JP6990032B2 - Method for Producing Olefin Polymer and Method for Preserving Transition Metal Complex - Google Patents

Description

The present invention relates to a method for producing an olefin polymer and the like, and more particularly to a method for producing an olefin polymer using a transition metal complex as a catalyst.

As a method for producing an olefin polymer, a production method using a transition metal complex such as a metallocene compound as a catalyst is known, and many such production methods have been reported so far (Patent Documents 1 to 3 and the like). ..

When the metallocene compound comes into contact with water or the like, it gradually deteriorates and cannot exhibit catalytic activity. Therefore, if the metallocene compound is left in a solvent (n-hexane, toluene, etc.) for a long period of time, the catalytic activity cannot be exhibited due to the contamination of water from the outside. Therefore, in the polymerization of an olefin using a metallocene compound dissolved in a solvent, the metallocene compound is subjected to the polymerization of the olefin without much time after being adjusted to a solution state.

On the other hand, when an olefin is polymerized using a metallocene compound, if impurities such as polar substances are present in the polymerization system, the catalytic activity of the metallocene compound is hindered. AlR ₃ (triisobutylaluminum, triethylaluminum, etc.) is known as a scavenger for such impurities and is often added into the polymerization system (Non-Patent Document 1, etc.).

International Publication No. 2004/029062 International Publication No. 2015/1242414 International Publication No. 2015/122415

Polypropylene Handbook, Kogyo Chosakai Co., Ltd., 1998, p. 61

Conventionally, it has been difficult to stably store a metallocene compound in a solution state dissolved in a solvent for a long period of time. Since it is not necessary to adjust the state, the degree of freedom in olefin polymerization (procurement plan, etc.) is increased, and the utility value of the technology is high.

Therefore, the present invention provides a method for producing an olefin polymer with high catalytic activity without adjusting a transition metal complex such as a metallocene compound used as a catalyst for olefin polymerization to a solution state immediately before olefin polymerization. I am aiming.
Another object of the present invention is to provide a storage method capable of stably storing a transition metal complex such as a metallocene compound dissolved in a solvent for a long period of time.

In order to solve the above problems, the present inventors first attempted to preserve a transition metal complex such as a metallocene compound in n-hexane from which impurities have been removed by activated alumina. However, as shown in the comparative example of the present specification, when the olefin polymerization was carried out using the transition metal complex preserved by this method, the catalytic activity of the transition metal complex decreased as the preservation period became longer. That is, the transition metal complex could not be stably stored for a long period of time.

Therefore, as a result of further diligent research, the present inventors can stably store the transition metal complex in a solution containing organic aluminum for a long period of time, and further polymerize the olefin using the stored solution. Therefore, it was found that the olefin polymer can be produced with high catalytic activity without adjusting the transition metal complex to a solution state immediately before the olefin polymerization, and the present invention has been completed.

The gist of the present invention is as follows.
[1]
A contact step in which the transition metal complex and organoaluminum in a ratio of 10,000 mol or less with respect to 1 mol of the transition metal atom in the transition metal complex in terms of the amount of aluminum atoms are brought into contact with the solvent, and the contact step. A method for producing an olefin polymer, which comprises a polymerization step of polymerizing an olefin in the presence of a solution containing a transition metal complex and containing organoaluminum at a concentration of 0.005 mmol / L or more in terms of aluminum atom.

[2]
The method for producing an olefin polymer according to [1], wherein in the contacting step, the transition metal complex, the organoaluminum, and the solvent are brought into contact with each other, and then the obtained solution is stored for 1 hour or more.

[3]
In the polymerization step, the olefin weight of the above [1] or [2] for preparing the solution by adding a solution containing the transition metal complex and the organoaluminum that have undergone the contact step in the polymerizer and further organoaluminum. Manufacturing method of coalescence.

