarbon group having 1 to 20 carbon atoms is bonded. Group, methoxymethyl group, ethoxymethyl group, t-butoxymethyl group, 1-hydroxyethyl group, 1-methoxyethyl group, 1-ethoxyethyl group, 2-hydroxyethyl group, 2-methoxyethyl group, 2-ethoxyethyl Group, n-2-oxabutylene group, n-2-oxapentylene group, n-3-oxapentylene group, aldehyde group, acetyl group, propionyl group, benzoyl group, Examples include trimethylsilylcarbonyl group, carbamoyl group, methylaminocarbonyl group, carboxy group, methoxycarbonyl group, carboxymethyl group, ethocarboxymethyl group, carbamoylmethyl group, furanyl group, pyranyl group and the like. As the oxygen-containing group, a methoxy group is preferable.

Examples of halogen atoms include group 17 elements such as fluorine, chlorine, bromine and iodine.
Examples of the halogen-containing group include a trifluoromethyl group in which a hydrogen atom is substituted with a halogen atom in the above-described hydrocarbon group having 1 to 20 carbon atoms, silicon-containing group, nitrogen-containing group or oxygen-containing group, tribromo Examples include a methyl group, a pentafluoroethyl group, a pentafluorophenyl group, and the like.

<M, Q, j>
M is a Group 4 transition metal, preferably Ti, Zr or Hf, more preferably Zr or Hf.
j is an integer of 1 to 4, preferably 2.
Q is a halogen atom, a hydrocarbon group, a neutral conjugated or non-conjugated diene having 10 or less carbon atoms, an anionic ligand, or a neutral ligand that can coordinate with a lone electron pair, and j is 2 or more. In this case, a plurality of Qs may be the same or different.

Examples of the halogen atom for Q include fluorine, chlorine, bromine, and iodine.
Examples of the hydrocarbon group for Q include the same groups as the hydrocarbon groups for R ¹ to R ^8, and an alkyl group such as a linear alkyl group or a branched alkyl group is preferable.

  Examples of the anionic ligand for Q include alkoxy groups such as methoxy and tert-butoxy; aryloxy groups such as phenoxy; carboxylate groups such as acetate and benzoate; sulfonate groups such as mesylate and tosylate; dimethylamide and diisopropylamide Amide groups such as methylanilide and diphenylamide.

  Examples of the neutral conjugated or nonconjugated diene having 10 or less carbon atoms in Q include 1,3-butadienyl group, isoprenyl group (2-methyl-1,3-butadienyl group), piperenyl group (1,3- Pentadienyl group), 2,4-hexadienyl group, 1,4-diphenyl-1,3-pentadienyl group, and cyclopentadienyl group.

Examples of the neutral ligand capable of coordinating with a lone pair in Q include, for example, organophosphorus compounds such as trimethylphosphine, triethylphosphine, triphenylphosphine, diphenylmethylphosphine; tetrahydrofuran, diethyl ether, dioxane, 1,2- Examples include ethers such as dimethoxyethane.
It is preferable that at least one Q is a halogen atom or an alkyl group.

The preferred embodiments of the configuration of the transition metal compound (A), that is, R ^{1 to} R ¹⁰ , M, Q, and j have been described above. In the present invention, any combination of the preferred embodiments is also a preferred embodiment.

  Although the specific example of the said transition metal compound (A) of this invention is shown, the range of this invention is not specifically limited by this. In the present invention, the transition metal compound (A) may be used alone or in combination of two or more.

  For the convenience of explanation, the ligand structure excluding MQj (metal part) of the transition metal compound (A) is divided into a pentalene derivative part (α) and a heterocyclic compound part (β). Specific examples of each partial structure are shown in Table 1 and Tables 2A to 2E.

好ましい前記遷移金属化合物（Ａ）としては、たとえば、下式で表される化合物が挙げられる。

Preferable examples of the transition metal compound (A) include compounds represented by the following formula.

According to the above table, when the ligand structure is a combination of α9 and β3 and the metal part MQj is ZrCl ₂ , the transition metal compound represented by the following formula is exemplified.

また、リガンド構造がα９とβ３の組み合わせからなるものであり、金属部分ＭＱｊがＨｆＣｌ₂の場合は、下記式で表される遷移金属化合物を例示している。

When the ligand structure is a combination of α9 and β3 and the metal part MQj is HfCl ₂ , transition metal compounds represented by the following formula are exemplified.

あるいは、リガンド構造がα７とβ３の組み合わせからなるものであり、金属部分ＭＱｊがＺｒＣｌ₂の場合は、下記式で表される遷移金属化合物を例示している。

Alternatively, when the ligand structure is composed of a combination of α7 and β3 and the metal part MQj is ZrCl ₂ , transition metal compounds represented by the following formula are exemplified.

さらに、リガンド構造がα７とβ３の組み合わせからなるものであり、金属部分ＭＱｊがＨｆＣｌ₂の場合は、下記式で表される遷移金属化合物を例示している。

Further, when the ligand structure is composed of a combination of α7 and β3 and the metal part MQj is HfCl ₂ , the transition metal compound represented by the following formula is exemplified.

<< Production Method of Transition Metal Compound [A] >>
The transition metal compound [A] can be produced using a conventionally known method, and examples of typical synthetic routes are shown below, but the production method is not particularly limited. Below, an example of the manufacturing method of the said transition metal compound [A] is demonstrated. In the following formulas, the definitions and specific aspects of R ^{1 to} R ¹⁰ , Q, M, X and j are the same as those described in the general formula [1] unless otherwise specified. is there.

  The method for producing the transition metal compound [A] includes, for example, a step (1) of preparing a pentalene compound represented by the general formula (1a). In the pentalene compound (1a), an isomer corresponding to the configuration of the target transition metal compound [A] can be used.

一実施態様は、工程（１）に続いて、ペンタレン化合物（1a）とヘテロ環化合物（2a）とを反応させて、遷移金属化合物［Ｉ］の前駆体化合物（3a）を得る工程（２）、および前駆体化合物（3a）から遷移金属化合物［Ｉ］を得る工程（３）を有する。

In one embodiment, following the step (1), the pentalene compound (1a) and the heterocyclic compound (2a) are reacted to obtain the precursor compound (3a) of the transition metal compound [I] (2) And a step (3) of obtaining a transition metal compound [I] from the precursor compound (3a).

  In the precursor compound (3a), it is possible to consider the presence of isomers that differ only in the position of the double bond in the cyclopentadienyl ring, and in the following, each reaction is exemplified by only one of them. . The precursor compound (3a) may be another isomer that differs only in the position of the double bond in the cyclopentadienyl ring, or may be a mixture thereof.

<Process (1)>
The pentalene compound (1a) can be produced, for example, by the method described in paragraphs [0089] to [0100] of International Publication No. 2014/50817.

<Process (2)>
In one embodiment, following the step (1), the pentalene compound (1a) and the heterocyclic compound (2a) are reacted to form a precursor compound (3a) of the transition metal compound [A] (the following formula (3a- 1) or a step (2) for obtaining a compound represented by (3a-2).
The heterocyclic compound (2a) is represented by the following formula (2a-1) or (2a-2) and can be obtained by a conventionally known method.

  During the above reaction, L is an alkali metal or alkaline earth metal. Examples of the alkali metal include lithium, sodium, and potassium, and examples of the alkaline earth metal include magnesium and calcium.

  Examples of the organic solvent that can be used in the above reaction include aliphatic hydrocarbons such as pentane, hexane, heptane, cyclohexane, and decalin; aromatic hydrocarbons such as benzene, toluene, and xylene; tetrahydrofuran, diethyl ether, dioxane, 1 , 2-dimethoxyethane, tert-butyl methyl ether, cyclopentyl methyl ether and other ethers; dichloromethane, chloroform and other halogenated hydrocarbons; or solvents obtained by mixing two or more of these.

  The reaction between the pentalene compound (1a) and the heterocyclic compound (2a) is preferably a molar ratio of 10: 1 to 1:10, more preferably 2: 1 to 1: 2, particularly preferably 1.2: 1. 1: 1.2. The reaction temperature is preferably −100 to 150 ° C., more preferably −40 to 120 ° C.

<Process (3)>
An example of producing the transition metal compound [A] from the precursor compound (3a) is shown below. This does not limit the scope of the present invention, and the transition metal compound [A] may be produced by any known method.

<Synthesis of dialkali metal salt>
By bringing the precursor compound (3a) into contact with at least one metal component selected from an alkali metal, an alkali metal hydrogen atom, an alkali metal alkoxide, an organic alkali metal and an organic alkaline earth metal in an organic solvent. To obtain a dialkali metal salt.

  Examples of the alkali metal that can be used in the above reaction include lithium, sodium, and potassium; examples of the hydrogen atom alkali metal include sodium hydrogen atom and potassium hydrogen atom; and examples of the alkali metal alkoxide include Examples include sodium methoxide, potassium ethoxide, sodium ethoxide, potassium tert-butoxide, etc .; examples of the organic alkali metal include methyl lithium, butyl lithium, and phenyl lithium; examples of the organic alkaline earth metal include methyl Examples thereof include magnesium halide, butyl magnesium halide, and phenyl magnesium halide; or two or more of these may be used in combination.