[4]
A transition comprising a preservation step of storing the transition metal complex in a solution containing organic aluminum in a proportion of 10,000 mol or less per 1 mol of the transition metal atom in the transition metal complex in terms of the amount of aluminum atoms. How to store a metal complex.

According to the production method of the present invention, it is possible to produce an olefin polymer with high catalytic activity without adjusting a transition metal complex such as a metallocene compound used as a catalyst for olefin polymerization to a solution state immediately before olefin polymerization. can.
Further, according to the storage method of the present invention, the transition metal complex can be stably stored for a long period of time in a solution state.

Hereinafter, the present invention will be described in more detail.
[Method for producing olefin polymer]
The method for producing an olefin polymer of the present invention includes a contact step and a polymerization step.
Hereinafter, each step will be described.

[Contact process]
In the contacting step, the transition metal complex and organic aluminum having a ratio of 10,000 mol or less per 1 mol of the transition metal atom in the transition metal complex in terms of the amount of aluminum atoms are brought into contact with the solvent.

<Transition metal complex>
The transition metal complex is not particularly limited, and examples thereof include a transition metal complex used in a conventionally known catalyst for olefin polymerization.
Examples of the transition metal complex used in the catalyst for olefin polymerization include the following transition metal complexes (1) to (9).

(Transition metal complex (1))
The transition metal complex (1) is a compound represented by the following general formula [A1].

<R ¹ to R ⁸ >
In the formula [A1], R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are independently hydrogen atoms, hydrocarbon groups, halogen-containing groups, oxygen-containing groups and nitrogen, respectively. It is selected from a 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-containing group, and may be the same or different from each other. It may be formed.

Examples of the hydrocarbon group include an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group and an arylalkyl group. Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, an s-butyl group, a t-butyl group, an n-pentyl group, a neopentyl group and an n-hexyl group. , N-octyl group, nonyl group, dodecyl group and eicosyl group. Examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a norbornyl group and an adamantyl group. Examples of the alkenyl group include a vinyl group, a propenyl group and a cyclohexenyl group. Examples of the aryl group include a phenyl group, a trill group, a dimethylphenyl group, a trimethylphenyl group, an ethylphenyl group, a propylphenyl group, a biphenyl group, an α- or β-naphthyl group, a methylnaphthyl group, an anthrasenyl group, a phenanthryl group and a benzyl group. Examples thereof include a phenyl group, a pyrenyl group, an acenaphthyl group, a phenalenyl group, an aceanthrylenyl group, a tetrahydronaphthyl group, an indanyl group and a biphenylyl group. Examples of the arylalkyl group include a benzyl group, a phenylethyl group and a phenylpropyl group.

<Y>
In the formula [A1], Y is a divalent group that binds two ligands, specifically, a divalent group, a hydrocarbon group having 1 to 20 carbon atoms, and a halogen-containing group. It is a group selected from a group, a silicon-containing group, a germanium-containing group and a tin-containing group, and is preferably a divalent hydrocarbon group having 1 to 20 carbon atoms or a divalent silicon-containing group.

Examples of the divalent hydrocarbon group include an alkylene group, a substituted alkylene group and an alkylidene group, and specific examples thereof include a divalent hydrocarbon group.
Alkylene groups such as methylene, ethylene, propylene and butylene;
Isopropyridene, diethylmethylene, dipropylmethylene, diisopropylmethylene, dibutylmethylene, methylethylmethylene, methylbutylmethylene, methyl-t-butylmethylene, dihexylmethylene, dicyclohexylmethylene, methylcyclohexylmethylene, methylphenylmethylene, diphenylmethylene, ditril Substituent alkylene groups such as methylene, methylnaphthylmethylene, dinaphthylmethylene, 1-methylethylene, 1,2-dimethylethylene and 1-ethyl-2-methylethylene; Included are cycloalkryllidene groups such as silidene, cycloheptylden, bicyclo [3.3.1] nonilidene, norbornylidene, adamantylidene, tetrahydronaphthylidene and dihydroindanilidene and alkylidene groups such as etylidene, propylidene and butylidene. ..

As a divalent silicon-containing group,
Silylen; as well as methylsilylene, dimethylsilylene, diisopropylsilylene, dibutylsilylene, methylbutylsilylene, methyl-t-butylsilylene, dicyclohexylsilylene, methylcyclohexylsilylene, methylphenylcilylene, diphenylcilylene, ditrilcilylene, methylnaphthylcilylene, dinaphthyl. Alkylylene groups such as silylene, cyclodimethylene silylene, cyclotrimethylene silylene, cyclotetramethylene silylene, cyclopentamethylene silylene, cyclohexamethylene silylene and cycloheptamethylene silylene can be mentioned, with particular preference being a dimethylsilylene group and a dibutylcyrylene. Examples thereof include a dialkylsilylene group such as a group.

<M>
In formula [A1], M is a Group 4 transition metal, preferably Ti, Zr or Hf, more preferably Zr or Hf, and particularly preferably Zr.

<X>
In the formula [A1], X is 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. Atom or group, preferably a halogen atom or a hydrocarbon group. Examples of the halogen atom include fluorine, chlorine, bromine and iodine, and chlorine is particularly preferable.
Specific examples of the transition metal complex (1) include the compounds listed in [0077] of JP2013-224408A.

(Transition metal complex (2))
The transition metal complex (2) is a compound represented by the following general formula [A2].

<R ¹ to R ⁶ and R ¹¹ to R ¹⁶ >
In the formula [A2], R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are independently hydrogen atoms, respectively. It is selected from 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-containing group, and may be the same or different from each other. Often, two adjacent groups may be linked to each other to form a ring.

Examples of the hydrocarbon group include the hydrocarbon groups listed as R ¹ to R ⁸ in the above-mentioned formula [A1].
R ¹ to R ⁶ and R ¹¹ to R ¹⁶ are independently, preferably a hydrogen atom or a hydrocarbon group, and more preferably a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.

<Y>
In the formula [A2], Y is a divalent group that binds two ligands, specifically, a divalent group, a hydrocarbon group having 1 to 20 carbon atoms, and a halogen-containing group. It is a group selected from a group, a silicon-containing group, a germanium-containing group and a tin-containing group, and is preferably a divalent hydrocarbon group having 1 to 20 carbon atoms or a divalent silicon-containing group.
Examples of these groups include divalent groups listed as Y in the above-mentioned formula [A1].

<M>
In formula [A2], M is a Group 4 transition metal, preferably Ti, Zr or Hf, more preferably Zr or Hf, and particularly preferably Zr.

<X>
In the formula [A2], X is 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. Atom or group, preferably a halogen atom or a hydrocarbon group. Examples of the halogen atom include fluorine, chlorine, bromine and iodine, and chlorine is particularly preferable.
Specific examples of the transition metal complex (2) include the compounds listed in [0071] of JP2013-224408A.

(Transition metal complex (3))
The transition metal complex (3) is a compound represented by the following general formula [A3].

<R ¹ to R ¹⁴ >
In equation [A3], R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are independent of each other. A hydrogen atom, a hydrocarbon group, a heteroatom-containing hydrocarbon group or a silicon-containing group, and any two of the substituents R ¹ to R ⁴ are bonded to each other to form a ring. Of the substituents from R ⁵ to R ¹² , any two substituents may be bonded to each other to form a ring, and R ¹³ and R ¹⁴ may be bonded to each other to form a ring. May be.

Examples of the hydrocarbon group in R ¹ to R ¹⁴ 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. A group formed by substituting a cyclic unsaturated hydrocarbon group with a cyclic unsaturated hydrocarbon group can be mentioned. The hydrocarbon group usually has 1 to 20, preferably 1 to 15, and more preferably 1 to 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. Examples thereof include a linear alkyl group such as a group and an n-decanyl group; and a linear alkenyl group such as an allyl group.