  Examples of the organic solvent used in the above reaction include aliphatic hydrocarbons such as pentane, hexane, heptane, cyclohexane, and decalin; aromatic hydrocarbons such as benzene, toluene, and xylene; tetrahydrofuran, diethyl ether, dioxane, 1, 2, and the like. -Ethers such as dimethoxyethane, tert-butyl methyl ether and cyclopentyl methyl ether; halogenated hydrocarbons such as dichloromethane and chloroform; or solvents obtained by mixing two or more of these.

  The reaction between the precursor compound (3a) and the metal component is preferably a molar ratio (precursor compound (3a): metal component) = 1: 1 to 1:20, more preferably 1: 1.5 to 1: 4, particularly preferably 1: 1.8 to 1: 2.5. The reaction temperature is preferably −100 to 200 ° C., more preferably −80 to 120 ° C.

  In order to promote the reaction, Lewis bases typified by tetramethylethylenediamine and the like, α-methylstyrene and the like as described in International Publication No. 2009/072505 pamphlet can also be used.

<Synthesis of transition metal compounds>
The transition metal compound [A] is synthesized by reacting the dialkali metal salt obtained by the above reaction with the compound represented by the general formula (4a) in an organic solvent.
MZ _{n + 2} (4a)
Examples of the compound (4a) include trivalent or tetravalent titanium fluoride, chloride, bromide and iodide; tetravalent zirconium fluoride, chloride, bromide and iodide; tetravalent hafnium fluoride, chloride. Products, bromides and iodides; or complexes thereof with ethers such as tetrahydrofuran, diethyl ether, dioxane or 1,2-dimethoxyethane.

  Examples of the organic solvent used in the above reaction include the organic solvents described in the section <Synthesis of dialkali metal salt>. The reaction between the dialkali metal salt and the compound (4a) is preferably a molar ratio of 10: 1 to 1:10, more preferably 2: 1 to 1: 2, particularly preferably 1.2: 1 to 1: 1. Perform in step 2. The reaction temperature is preferably -80 to 200 ° C, more preferably -75 to 120 ° C.

<Other methods>
As another method, the precursor compound (3a) is converted into an organometallic reagent such as tetrabenzyl titanium, tetrabenzyl zirconium, tetrabenzyl hafnium, tetrakis (trimethylsilylmethylene) titanium, tetrakis (trimethylsilylmethylene) zirconium, tetrakis (trimethylsilylmethylene) hafnium. Dibenzyldichlorotitanium, dibenzyldichlorozirconium, dibenzyldichlorohafnium, and titanium, zirconium, or hafnium amide salts may be reacted directly.

The transition metal compound [A] obtained by the above reaction can be isolated and purified by methods such as extraction, recrystallization and sublimation. The transition metal compound [A] obtained by such a method is identified by using analytical techniques such as proton nuclear magnetic resonance spectrum, ¹³ C-nuclear magnetic resonance spectrum, mass spectrometry, and elemental analysis.

[Olefin polymerization catalyst]
The catalyst for olefin polymerization according to the present invention contains the transition metal compound [A] of the present invention.
The olefin polymerization catalyst of the present invention is preferably
[B] selected from the group consisting of [B-1] organometallic compounds, [B-2] organoaluminum oxy compounds, and [B-3] transition metal compounds [A] to form ion pairs. At least one compound (hereinafter also referred to as “compound [B]”)
Is further contained.

The olefin polymerization catalyst of the present invention is preferably, if necessary,
(C) It further contains a carrier.
The olefin polymerization catalyst of the present invention, if necessary,
(D) An organic compound component may be further contained.

The olefin polymerization catalyst according to the present invention is not limited to the polymerization of ethylene described later, but also other olefins such as α-olefins having 3 to 20 carbon atoms (α-olefins having 3 to 20 carbon atoms) Ethylene may also be used for copolymerization carried out such that the proportion of structural units derived from ethylene in the olefin polymer is less than 50 mol% with respect to the total structural units. .
Hereinafter, each component other than the transition metal compound [A] will be specifically described.

(Compound [B])
Compound [B] (hereinafter sometimes referred to as “component (B)”)
[B-1] Organometallic compound (hereinafter also referred to as “component (B-1)”), preferably an organoaluminum compound [B-1a] represented by the following general formula (B-1a), B-1b) complex alkylated product of group 1 metal and aluminum [B-1b], or dialkyl compound of group 2 or group 12 metal represented by the following general formula (B-1c) [ B-1c],
R ^a _m Al (OR ^b ) _n H _p X _q (B-1a)
[In the general formula (B-1a), R ^a and R ^b represent a hydrocarbon group having 1 to 15 carbon atoms, which may be the same or different, X represents a halogen atom, and m represents 0. <M ≦ 3, n is 0 ≦ n <3, p is 0 ≦ p <3, q is a number of 0 ≦ q <3, and m + n + p + q = 3. ]
M ^a AlR ^a ₄ (B-1b)
[In the general formula (B-1b), M ^a represents Li, Na or K, and R ^a represents a hydrocarbon group having 1 to 15 (preferably 1 to 4) carbon atoms. ]
R ^a _r M ^b R ^b _s X _t (B-1c)
[In the general formula (B-1c), R ^a and R ^b represent a hydrocarbon group having 1 to 15 carbon atoms, which may be the same or different from each other, and M ^b is selected from Mg, Zn and Cd. X is a halogen atom, r is 0 <r ≦ 2, s is 0 ≦ s ≦ 1, t is 0 ≦ t ≦ 1, and r + s + t = 2. ],
[B-2] an organoaluminum oxy compound (hereinafter also referred to as “component (B-2)”), and [B-3] a compound that forms an ion pair by reacting with the transition metal compound [A] (hereinafter referred to as “component”). (B-3) ".)
At least one compound selected from the group consisting of:

<< Organic metal compound [B-1] >>
Examples of the organoaluminum compound [B-1a] include trialkylaluminum such as trimethylaluminum, triethylaluminum, and triisobutylaluminum, dialkylaluminum hydride such as diisobutylaluminum hydride, and tricycloalkylaluminum.

Examples of the complex alkylated product [B-1b] of Group 1 metal and aluminum include LiAl (C ₂ H ₅ ) ₄ and LiAl (C ₇ H ₁₅ ) ₄ .
Examples of the group 2 or group 12 metal dialkyl compound [B-1c] include dimethylmagnesium, diethylmagnesium, di-n-butylmagnesium, ethyl n-butylmagnesium, diphenylmagnesium, dimethylzinc, diethylzinc, and din. -Butyl zinc and diphenyl zinc are mentioned.
Among these, the organoaluminum compound [B-1a] is preferable.
Organometallic compound [B-1] may be used individually by 1 type, and may use 2 or more types together.

<< Organic aluminum oxy compound [B-2] >>
The organoaluminum oxy compound [B-2] may be, for example, a conventionally known aluminoxane, which is insoluble or hardly soluble in benzene as exemplified in JP-A-2-78687. It may be a compound. A conventionally well-known aluminoxane can be manufactured, for example by the method of following (1)-(4), and is normally obtained as a solution of a hydrocarbon solvent.

  (1) A compound containing adsorbed water or a salt containing water of crystallization, such as magnesium chloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate, first cerium chloride hydrate A method of reacting adsorbed water or crystal water with an organoaluminum compound by adding an organoaluminum compound such as trialkylaluminum to a hydrocarbon medium suspension such as

  (2) A method in which water, ice or water vapor is directly applied to an organoaluminum compound such as trialkylaluminum in a medium such as benzene, toluene, diethyl ether or tetrahydrofuran.

  (3) A method in which an organotin oxide such as dimethyltin oxide or dibutyltin oxide is reacted with an organoaluminum compound such as trialkylaluminum in a medium such as decane, benzene, or toluene.

  (4) A non-hydrolytic reaction such as a thermal decomposition reaction is performed on a compound formed by reacting an organic aluminum such as a trialkylaluminum with an organic compound having a carbon-oxygen bond such as a tertiary alcohol, ketone, or carboxylic acid. How to convert.

  The aluminoxane may contain a small amount of an organometallic component. Alternatively, the solvent or the unreacted organoaluminum compound may be removed by distillation from the recovered aluminoxane solution, and then redissolved in a solvent or suspended in a poor aluminoxane solvent.

  Specific examples of the organoaluminum compound used when preparing the aluminoxane include the same organoaluminum compounds as those exemplified as the organoaluminum compound [B-1a]. Among these, trialkylaluminum and tricycloalkylaluminum are preferable, and trimethylaluminum is particularly preferable.

  Other examples of the organoaluminum oxy compound [B-2] include modified methylaluminoxane. Modified methylaluminoxane is an aluminoxane prepared using trimethylaluminum and an alkylaluminum other than trimethylaluminum. Such a compound is generally called MMAO. MMAO can be prepared by the methods listed in US Pat. No. 4,960,878 and US Pat. No. 5,041,584. In addition, aluminoxanes prepared by using trimethylaluminum and triisobutylaluminum from Tosoh Finechem Co., Ltd. and the like, in which R is an isobutyl group, are commercially produced under the names MMAO and TMAO.

  Such MMAO is an aluminoxane having improved solubility in various solvents and storage stability. Specifically, unlike MMAO, which is insoluble or hardly soluble in benzene, aliphatic hydrocarbons and It has the feature of being soluble in alicyclic hydrocarbons.

Furthermore, as the organoaluminum oxy compound [B-2], for example, an organoaluminum oxy compound containing a boron atom, or a halogen as exemplified in International Publication No. 2005/066191 and International Publication No. 2007/131010. Examples of the aluminoxane include ionic aluminoxane as exemplified in International Publication No. WO2003 / 082879.
The organoaluminum oxy compound [B-2] may be used alone or in combination of two or more.

<< Compound [B-3] which reacts with transition metal compound [A] to form an ion pair >>
As the compound [B-3] (hereinafter also referred to as “ionic compound [B-3]”) that reacts with the transition metal compound [A] to form an ion pair, for example, JP-A-1-501950 JP-A-1-502036, JP-A-3-179005, JP-A-3-179006, JP-A-3-207703, JP-A-3-207704, US Pat. No. 5,321,106, etc. And Lewis acids, ionic compounds, borane compounds and carborane compounds described in 1). Furthermore, heteropoly compounds and isopoly compounds can also be mentioned.
As the ionic compound [B-3], a compound represented by the general formula (B-3a) is preferable.

In the formula (B-3a), examples of R ^{e +} include H ⁺ , carbenium cation, oxonium cation, ammonium cation, phosphonium cation, cycloheptyltrienyl cation, and ferrocenium cation having a transition metal. R ^{f to} R ⁱ are each independently an organic group, preferably an aryl group.

  Examples of the carbenium cation include trisubstituted carbenium cations such as a triphenyl carbenium cation, a tris (methylphenyl) carbenium cation, and a tris (dimethylphenyl) carbenium cation.

  Examples of the ammonium cation include trialkylammonium cations such as trimethylammonium cation, triethylammonium cation, tri (n-propyl) ammonium cation, triisopropylammonium cation, tri (n-butyl) ammonium cation, and triisobutylammonium cation; N N, N-dimethylanilinium cation, N, N-diethylanilinium cation, N, N-2,4,6-pentamethylanilinium cation, etc., N, N-dialkylanilinium cation; diisopropylammonium cation, dicyclohexylammonium cation And dialkyl ammonium cations.

  Examples of the phosphonium cation include triarylphosphonium cations such as a triphenylphosphonium cation, a tris (methylphenyl) phosphonium cation, and a tris (dimethylphenyl) phosphonium cation.

As R ^{e +} , for example, a carbenium cation and an ammonium cation are preferable, and a triphenylcarbenium cation, an N, N-dimethylanilinium cation, and an N, N-diethylanilinium cation are particularly preferable.

  Examples of the carbenium salt include triphenylcarbenium tetraphenylborate, triphenylcarbeniumtetrakis (pentafluorophenyl) borate, triphenylcarbeniumtetrakis (3,5-ditrifluoromethylphenyl) borate, and tris (4-methylphenyl). ) Carbenium tetrakis (pentafluorophenyl) borate, tris (3,5-dimethylphenyl) carbenium tetrakis (pentafluorophenyl) borate.

Examples of ammonium salts include trialkyl-substituted ammonium salts, N, N-dialkylanilinium salts, and dialkylammonium salts.
Examples of the trialkyl-substituted ammonium salt include triethylammonium tetraphenylborate, tripropylammonium tetraphenylborate, tri (n-butyl) ammonium tetraphenylborate, trimethylammonium tetrakis (p-tolyl) borate, trimethylammonium tetrakis (o- Tolyl) borate, tri (n-butyl) ammonium tetrakis (pentafluorophenyl) borate, triethylammonium tetrakis (pentafluorophenyl) borate, tripropylammonium tetrakis (pentafluorophenyl) borate, tripropylammonium tetrakis (2,4-dimethyl) Phenyl) borate, tri (n-butyl) ammonium tetrakis (3,5-dimethylphenyl) bore Tri (n-butyl) ammonium tetrakis (4-trifluoromethylphenyl) borate, tri (n-butyl) ammonium tetrakis (3,5-ditrifluoromethylphenyl) borate, tri (n-butyl) ammonium tetrakis (o -Tolyl) borate, dioctadecylmethylammonium tetraphenylborate, dioctadecylmethylammonium tetrakis (p-tolyl) borate, dioctadecylmethylammonium tetrakis (o-tolyl) borate, dioctadecylmethylammonium tetrakis (pentafluorophenyl) borate, di Octadecylmethylammonium tetrakis (2,4-dimethylphenyl) borate, dioctadecylmethylammonium tetrakis (3,5-dimethylphenyl) borate , Dioctadecyl methyl ammonium tetrakis (4-trifluoromethylphenyl) borate, dioctadecyl methyl ammonium tetrakis (3,5-ditrifluoromethylphenyl) borate include dioctadecyl methyl ammonium.

  Examples of the N, N-dialkylanilinium salt include N, N-dimethylanilinium tetraphenyl borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (3, 5-ditrifluoromethylphenyl) borate, N, N-diethylanilinium tetraphenylborate, N, N-diethylanilinium tetrakis (pentafluorophenyl) borate, N, N-diethylanilinium tetrakis (3,5-ditrifluoro) Methylphenyl) borate, N, N-2,4,6-pentamethylanilinium tetraphenylborate, N, N-2,4,6-pentamethylanilinium tetrakis (pentafluorophenyl) borate.

  Examples of the dialkylammonium salt include di (1-propyl) ammonium tetrakis (pentafluorophenyl) borate and dicyclohexylammonium tetraphenylborate.

As the ionic compound [B-3], other ionic compounds disclosed in JP-A-2004-51676 can be used without limitation.
An ionic compound [B-3] may be used individually by 1 type, and may use 2 or more types together.

<Carrier [C]>
Examples of the carrier [C] include inorganic or organic compounds, and granular or fine particle solids. In the method for producing an olefin polymer of the present invention described later, the transition metal compound [A] is preferably used in a form supported on a carrier [C].

<Inorganic compounds>
The inorganic compound in the carrier [C] is preferably a porous oxide, inorganic chloride, clay, clay mineral or ion-exchangeable layered compound.

Examples of the porous oxide include oxides such as SiO ₂ , Al ₂ O ₃ , MgO, ZrO ₂ , TiO ₂ , B ₂ O ₃ , CaO, ZnO, BaO, and ThO ₂ , or composites containing these, Mixtures can be used. For example, natural or synthetic zeolites, SiO ₂ -MgO, a _{SiO 2 -Al 2 O 3, SiO} 2 -TiO 2, SiO 2 -V 2 O 5, SiO 2 -Cr 2 O 3, SiO 2 -TiO 2 -MgO Can be used. Among these, a porous oxide containing SiO ₂ and / or Al ₂ O ₃ as a main component is preferable.

The properties of porous oxides vary depending on the type and production method. The carrier preferably used in the present invention has a particle size of preferably 1 to 300 μm, more preferably 3 to 100 μm; a specific surface area of preferably 50 to 1300 m ² / g, more preferably 200 to 1200 m ² / g. The pore volume is preferably 0.3 to 3.0 cm ³ / g, more preferably 0.5 to 2.0 cm ³ / g. Such a carrier is used after drying and / or baking at 100 to 1000 ° C., preferably 150 to 700 ° C., if necessary. The particle shape is not particularly limited, but is particularly preferably spherical.

As the inorganic chloride, for example, MgCl ₂ , MgBr ₂ , MnCl ₂ , and MnBr ₂ are used. The inorganic chloride may be used as it is or after being pulverized by a ball mill or a vibration mill. Moreover, after dissolving inorganic chloride in solvent, such as alcohol, what was made to precipitate into a fine particle form with a depositing agent can also be used.

Clay is usually composed mainly of clay minerals. An ion-exchange layered compound is a compound having a crystal structure in which planes formed by ionic bonds or the like are stacked in parallel with a weak binding force, and the contained ions can be exchanged. Most clay minerals are ion-exchangeable layered compounds. In addition, these clays, clay minerals, and ion-exchange layered compounds are not limited to natural products, and artificial synthetic products can also be used. In addition, as clay, clay mineral or ion-exchange layered compound, clay, clay mineral, or ion crystalline compound having a layered crystal structure such as hexagonal closest packing type, antimony type, CdCl ₂ type, CdI ₂ type, etc. It can be illustrated.