Examples of the branched hydrocarbon group include an isopropyl group, a tert-butyl group, a tert-amyl group, a 3-methylpentyl group, a 1,1-diethylpropyl group, a 1,1-dimethylbutyl group and a 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; polycyclic groups such as norbornyl group, adamantyl group and methyladamantyl group. Be 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 anthrasenyl group; a cycloalkenyl group such as a cyclohexenyl group; 5-bicyclo [2.2. 1] Examples thereof include a polycyclic unsaturated alicyclic group such as a hepta-2-enyl group.

Examples of the group formed by substituting one or more hydrogen atoms of the 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. Examples thereof include a group in which one or more hydrogen atoms of the alkyl group of the above are substituted with an aryl group.

Examples of the heteroatom-containing hydrocarbon group in R ¹ to R ¹⁴ include an alkoxy group such as a methoxy group and an ethoxy group, an aryloxy group such as a phenoxy group, and an oxygen atom-containing hydrocarbon group such as a frill group; N-methylamino. Examples include an amino group such as a group, an N, N-dimethylamino group and an N-phenylamino group, a nitrogen atom-containing hydrocarbon group such as a pyryl group; and a sulfur atom-containing hydrocarbon group such as a thienyl group. The number of carbon atoms of the heteroatom-containing hydrocarbon group is usually 1 to 20, preferably 2 to 18, and more preferably 2 to 15. However, the silicon-containing group is excluded from the heteroatom-containing hydrocarbon group.

Examples of the silicon-containing group in R ¹ to R ¹⁴ include a trimethylsilyl group, a triethylsilyl group, a dimethylphenylsilyl group, a diphenylmethylsilyl group, a triphenylsilyl group and the like-SiR ₃ (in the formula, a plurality of Rs are each. Examples thereof include a group represented by an alkyl group or a phenyl group having 1 to 15 carbon atoms independently.

Of the substituents R ¹ to R ¹⁴ , any two substituents, such as two adjacent substituents (eg R ¹ and R ² , R ² and R ³ , R ³ and R ⁴ , R ⁵ and R ⁶ , R ⁶ and R ⁷ , R ⁷ and R ⁸ , R ⁹ and R ¹⁰ , R ¹⁰ and R ¹¹ , R ¹¹ and R ¹² , R ¹³ and R ¹⁴ ) are bonded to each other to form a ring. May be good. The ring formation may be present in two or more places in the molecule.

In the present specification, examples of the ring (additional ring) formed by bonding two substituents to each other include an alicyclic ring, an aromatic ring, and a heterocycle. Specific examples thereof include a cyclohexane ring; a benzene ring; a hydrogenated benzene ring; a cyclopentene ring; a heterocycle such as a furan ring and a thiophene ring, and a corresponding hydrogenated heterocycle, preferably a cyclohexane ring; a benzene ring and hydrogen. It is a benzene ring. Further, such a ring structure may further have a substituent such as an alkyl group on the ring.

R ⁵ , R ⁸ , R ⁹ and R ¹² are preferably hydrogen atoms.
R ⁶ , R ⁷ , R ¹⁰ and R ¹¹ are preferably a hydrogen atom, a hydrocarbon group, an oxygen atom-containing hydrocarbon group or a nitrogen atom-containing hydrocarbon group, and more preferably a hydrocarbon group. R ⁶ and R ⁷ may be coupled to each other to form a ring, and R ¹⁰ and R ¹¹ may be coupled to each other to form a ring. Examples of the structure of the fluorenyl group portion as described above include those represented by the following formula.

Ｒ¹³およびＲ¹⁴は、好ましくは炭化水素基、ヘテロ原子含有炭化水素基またはケイ素含有基であり、さらに好ましくはアリール基または置換アリール基（ヘテロ原子含有炭化水素基またはケイ素含有基を有するアリール基）である。

R ¹³ and R ¹⁴ are preferably a hydrocarbon group, a heteroatom-containing hydrocarbon group or a silicon-containing group, and more preferably an aryl group or a substituted aryl group (an aryl group having a heteroatom-containing hydrocarbon group or a silicon-containing group). ).