  Examples of clay and clay minerals include kaolin, bentonite, kibushi clay, gyrome clay, allophane, hysinger gel, pyrophyllite, unmo group, montmorillonite group, vermiculite, ryokdeite group, palygorskite, kaolinite, nacrite, dickite, Halloysite, pectolite, teniolite.

Examples of the ion-exchange layered compound include α-Zr (HAsO ₄ ) ₂ · H ₂ O, α-Zr (HPO ₄ ) ₂ , α-Zr (KPO ₄ ) ₂ · 3H ₂ O, α-Ti (HPO ₄ ) ₂ , α-Ti (HAsO ₄ ) ₂ · H ₂ O, α-Sn (HPO ₄ ) ₂ · H ₂ O, γ-Zr (HPO ₄ ) ₂ , γ-Ti (HPO ₄ ) ₂ , γ- Examples include crystalline acidic salts of polyvalent metals such as Ti (NH ₄ PO ₄ ) ₂ .H ₂ O.

  It is also preferable to subject the clay and clay mineral to chemical treatment. As the chemical treatment, any of a surface treatment that removes impurities adhering to the surface and a treatment that affects the crystal structure of clay can be used. Specific examples of the chemical treatment include acid treatment, alkali treatment, salt treatment, organic matter treatment, and the like.

  The ion-exchangeable layered compound may be a layered compound in which the layers are expanded by exchanging the exchangeable ions between the layers with another large and bulky ion using the ion-exchangeability. Such bulky ions play a role of supporting pillars to support the layered structure and are usually called pillars. Moreover, introducing another substance between the layers of the layered compound in this way is called intercalation.

Examples of the guest compounds to be intercalated include, for example, TiCl _4, ZrCl ₄ cationic inorganic compounds such _{as, Ti (OR) 4, Zr} (OR) 4, PO (OR) 3, B (OR) 3 or the like of metal Metal hydroxide such as alkoxide (R is hydrocarbon group, etc.), [Al ₁₃ O ₄ (OH) ₂₄ ] ⁷⁺ , [Zr ₄ (OH) ₁₄ ] ²⁺ , [Fe ₃ O (OCOCH ₃ ) ₆ ] ⁺ Examples include physical ions. These compounds may be used individually by 1 type, and may use 2 or more types together. In addition, when intercalating these compounds, obtained by hydrolyzing metal alkoxides such as Si (OR) ₄ , Al (OR) ₃ , Ge (OR) ₄ (R is a hydrocarbon group, etc.) Polymers, colloidal inorganic compounds such as SiO _{2, and the} like can also coexist.

Examples of the pillar include an oxide generated by heat dehydrating after intercalating the metal hydroxide ions between layers.
Among the supports [C], a porous oxide containing SiO ₂ and / or Al ₂ O ₃ as a main component is preferable. Also preferred are clays or clay minerals, particularly preferred are montmorillonite, vermiculite, pectolite, teniolite and synthetic mica.

《Organic compound》
Examples of the organic compound in the carrier [C] include a granular or fine particle solid having a particle size in the range of 5 to 300 μm. Specifically, a (co) polymer produced mainly from an α-olefin having 2 to 14 carbon atoms such as ethylene, propylene, 1-butene and 4-methyl-1-pentene, vinylcyclohexane and styrene are mainly used. The (co) polymer produced | generated as a component, and those modifications can be illustrated.

<Organic compound component [D]>
In the present invention, the organic compound component [D] is used for the purpose of improving the polymerization performance and the physical properties of the produced polymer, if necessary. Examples of the organic compound [D] include alcohols, phenolic compounds, carboxylic acids, phosphorus compounds, amides, polyethers, and sulfonates.

<Usage and order of addition of each component>
In the case of olefin polymerization, the method of using each component and the order of addition are arbitrarily selected, and the following methods are exemplified. Hereinafter, the transition metal compound [A], the compound [B], the carrier [C], and the organic compound component [D] are also referred to as “components (A) to (D)”, respectively.
(1) A method of adding the component (A) alone to the polymerization vessel.
(2) A method of adding the component (A) and the component (B) to the polymerization vessel in an arbitrary order.
(3) a catalyst component having component (A) supported on component (C);
A method of adding the component (B) to the polymerization vessel in an arbitrary order.
(4) a catalyst component carrying component (B) on component (C);
A method of adding the component (A) to the polymerization vessel in an arbitrary order.
(5) A method in which a catalyst component in which component (A) and component (B) are supported on component (C) is added to a polymerization vessel.

  In each of the above methods (2) to (5), at least two of the catalyst components may be contacted in advance. In the above methods (4) and (5) in which the component (B) is supported, the component (B) that is not supported may be added in any order as necessary. In this case, the component (B) may be the same or different. Further, the solid catalyst component in which the component (C) is supported on the component (C) and the solid catalyst component in which the component (A) and the component (B) are supported on the component (C) In addition, a catalyst component may be further supported on the prepolymerized solid catalyst component.

[Olefin polymer production method]
The method for producing an olefin polymer according to the present invention includes a step [P] of polymerizing ethylene in the presence of the above-mentioned catalyst for olefin polymerization. Here, “polymerization” is a general term for homopolymerization and copolymerization. In addition, “polymerize ethylene in the presence of an olefin polymerization catalyst” means that each component of the olefin polymerization catalyst is added to the polymerization vessel by any method as in the above methods (1) to (5). And an embodiment in which ethylene is polymerized.

  In the present invention, the 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. Examples of the inert hydrocarbon medium used in the liquid phase polymerization method include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; cyclopentane, cyclohexane, methylcyclopentane, and the like. And alicyclic hydrocarbons; aromatic hydrocarbons such as benzene, toluene and xylene; and halogenated hydrocarbons such as ethylene chloride, chlorobenzene and dichloromethane. An inert hydrocarbon medium may be used individually by 1 type, and 2 or more types may be mixed and used for it. In addition, a so-called bulk polymerization method in which liquefied olefin itself that can be supplied to the polymerization is used as a solvent can also be used.

  When ethylene is polymerized using the olefin polymerization catalyst, the amount of each component that can constitute the olefin polymerization catalyst is as follows. In the olefin polymerization catalyst, the content of each component can be adjusted as follows.

Component (A) is usually used in an amount of 1 × 10 ⁻¹⁰ to 1 × 10 ⁻² mol, preferably 1 × 10 ⁻⁸ to 1 × 10 ⁻³ mol per liter of reaction volume.
Component (B-1) has a molar ratio [(B-1) / M] of component (B-1) to all transition metal atoms (M) in component (A) of usually 1 to 50,000, preferably Can be used in an amount of 10 to 20,000, particularly preferably 50 to 10,000.

  Component (B-2) has a molar ratio [Al / M] of aluminum atoms in component (B-2) to all transition metal atoms (M) in component (A) of usually 10 to 5,000, preferably Can be used in an amount of 20 to 2,000.

  Component (B-3) has a molar ratio [(B-3) / M] of component (B-3) to all transition metal atoms (M) in component (A) of usually 1 to 1000, preferably 1 It can be used in such an amount that it becomes ~ 200.

  When component (C) is used, the weight ratio of component (A) to component (C) [(A) / (C)] is preferably 0.0001 to 1, more preferably 0.0005 to 0.5. More preferably, it can be used in an amount of 0.001 to 0.1.

When using component (D),
When component (B) is component (B-1), the molar ratio [(D) / (B-1)] is usually 0.01 to 10, preferably 0.1 to 5. ,
When component (B) is component (B-2), the molar ratio [(D) / (B-2)] is usually 0.005 to 2, preferably 0.01 to 1. ,
When component (B) is component (B-3), the molar ratio [(D) / (B-3)] is usually 0.01 to 10, preferably 0.1 to 5. be able to.

  In the production method of the present invention, the polymerization temperature of ethylene is usually −50 to + 200 ° C., preferably 0 to 180 ° C., more preferably 40 to 180 ° C., further preferably 45 to 150 ° C., and the polymerization pressure is usually Normal pressure to 10 MPa gauge pressure, preferably normal pressure to 5 MPa gauge pressure. The polymerization reaction can be carried out in any of batch, semi-continuous and continuous methods. Furthermore, the polymerization can be carried out in two or more stages having different reaction conditions. The molecular weight of the resulting olefin polymer (ethylene polymer) can be adjusted by allowing hydrogen or the like to exist in the polymerization system, changing the polymerization temperature, or using the component (B).

  In particular, hydrogen can be said to be a preferable additive because it can improve the polymerization activity of the catalyst and increase or decrease the molecular weight of the polymer. When hydrogen is added to the system, the amount is suitably about 0.00001 to 100 NL per mole of olefin. In addition to adjusting the amount of hydrogen supplied, the hydrogen concentration in the system is not limited to the method of generating or consuming hydrogen in the system, the method of separating hydrogen using a membrane, It can also be adjusted by releasing the gas out of the system.