<Y>
In the formula [A3], Y is a carbon atom, a silicon atom, a germanium atom or a tin atom, and is preferably a carbon atom.

<M, Q, j>
In formula [A3], M is a Group 4 transition metal, preferably Ti, Zr or Hf, more preferably Zr or Hf.

Q is a neutral ligand that can be coordinated with a halogen atom, a hydrocarbon group, an anionic ligand or a lone electron pair, and when j is an integer of 2 or more, Q is selected in the same or different combinations.

Examples of the halogen atom in Q include fluorine, chlorine, bromine and iodine.
Examples of the hydrocarbon group in Q include the same groups as the hydrocarbon groups in R ¹ to R ¹⁴ , preferably an alkyl group such as a linear alkyl group or a branched alkyl group.

Examples of the anion ligand in Q include an alkoxy group such as methoxy and tert-butoxy; an aryloxy group such as phenoxy; a carboxylate group such as acetate and benzoate; a sulfonate group such as mesylate and tosylate; dimethylamide and diisopropylamide. , Methylanilide, diphenylamide and other amide groups.

Examples of the neutral ligand capable of coordinating with a lone electron pair in Q include organic phosphorus compounds such as trimethylphosphine, triethylphosphine, triphenylphosphine, and diphenylmethylphosphine; tetrahydrofuran, diethyl ether, dioxane, 1,2-. Examples include ethers such as dimethoxyethane.

It is preferable that at least one of Q is a halogen atom or an alkyl group.
j is an integer of 1 to 4, preferably 2. When j is an integer of 2 or more, Q may be selected in the same or different combinations.

Specific examples of the transition metal complex (3) include the compounds listed on pages 29 to 43 of International Publication No. 2004/87775, and the compounds listed on pages 9 to 37 of International Publication No. 2006/25540. , The compounds listed in [0117] of International Publication No. 2015/122414, and the compounds listed in [0143] of International Publication No. 2015/122415.

(Transition metal complex (4))
The transition metal complex (4) is a compound represented by the following general formula [A4].

<R ¹ to R ¹⁶ >
In equation [A4], R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ And R ¹⁶ are each independently a hydrogen atom, a hydrocarbon group, a heteroatom-containing hydrocarbon group or a silicon-containing group, and any two substituents from R ¹ to R ¹⁶ are bonded to each other. It may form a ring.

The hydrocarbon groups, heteroatom-containing hydrocarbon groups and silicon-containing groups in R ¹ to R ¹⁶ include the hydrocarbon groups exemplified as R ¹ to R ¹⁴ in the above-mentioned formula [A3], heteroatom-containing hydrocarbon groups and silicon. Containing groups can be mentioned.

Of the substituents from R ¹ to R ¹⁶ , two adjacent substituents (eg R ¹ and R ² , R ² and R ³ , R ⁴ and R ⁶ , R ⁴ and R ⁷ , R ⁵ and R ⁶ ). , R ⁵ and R ⁷ , R ⁶ and R ⁸ , R ⁷ and R ⁸ , R ⁹ and R ¹⁰ , R ¹⁰ and R ¹¹ , R ¹¹ and R ¹² , R ¹³ and R ¹⁴ , R ¹⁴ and R ¹⁵ , R ¹⁵ and R ¹⁶ ) may be bonded to each other to form a ring, R ⁴ and R ⁵ may be bonded to each other to form a ring, and R ⁶ and R ⁷ may be bonded to each other to form a ring. It may be formed, R ¹ and R ⁸ may be bonded to each other to form a ring, R ³ and R ⁴ may be bonded to each other to form a ring, and R ³ and R ⁵ may be formed. May combine with each other to form a ring. The ring formation may be present in two or more places in the molecule.