  For the olefin polymer (ethylene polymer) obtained by the production method of the present invention, after synthesis by the above method, a known catalyst deactivation treatment step, a catalyst residue removal step, a drying step, etc., if necessary. A post-processing step may be performed.

<Olefin>
In the production method of the present invention, the olefin supplied to the polymerization reaction is ethylene.
In the production method of the present invention, ethylene may be homopolymerized or ethylene and an α-olefin having 3 to 20 carbon atoms may be copolymerized. In this case, the α-olefin is such that the proportion of structural units derived from the α-olefin in the resulting olefin polymer (ethylene polymer) is less than 50 mol%, preferably 30 mol% or less, based on the total structural units. More preferably, the copolymerization is carried out at such a ratio that it is 20 mol% or less.

As the α-olefin, an α-olefin having 3 to 10 carbon atoms is particularly preferable.
Examples of the α-olefin include a linear or branched α-olefin. Examples of the linear or branched α-olefin include propylene, 1-butene, 2-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3 -Methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-icocene.

  In the production method of the present invention, a cyclic olefin, an olefin having a polar group, a terminal hydroxylated vinyl compound, and an aromatic vinyl compound are selected together with ethylene or with ethylene and the α-olefin having 3 to 20 carbon atoms. Polymerization can also proceed by coexisting at least one selected from the reaction system. It is also possible to use polyene in combination. Further, other components such as vinylcyclohexane may be copolymerized without departing from the spirit of the present invention.

  Examples of the cyclic olefin include cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene, 2-methyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene.

As the olefin having a polar group, for example,
Α, β-unsaturated carboxylic acids such as acrylic acid, methacrylic acid, fumaric acid, maleic anhydride, itaconic acid, itaconic anhydride, bicyclo (2,2,1) -5-heptene-2,3-dicarboxylic anhydride Acids and their metal salts such as sodium, potassium, lithium, zinc, magnesium, calcium, and aluminum salts;
Methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, methacrylic acid α, β-unsaturated carboxylic acid esters such as n-propyl, isopropyl methacrylate, n-butyl methacrylate, and isobutyl methacrylate;
Vinyl esters such as vinyl acetate, vinyl propionate, vinyl caproate, vinyl caprate, vinyl laurate, vinyl stearate, vinyl trifluoroacetate; unsaturated glycidyl acrylate, glycidyl methacrylate, monoglycidyl itaconate, etc. Glycidyl;
Is mentioned.

  Examples of the terminal hydroxylated vinyl compound include hydroxyl-1-butene, hydroxyl-1-pentene, hydroxyl-1-hexene, hydroxyl-1-octene, hydroxyl-1-decene, hydroxyl-1- Linear terminal hydroxylated vinyl compounds such as undecene, hydroxylated 1-dodecene, hydroxylated 1-tetradecene, hydroxylated 1-hexadecene, hydroxylated 1-octadecene, hydroxylated 1-eicocene; -3-methyl-1-butene, hydroxyl-3-methyl-1-pentene, hydroxyl-4-methyl-1-pentene, hydroxyl-3-ethyl-1-pentene, hydroxyl-4,4-dimethyl -1-pentene, hydroxyl-4-methyl-1-hexene, hydroxyl-4,4-dimethyl-1-hexene, hydroxyl-4-ethyl-1-hexene, hydroxyl-3-ethyl-1-hexene Branched terminal hydroxyl acid such as Vinyl compounds.

  Examples of the aromatic vinyl compound include styrene; o-methyl styrene, m-methyl styrene, p-methyl styrene, o, p-dimethyl styrene, o-ethyl styrene, m-ethyl styrene, p-ethyl styrene, and the like. Or polyalkylstyrene; methoxystyrene, ethoxystyrene, vinyl benzoic acid, methyl vinyl benzoate, vinyl benzyl acetate, hydroxystyrene, o-chlorostyrene, p-chlorostyrene, divinylbenzene, and other functional group-containing styrene derivatives; 3-phenyl Examples include propylene, 4-phenylpropylene, and α-methylstyrene.

  The polyene is preferably selected from diene and triene. It is also a preferred embodiment that polyene is used in the range of 0.0001 to 1 mol% with respect to the total olefin supplied to the polymerization reaction.

  Examples of the dienes include 1,4-pentadiene, 1,5-hexadiene, 1,4-hexadiene, 1,4-octadiene, 1,5-octadiene, 1,6-octadiene, 1,7-octadiene, 1, Α, ω-non-conjugated dienes such as 9-decadiene; non-conjugated such as ethylidene norbornene, vinyl norbornene, dicyclopentadiene, 7-methyl-1,6-octadiene, 4-ethylidene-8-methyl-1,7-nonadiene Diene; conjugated dienes such as butadiene and isoprene are exemplified. Among these, α, ω-nonconjugated dienes and dienes having a norbornene skeleton are preferable.

  Examples of the triene include 6,10-dimethyl-1,5,9-undecatriene, 4,8-dimethyl-1,4,8-decatriene, 5,9-dimethyl-1,4,8-decatriene, 6,9-dimethyl-1,5,8-decatriene, 6,8,9-trimethyl-1,5,8-decatriene, 6-ethyl-10-methyl-1,5,9-undecatriene, 4- Ethylidene-1,6, -octadiene, 7-methyl-4-ethylidene-1,6-octadiene, 4-ethylidene-8-methyl-1,7-nonadiene (EMND), 7-methyl-4-ethylidene-1, 6-nonadiene, 7-ethyl-4-ethylidene-1,6-nonadiene, 6,7-dimethyl-4-ethylidene-1,6-octadiene, 6,7-dimethyl-4-ethylidene-1,6-nonadiene, 4-ethylidene-1,6-decadiene, 7-methyl-4-ethylidene-1,6-decadiene, 7-methyl-6-propyl-4-ethylidene-1,6-octadiene, 4-ethylidene-1,7- Nonadiene, 8-methyl-4-ethylidene-1,7-nonadiene, 4-ethylidene-1,7-undecane Nonconjugated trienes such as ene; include trienes such as 1,3,5-hexatriene. Among these, non-conjugated triene having a double bond at the terminal, 4,8-dimethyl-1,4,8-decatriene, 4-ethylidene-8-methyl-1,7-nonadiene (EMND) is preferable.

  Each of the diene or triene may be used alone or in combination of two or more. A combination of diene and triene may also be used. Among the polyenes, α, ω-nonconjugated dienes and polyenes having a norbornene skeleton are particularly preferable.

  In the step [P], when ethylene and an α-olefin having 3 to 20 carbon atoms are copolymerized, or ethylene and an α-olefin having 3 to 20 carbon atoms and another monomer are copolymerized. The supply amount of each component is appropriately set according to the composition of the olefin polymer to be produced.

EXAMPLES Hereinafter, although this invention is demonstrated further more concretely based on an Example, this invention is not limited to these Examples.
[Measurement of various physical properties]
[Melting point (Tm)]
The melting point (Tm) of the olefin polymer was measured as follows using DSC Pyris1 manufactured by PerkinElmer or DSC7020 manufactured by SII Nanotechnology.

  Under a nitrogen atmosphere (nitrogen flow rate: 20 mL / min), the sample (about 5 mg) was heated to 200 ° C. at (1) a temperature increase rate of 10 ° C./min and held at 200 ° C. for 5 minutes, and (2) a temperature decrease rate of 10 After cooling to 20 ° C. at 20 ° C./minute and holding at 20 ° C. for 5 minutes, (3) the temperature was raised to 200 ° C. at a heating rate of 10 ° C./minute. The melting point (Tm) was observed and written together from the peak of the crystal melting peak in the temperature raising process of (1) and (3). In the olefin polymers described in Examples and Comparative Examples, when a plurality of crystal melting peaks are observed, the melting point observed from each peak apex (for example, the melting point (Tm1) observed from the low temperature side peak apex, Among the melting points (Tm2) observed from the peak peak on the high temperature side, the melting point calculated from the peak peak on the highest temperature side was defined as the melting point (Tm) of the olefin polymer.

[Weight average molecular weight (Mw), molecular weight distribution (Mw / Mn)]
The weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) were measured as follows using a gel permeation chromatograph HLC-8321 manufactured by Tosoh Corporation. The separation columns are TSKgel GMH6-HT: 2 and TSKgel GMH6-HTL: 2, the column size is 7.5 mm in diameter and 300 mm in length, the column temperature is 140 ° C., and the mobile phase is o- Using dichlorobenzene (containing 0.025 wt% BHT), the mobile phase was moved at 1.0 mL / min, the sample concentration was 30 mg / 20 mL or 15 mg / 10 mL, the sample injection volume was 400 microliters, and the detector A differential refractometer was used. As the standard polystyrene, monodispersed polystyrene manufactured by Tosoh Corporation was used. The molecular weight distribution and various average molecular weights were calculated in terms of polystyrene molecular weight according to the general calibration procedure.

(Identification of target)
The structure of the transition metal compound (metallocene compound) obtained in Examples was determined using 270 MHz ¹ H-NMR (GSH-270 manufactured by JEOL) and FD-MS (JMS-T100GC manufactured by JEOL).

<Production of transition metal compound>
The metallocene compounds of the following examples can be produced by changing the fluorene compound to a dithiophene compound in the method for producing a metallocene compound described in JP-A-2016-164264.

[Example c1]
Synthesis of transition metal compound (A1) represented by the following formula

(1) Synthesis of Ligand (A1) In a 100 mL three-necked flask under a nitrogen atmosphere, 1.03 g of 2,5-dimethyl-7H-cyclopenta [1,2-b: 4,3-b ′]-dithiophene (5. 00 mmol) and 65 mL of dehydrated t-butyl methyl ether were added. While cooling in an ice bath, 3.55 mL of a hexane solution (1.55 M) of n-butyllithium (5.50 mmol) was gradually added, and the mixture was stirred at room temperature for 1 hour. (1S, 3s) -1- (8-Methyl-3b, 4,5,6,7,7a-hexahydrocyclopenta [a] inden-2-yl) adamantane 1.84 g (6.00 mmol) was added. Thereafter, the mixture was stirred for 5 hours under heating and reflux. While cooling with an ice bath, 50 mL of an aqueous ammonium chloride solution was gradually added, and the resulting bilayer solution was transferred to a 300 mL separatory funnel. After adding 200 mL of methylene chloride and shaking several times, the aqueous layer was removed, and the organic layer was washed 3 times with 50 mL of water and once with 50 mL of saturated brine, then dried over anhydrous magnesium sulfate for 30 minutes, and then the solvent was removed under reduced pressure. Distilled off. Purification by silica gel column chromatography gave 1.15 g (2.24 mmol, yield: 44.9%) of a white solid (hereinafter referred to as “ligand (A1)”). Formation of the ligand (A1) was confirmed by FD-MS measurement.
FD-MS: m / Z = 512 (M ⁺ )
According to ¹ H-NMR measurement, the product was a mixture of isomers.

(2) Synthesis of transition metal compound (A1) In a nitrogen atmosphere, 0.513 g (1.00 mmol) of ligand (A1), 30 mL of dehydrated hexane, 1.00 g (10.0 mmol) of cyclopentyl methyl ether, Then, 260 mg (2.20 mmol) of α-methylstyrene was sequentially added. While cooling in a methanol / dry ice bath, 1.42 mL of a hexane solution (1.55 M) of n-butyllithium (2.20 mmol) was gradually added, and the mixture was stirred at 65 ° C. for 4 hours. The solvent was distilled off under reduced pressure, and 30 mL of dehydrated diethyl ether was added to give an orange solution. While cooling in a methanol / dry ice bath, 0.233 g (1.00 mmol) of zirconium tetrachloride was added, and the mixture was stirred for 16 hours while gradually warming to room temperature, whereby an orange slurry was obtained. The solid obtained by distilling off the solvent under reduced pressure was brought into a glove box and extracted with dichloromethane. After evaporating the solvent under reduced pressure and concentrating, a small amount of diethyl ether was added, and the solid was filtered off. The solid was washed with a small amount of hexane and then dried under reduced pressure to obtain 340 mg (0.505 mmol, yield: 50.5%) of an orange solid. The target product (hereinafter referred to as “transition metal compound (A1)”) was identified by ¹ H NMR spectrum and FD-MS spectrum. The measured values are shown below.
¹ H NMR (270 MHz, C ₆ D ₆ ): δ / ppm 6.67 (d, J = 1.1 Hz, 1H), 6.74 (d, J = 1.6 Hz, 1H), 6.35 (d , J = 1.4 Hz, 1H), 5.69 (d, J = 1.6 Hz, 1H), 4.17 (q, J = 6.5 Hz, 1H), 3.09 (t, J = 6. 5 Hz, 1H), 2.22 (d, J = 1.1 Hz, 3H), 2.19 (d, J = 1.6 Hz, 3H), 2.19-1.27 (m, 23H), 1 .74 (s, 3H)
FD-MS: M / z 672 (M ⁺ )

[Example c2]
Synthesis of transition metal compound (B1) represented by the following formula

窒素雰囲気下、１００ｍＬシュレンク管に配位子（Ａ１）０．５１３ｇ（１．００ｍｍｏｌ）、脱水ヘキサン３０ｍＬ、シクロペンチルメチルエーテル１．００ｇ（１０．０ｍｍｏｌ）、およびα−メチルスチレン２６０ｍｇ（２．２０ｍｍｏｌ）を順次添加した。メタノール／ドライアイス浴で冷却しながらｎ−ブチルリチウム（２．２０ｍｍｏｌ）のヘキサン溶液（１．５５Ｍ）１．４２ｍＬを徐々に添加し、６５℃で４時間攪拌した。減圧下で溶媒を留去し、脱水ジエチルエーテル３０ｍＬを添加して橙色溶液とした。メタノール／ドライアイス浴で冷却しながら四塩化ハフニウム０．３２０ｇ（１．００ｍｍｏｌ）を添加し、室温まで徐々に昇温しながら１６時間攪拌したところ、橙色スラリーが得られた。減圧下で溶媒を留去して得られた固体をグローブボックス内に持ち込み、ジクロロメタンで抽出した。減圧下で溶媒を留去して濃縮した後、少量のジエチルエーテルを加え、固体を濾別した。この固体を少量のヘキサンで洗浄した後、減圧下で乾燥することにより、橙色固体を３０８ｍｇ（０．４０５ｍｍｏｌ、収率：４０．５％）得た。目的物（以下「遷移金属化合物（Ｂ１）」と記載する。）の同定は¹Ｈ ＮＭＲスペクトルおよびＦＤ−ＭＳスペクトルにて行った。以下にその測定値を示す。
¹Ｈ ＮＭＲ（２７０ＭＨｚ，Ｃ₆Ｄ₆）： δ／ｐｐｍ ６．６４（ｄ， Ｊ＝１．１Ｈｚ，１Ｈ），６．４１（ｄ，Ｊ＝１．６Ｈｚ，１Ｈ），６．３５（ｄ， Ｊ＝１．１Ｈｚ，１Ｈ），５．６６（ｄ，Ｊ＝１．６Ｈｚ，１Ｈ），４．２６（ｑ，Ｊ＝ ７．０ Ｈｚ，１Ｈ），３．１１（ｔ，Ｊ＝６．５Ｈｚ，１Ｈ），２．２５（ｄ，Ｊ＝１．１ Ｈｚ，３Ｈ），２．２２（ｄ，Ｊ＝１．６Ｈｚ，３Ｈ），２．１０−１．３０（ｍ， ２３Ｈ），１．７３（ｓ，３Ｈ）
ＦＤ−ＭＳ： Ｍ／ｚ ７６０（Ｍ⁺）

Under a nitrogen atmosphere, a 100 mL Schlenk tube was charged with 0.513 g (1.00 mmol) of ligand (A1), 30 mL of dehydrated hexane, 1.00 g (10.0 mmol) of cyclopentyl methyl ether, and 260 mg (2.20 mmol) of α-methylstyrene. Were added sequentially. While cooling in a methanol / dry ice bath, 1.42 mL of a hexane solution (1.55 M) of n-butyllithium (2.20 mmol) was gradually added, and the mixture was stirred at 65 ° C. for 4 hours. The solvent was distilled off under reduced pressure, and 30 mL of dehydrated diethyl ether was added to give an orange solution. While cooling in a methanol / dry ice bath, 0.320 g (1.00 mmol) of hafnium tetrachloride was added, and the mixture was stirred for 16 hours while gradually warming to room temperature, whereby an orange slurry was obtained. The solid obtained by distilling off the solvent under reduced pressure was brought into a glove box and extracted with dichloromethane. After evaporating the solvent under reduced pressure and concentrating, a small amount of diethyl ether was added, and the solid was filtered off. This solid was washed with a small amount of hexane, and then dried under reduced pressure to obtain 308 mg (0.405 mmol, yield: 40.5%) of an orange solid. The target product (hereinafter referred to as “transition metal compound (B1)”) was identified by ¹ H NMR spectrum and FD-MS spectrum. The measured values are shown below.
¹ H NMR (270 MHz, C ₆ D ₆ ): δ / ppm 6.64 (d, J = 1.1 Hz, 1H), 6.41 (d, J = 1.6 Hz, 1H), 6.35 (d , J = 1.1 Hz, 1H), 5.66 (d, J = 1.6 Hz, 1H), 4.26 (q, J = 7.0 Hz, 1H), 3.11 (t, J = 6) .5 Hz, 1H), 2.25 (d, J = 1.1 Hz, 3H), 2.22 (d, J = 1.6 Hz, 3H), 2.10-1.30 (m, 23H), 1.73 (s, 3H)
FD-MS: M / z 760 (M ⁺ )

[Example c3]
Synthesis of transition metal compound (A2) represented by the following formula

(1) Synthesis of Ligand (A2) Under a nitrogen atmosphere, 1.03-g (5.00 mmol) of 2,5-dimethyl-7H-cyclopenta [1,2-b: 4,3-b ′]-dithiophene was placed in a flask. And 65 mL of dehydrated t-butyl methyl ether was added. While cooling in an ice bath, 3.60 mL of a hexane solution (1.55 M) of n-butyllithium (5.58 mmol) was gradually added, and the mixture was stirred at room temperature for 1 hour. After adding 1.68 g (6.00 mmol) of (1S, 3s) -1- (4,4,6-trimethyl-4,5-dihydropentalen-2-yl) adamantane, the mixture was stirred for 5 hours under reflux with heating. And stirred at room temperature for 17 hours. A saturated aqueous ammonium chloride solution was added, the organic layer was separated, and the aqueous layer was extracted with hexane. The organic layer was washed with a saturated aqueous sodium hydrogen carbonate solution, water, and a saturated aqueous sodium chloride solution. The extract was dried over magnesium sulfate and concentrated under reduced pressure. The obtained crude product was washed with methanol to obtain 2.12 g (yield 87%) of the desired product. Formation of the target product (hereinafter referred to as “ligand (A2)”) was confirmed by FD-MS measurement.
FD-MS: m / Z = 468 (M ⁺ )
According to ¹ H-NMR measurement, the product was a mixture of isomers.