In the present specification, examples of the ring (additional ring) formed by bonding two substituents to each other include an alicyclic ring, an aromatic ring, and a heterocycle. Specific examples thereof include a cyclohexane ring; a benzene ring; a hydrogenated benzene ring; a cyclopentene ring; a heterocycle such as a furan ring and a thiophene ring, and a corresponding hydrogenated heterocycle, preferably a cyclohexane ring; a benzene ring and hydrogen. It is a benzene ring. Further, such a ring structure may further have a substituent such as an alkyl group on the ring.

R ¹ and R ³ are preferably hydrogen atoms.
R ² is preferably a hydrocarbon group, a heteroatom-containing hydrocarbon group or a silicon-containing group, more preferably a hydrocarbon group, and even more preferably a hydrocarbon group having 1 to 20 carbon atoms. It is more preferably not an aryl group, more preferably a linear hydrocarbon group, a branched hydrocarbon group or a cyclic saturated hydrocarbon group, and a carbon having a free valence (a carbon bonded to a cyclopentadienyl ring). ) Is a substituent that is a tertiary carbon, which is particularly preferable.

Specific examples of R ² 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, which are more preferable. Is a substituent in which the carbon having a free atomic value such as tert-butyl group, tert-pentyl group, 1-methylcyclohexyl group, 1-adamantyl group is a tertiary carbon, and particularly preferably 1-adamantyl group, tert-. It is a butyl group.

R ⁴ is one of the preferable forms when the transition metal complex (4) is represented by the following general formula [A4'] and is a hydrogen atom.

この場合、前記遷移金属錯体（４）は、本発明の趣旨を逸脱しない範囲で、一般式［A4'］で表される遷移金属錯体の全ての鏡像異性体、例えば一般式［A4''］で表される遷移金属錯体を包含する。

In this case, the transition metal complex (4) is a mirror image isomer of the transition metal complex represented by the general formula [A4'], for example, the general formula [A4''], as long as the gist of the present invention is not deviated. Includes transition metal complexes represented by.

式［A4'］および［A4''］の表記において、ＭＱ_j部分が紙面手前に、架橋部が紙面奥側に存在するものとする。すなわち、これらの遷移金属錯体では、シクロペンタジエン環のα位（架橋部位が置換した炭素原子を基準とする）に、中心金属側に向いた水素原子（Ｒ⁴）が存在する。

In the notation of the formulas [A4'] and [A4''], it is assumed that the MQ _j portion exists in front of the paper surface and the cross-linking portion exists in the back side of the paper surface. That is, in these transition metal complexes, a hydrogen atom (R ⁴ ) facing the central metal side exists at the α-position of the cyclopentadiene ring (based on the carbon atom substituted at the cross-linking site).

On the other hand, in the above-mentioned general formula [A4], it is not specified whether the MQ _j portion and the cross-linked portion are present in front of the paper surface or in the back side of the paper surface. That is, the transition metal compound (A4) represented by the general formula [A4] includes a transition metal compound having a specific structure and an enantiomer thereof.

At least one selected from R ⁴ , R ⁵ , R ⁶ and R ⁷ is preferably a hydrocarbon group, a heteroatom-containing hydrocarbon group or a silicon-containing group, where R ⁴ and R ⁵ are hydrogen atoms or hydrocarbons. It is more preferably a group, and R ⁵ is more preferably an alkyl group such as a linear alkyl group or a branched alkyl group, a cycloalkyl group or a cycloalkenyl group, and is an alkyl group having 1 to 10 carbon atoms. Is particularly preferred. Further, from the viewpoint of synthesis, it is one of the preferable forms that both R ⁴ and R ⁵ are alkyl groups, and an alkyl group having 1 to 10 carbon atoms is particularly preferable. Similarly, from a synthetic point of view, it is also preferable that R ⁶ and R ⁷ are hydrogen atoms. It is more preferable that R ⁵ and R ⁷ are bonded to each other to form a ring, and it is particularly preferable that the ring is a 6-membered ring such as a cyclohexane ring.