(2) Synthesis of transition metal compound (A2) Under a nitrogen atmosphere, 730 mg (1.50 mmol) of ligand (A2), 0.43 mL (3.30 mmol) of α-methylstyrene, 1.75 mL of cyclopentyl methyl ether were placed in a Schlenk flask. (15.00 mmol) and 45 mL of hexane were charged. 2.13 mL of a hexane solution (1.55 M) of n-butyllithium (3.30 mmol) was added and heated to reflux for 4 hours. The solvent was distilled off under reduced pressure, then washed with hexane and filtered to obtain 595 mg of an orange solid. The orange solid obtained and 30 mL of diethyl ether were added to the Schlenk flask. The mixture was cooled to -78 ° C, charged with 320 mg (1.37 mmol) of zirconium tetrachloride, and stirred for 30 minutes. The mixture was stirred for 17 hours while returning to room temperature. The solvent was distilled off, and the soluble component was extracted with dichloromethane and hexane. The resulting solution was concentrated, washed with hexane, and then dried under reduced pressure. 175.5 mg of the desired product was obtained. ^The target product (hereinafter referred to as “transition metal compound (A2)”) was identified from the measurement results of ¹ H-NMR (CDCl ₃ ) and FD-MS.
¹ H-NMR (270 MHz, CDCl ₃ ): δ / ppm 6.81 (d, J = 1.3 Hz, 1H), 6.77 (d, J = 1.3 Hz, 1H), 6.18 (d, J = 1.6 Hz, 1H), 5.49 (d, J = 2.0 Hz, 1H), 3.05 (d, J = 14.8 Hz, 1H), 2.55-2.47 (m, 7H) ), 2.04-1.54 (m, 21H), 1.32 (s, 3H)
FD-MS: m / Z = 644 (M ⁺ )

[Example c4]
Synthesis of transition metal compound (B2) represented by the following formula

窒素雰囲気下、シュレンクフラスコに配位子（Ａ２）７３０ｍｇ（１．５０ｍｍｏｌ）、α−メチルスチレン０．４３ｍＬ（３．３０ｍｍｏｌ）、シクロペンチルメチルエーテル１．７５ｍＬ（１５．００ｍｍｏｌ）、ヘキサン４５ｍＬを装入した。ｎ−ブチルリチウム（３．３０ｍｍｏｌ）のヘキサン溶液（１．５５Ｍ）２．１３ｍＬを添加し、４時間加熱還流した。減圧下で溶媒を留去した後、ヘキサンで洗浄してろ過することにより薄茶色固体５６０ｍｇを得た。シュレンクフラスコに得られた薄茶色固体とジエチルエーテル４５ｍＬを添加した。−７８℃に冷却し、四塩化ハフニウムを３６６ｍｇ（１．０６ｍｍｏｌ）装入し、３０分撹拌した。室温に戻しながら１７時間撹拌した。溶媒を留去し、ジクロロメタン、ヘキサンで可溶分を抽出した。得られた溶液を濃縮しヘキサンで洗浄した後、減圧下で乾燥させた。目的物２７２．４ｍｇ得た。¹Ｈ−ＮＭＲ（ＣＤＣｌ₃）とＦＤ−ＭＳの測定結果により、目的物（以下「遷移金属化合物（Ｂ２）」と記載する。）を同定した。
¹Ｈ−ＮＭＲ（２７０ＭＨｚ，ＣＤＣｌ₃）： δ／ｐｐｍ ６．７８（ｄ，Ｊ＝１．３Ｈｚ，１Ｈ），６．７４（ｄ，Ｊ＝１．３Ｈｚ，１Ｈ），６．１３（ｄ，Ｊ＝１．６Ｈｚ，１Ｈ），５．４４（ｄ，Ｊ＝２．０Ｈｚ，１Ｈ），３．０５（ｄ，Ｊ＝１４．８Ｈｚ，１Ｈ），２．５７（ｄ，Ｊ＝１．３Ｈｚ，３Ｈ）, ２．５５（ｄ，Ｊ＝１．３Ｈｚ，３Ｈ）２．４７（ｄ，Ｊ＝１４．８Ｈｚ，１Ｈ），２．１０−１．５６（ｍ，２１Ｈ），１．３３（ｓ， ３Ｈ）
ＦＤ−ＭＳ ：ｍ／Ｚ＝７３４（Ｍ⁺）

Under a nitrogen atmosphere, a Schlenk flask was charged with 730 mg (1.50 mmol) of ligand (A2), 0.43 mL (3.30 mmol) of α-methylstyrene, 1.75 mL (15.00 mmol) of cyclopentyl methyl ether, and 45 mL of hexane. did. 2.13 mL of a hexane solution (1.55 M) of n-butyllithium (3.30 mmol) was added and heated to reflux for 4 hours. After distilling off the solvent under reduced pressure, 560 mg of a light brown solid was obtained by washing with hexane and filtering. The light brown solid obtained and 45 mL of diethyl ether were added to the Schlenk flask. The mixture was cooled to −78 ° C., charged with 366 mg (1.06 mmol) of hafnium tetrachloride, and stirred for 30 minutes. The mixture was stirred for 17 hours while returning to room temperature. The solvent was distilled off, and the soluble component was extracted with dichloromethane and hexane. The resulting solution was concentrated, washed with hexane, and then dried under reduced pressure. 272.4 mg of the desired product was obtained. ^The target product (hereinafter referred to as “transition metal compound (B2)”) was identified from the measurement results of ¹ H-NMR (CDCl ₃ ) and FD-MS.
¹ H-NMR (270 MHz, CDCl ₃ ): δ / ppm 6.78 (d, J = 1.3 Hz, 1H), 6.74 (d, J = 1.3 Hz, 1H), 6.13 (d, J = 1.6 Hz, 1H), 5.44 (d, J = 2.0 Hz, 1H), 3.05 (d, J = 14.8 Hz, 1H), 2.57 (d, J = 1.3 Hz) , 3H), 2.55 (d, J = 1.3 Hz, 3H) 2.47 (d, J = 14.8 Hz, 1H), 2.10-1.56 (m, 21H), 1.33 ( s, 3H)
FD-MS: m / Z = 734 (M ⁺ )

[Comparative Example c1]
Synthesis of transition metal compound (a1) represented by the following formula

Macromol. Chem. Phys. 2005, 206, 1405-1438に記載の方法で遷移金属化合物（ａ１）を合成した。

A transition metal compound (a1) was synthesized by the method described in Macromol. Chem. Phys. 2005, 206, 1405-1438.

[Comparative Example c2]
Synthesis of transition metal compound (b1) represented by the following formula

Macromol. Chem. Phys. 2005, 206, 1405-1438に記載の方法で遷移金属化合物（ｂ１）を合成した。

A transition metal compound (b1) was synthesized by the method described in Macromol. Chem. Phys. 2005, 206, 1405-1438.

<Manufacture of ethylene polymer>
[Example p1]
Under a nitrogen atmosphere, 3.30 mg (5.10 μmol) of the transition metal compound (A2) produced in Example c3 was placed in a Schlenk tube, and modified methylaluminoxane (manufactured by Tosoh Corporation, 1.52 mmol in terms of Al atom) was suspended. After adding 0.52 mL of a turbid liquid (n-hexane solvent, 2.93 M), 9.6 mL of dehydrated heptane was added, and the mixture was stirred at room temperature for 60 minutes or more to form a catalyst having a transition metal compound (A2) concentration of 0.0005 M A liquid was prepared.

  A 0.2 mL (0.05 M) heptane solution of triisobutylaluminum (10 μmol) and 3.0 mL of heptane as a polymerization solvent are placed in a 15 mL SUS autoclave sufficiently purged with nitrogen at 600 rpm. Stirring was performed. The obtained solution was heated to 60 ° C., and then the inside of the autoclave was pressurized with ethylene until the total pressure became 7 bar.

  To the autoclave, 0.1 mL of the catalyst solution (the concentration of the transition metal compound (A2) was 0.0005 M, the amount was 0.05 μmol), and then 0.7 mL of heptane was added to initiate polymerization. After polymerization at 60 ° C. for 10 minutes, a small amount of isobutyl alcohol was added to terminate the polymerization. After removing the solvent from the obtained polymer solution, it was dried under reduced pressure at 80 ° C. for 12 hours to obtain 0.21 g of an ethylene polymer. Table 3 shows the physical properties and the like of the ethylene polymer.

[Comparative Example p1]
Under a nitrogen atmosphere, 3.60 mg (5.30 μmol) of the transition metal compound (a1) produced in Comparative Example c1 was placed in a Schlenk tube, and a modified methylaluminoxane (manufactured by Tosoh Corporation, 1.58 mmol in terms of Al atom) was suspended. 0.54 mL of a turbid liquid (n-hexane solvent, 2.93 M) was added, 10.0 mL of dehydrated toluene was added, and the mixture was stirred at room temperature for 60 minutes or more to prepare a catalyst having a transition metal compound (a1) concentration of 0.0005 M A liquid was prepared.

  A 0.2 mL (0.05 M) heptane solution of triisobutylaluminum (10 μmol) and 3.0 mL of heptane as a polymerization solvent are placed in a 15 mL SUS autoclave sufficiently purged with nitrogen at 600 rpm. Stirring was performed. The obtained solution was heated to 60 ° C., and then the inside of the autoclave was pressurized with ethylene until the total pressure became 7 bar.

  To the autoclave, 0.1 mL of the catalyst solution (the concentration of the transition metal compound (a1) was 0.0005 M, the amount was 0.05 μmol), and then 0.7 mL of heptane was added to initiate polymerization. After polymerization at 60 ° C. for 5 minutes, a small amount of isobutyl alcohol was added to terminate the polymerization. After removing the solvent from the obtained polymer liquid, it was dried under reduced pressure at 80 ° C. for 12 hours to obtain 0.27 g of an ethylene polymer. Table 3 shows the physical properties and the like of the ethylene polymer.

[Example p2]
Under a nitrogen atmosphere, 3.60 mg (4.74 μmol) of the transition metal compound (B1) produced in Example c2 was placed in a Schlenk tube, and 0.47 mL (1.0 M) of a toluene solution of triisobutylaluminum (0.47 mmol) was added. After the addition, 9.0 mL of dehydrated heptane was added, and the mixture was stirred at room temperature for 30 minutes or more to prepare a catalyst solution having a transition metal compound (B1) concentration of 0.0005M.

  A SUS autoclave with an internal volume of 15 mL sufficiently purged with nitrogen was charged with 0.1 mL (0.05 M) of a heptane solution of triisobutylaluminum (5.0 μmol) and 2.9 mL of heptane as a polymerization solvent, and 600 rpm. Was stirred. The obtained solution was heated to 60 ° C., and then the inside of the autoclave was pressurized with ethylene until the total pressure became 7 bar.

  In the autoclave, 0.1 mL of the catalyst solution (concentration of transition metal compound (B1) 0.0005M, amount 0.05 μmol), 0.3 mL of heptane, triphenylcarbenium tetrakis (pentafluorophenyl) borate (0. Polymerization was initiated by sequentially adding 0.1 mL (0.005 M) of a 5 μmol) toluene solution and then 0.5 mL of heptane. After polymerization at 60 ° C. for 20 minutes, a small amount of isobutyl alcohol was added to terminate the polymerization. After removing the solvent from the obtained polymer solution, it was dried under reduced pressure at 80 ° C. for 12 hours to obtain 0.23 g of an ethylene polymer. Table 3 shows the physical properties and the like of the ethylene polymer.

[Example p3]
The same operation as in Example 2 was performed except that the transition metal compound (B1) was changed to the transition metal compound (B2) produced in Example c4 to obtain 0.29 g of an ethylene polymer. Table 3 shows the physical properties and the like of the ethylene polymer.

[Comparative Example p2]
Under a nitrogen atmosphere, 2.10 mg (2.74 μmol) of the transition metal compound (b1) produced in Comparative Example c2 was placed in a Schlenk tube, and 0.27 mL (1.0 M) of a toluene solution of triisobutylaluminum (0.27 mmol) was added. After the addition, 5.2 mL of dehydrated heptane was added, and the mixture was stirred at room temperature for 30 minutes or more to prepare a 0.0005 M catalyst solution.

  A SUS autoclave with an internal volume of 15 mL sufficiently purged with nitrogen was charged with 0.1 mL (0.05 M) of a heptane solution of triisobutylaluminum (5.0 μmol) and 2.9 mL of heptane as a polymerization solvent, and 600 rpm. Was stirred. The resulting solution was heated to 60 ° C. and then pressurized with ethylene until the total pressure was 7 bar.

  In the autoclave, 0.1 mL of the catalyst solution (the concentration of the transition metal compound (b1) is 0.0005 M, the amount is 0.05 μmol), 0.3 mL of heptane, triphenylcarbenium tetrakis (pentafluorophenyl) borate (0. Polymerization was initiated by sequentially adding 0.1 mL (0.005 M) of a 5 μmol) toluene solution and then 0.5 mL of heptane. After polymerization at 60 ° C. for 20 minutes, a small amount of isobutyl alcohol was added to terminate the polymerization. After removing the solvent from the obtained polymer liquid, the resultant was dried under reduced pressure at 80 ° C. for 12 hours to obtain 0.24 g of an ethylene polymer. Table 3 shows the physical properties and the like of the ethylene polymer.

  In Example p1, an ethylene polymer having a higher Mw than that of Comparative Example p1 was obtained. Similarly, in Examples p2 and 3, an ethylene polymer having a higher Mw than that of Comparative Example p2 was obtained.

Claims (9)

Transition metal compound [A] represented by the following general formula [I].

[In the formula [I], R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently a hydrogen atom, a hydrocarbon group, a silicon-containing group, a halogen atom or A halogen-containing hydrocarbon group,
The adjacent substituents of R ^{1 to} R ⁸ may be bonded to each other to form a ring,
R ⁹ and R ¹⁰ are each independently a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an aryl group, a substituted aryl group, a silicon-containing group, a nitrogen-containing group, an oxygen-containing group, a halogen atom or a halogen-containing group. An atom or substituent selected from the group consisting of
A and B are a sulfur atom, an oxygen atom, N = CR ¹¹ or CR ¹¹ , and a plurality of R ¹¹ are each independently a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an aryl group, or a substituted aryl. An atom or a substituent selected from the group consisting of a group, a silicon-containing group, a nitrogen-containing group, an oxygen-containing group, a halogen atom and a halogen-containing group, and when A is a sulfur atom, an oxygen atom or N = CR ¹¹ , B Is CR ¹¹ and when B is a sulfur atom, oxygen atom or N = CR ¹¹ , A is CR ¹¹ and the ring containing A and B has a double bond at a position where a double bond can be formed. And
M is a group 4 transition metal atom in the periodic table,
j is an integer of 1 to 4,
Q is a halogen atom, a hydrocarbon group, a neutral conjugated or non-conjugated diene having 10 or less carbon atoms, an anionic ligand, or a neutral ligand that can coordinate with a lone electron pair, and j is 2 or more. In this case, a plurality of Qs may be the same or different. ] The transition metal compound [A] according to claim 1, wherein R ¹ in the general formula [I] is a tert-butyl group or a 1-adamantyl group.   An olefin polymerization catalyst comprising the transition metal compound [A] according to claim 1 or 2. [B] [B-1] organometallic compound,
[B-2] further containing at least one compound selected from the group consisting of an organoaluminumoxy compound and [B-3] a compound that reacts with the transition metal compound [A] to form an ion pair. The catalyst for olefin polymerization described in 1.   The catalyst for olefin polymerization according to claim 3 or 4, further comprising a support [C], wherein the transition metal compound [A] is supported on the support [C].   The manufacturing method of an olefin polymer including the process [P] which superposes | polymerizes ethylene in presence of the catalyst for olefin polymerization as described in any one of Claims 3-5.   The method for producing an olefin polymer according to claim 6, wherein the step [P] is a step of polymerizing ethylene at a temperature of 40 ° C or higher and 200 ° C or lower.   The method for producing an olefin polymer according to claim 6 or 7, wherein the step [P] is a step of homopolymerizing ethylene.   The step [P] is an α-olefin having 3 to 20 carbon atoms together with ethylene, and the proportion of structural units derived from the α-olefin in the olefin polymer is less than 50 mol% with respect to the total structural units. The manufacturing method of the olefin polymer of Claim 6 or 7 which is a process of copolymerizing so that it may become a ratio.