R ⁸ is preferably a hydrocarbon group, and particularly preferably an alkyl group such as a methyl group.
In the general formula [A4], the fluorene ring moiety is not particularly limited as long as it has a structure obtained from a known fluorene derivative. R ⁹ , R ¹² , R ¹³ and R ¹⁶ are preferably hydrogen atoms.

R ¹⁰ , R ¹¹ , R ¹⁴ and R ¹⁵ are preferably a hydrogen atom, a hydrocarbon group, an oxygen atom-containing hydrocarbon group or a nitrogen atom-containing hydrocarbon group, more preferably a hydrocarbon group, and even more preferably. It is a hydrocarbon group having 1 to 20 carbon atoms, for example, 2,7-di-tert-butylfluorenyl group, 3,6-di-tert-butylfluorenyl group, 2,7-diphenyl-3, Examples thereof include a 6-di-tert-butylfluorenyl group, particularly preferably a 2,7-di-tert-butylfluorenyl group.

R ¹⁰ and R ¹¹ may be coupled to each other to form a ring, and R ¹⁴ and R ¹⁵ may be coupled to each other to form a ring. Examples of such substituted fluorenyl groups include benzofluorenyl group, dibenzofluorenyl group, octahydrodibenzofluorenyl group, 1,1,4,4,7,7,10,10-octamethyl-2. , 3,4,7,8,9,10,12-octahydro-1H-dibenzo [b, h] fluorenyl group, 1,1,3,3,6,6,8,8-octamethyl-2,3, 6,7,8,10-Hexahydro-1H-dicyclopenta [b, h] fluorenyl group, 1', 1', 3', 6', 8', 8'-hexamethyl-1'H, 8'H-dicyclopenta [B, h] fluorenyl group is mentioned, and particularly preferably 1,1,4,4,7,7,10,10-octamethyl-2,3,4,7,8,9,10,12-octahydro-. Examples include the 1H-dibenzo [b, h] fluorenyl group.

<M, Q, j>
In formula [A4], M is a Group 4 transition metal, preferably Ti, Zr or Hf, more preferably Zr or Hf, and particularly preferably Zr.

Q is a neutral ligand that can be coordinated with a halogen atom, a hydrocarbon group, an anionic ligand or a lone electron pair.
Examples of the neutral ligand that can be coordinated with the halogen atom, hydrocarbon group, anionic ligand and lone electron pair in Q include the halogen atom, hydrocarbon group, anionic ligand and lone pair in the above formula [A3]. Examples thereof include neutral ligands that can be coordinated with an electron pair.

j is an integer of 1 to 4, preferably 2. When j is an integer of 2 or more, Q may be selected in the same or different combinations.
Specific examples of the transition metal complex (4) are listed in the compounds listed on pages 11 to 15 of International Publication No. 2006/68308, and [0075]-[0086] of International Publication No. 2014/5086. Examples thereof include the compounds listed in [0072]-[0084] of JP-A-2008 / 040508.

(Transition metal complex (5))
The transition metal complex (5) is a metal complex corresponding to the following general formula [A5] described in JP-A-2000-516228.

（式中、Ｍは、元素の周期律表の３－１３族の１、ランタニド又はアクチニドからの金属であり、それは＋２、＋３又は＋４形式酸化状態にあり、そして５個の置換基、即ちＲ^A、（Ｒ^B）_j－Ｔ（但し、ｊは０、１又は２である）、Ｒ^C、Ｒ^D及びＺ（但し、Ｒ^A、Ｒ^B、Ｒ^C及びＲ^DはＲ基である）を有する環状の非局在化π－結合リガンド基である１個のシクロペンタジエニル（Ｃｐ）基にπ結合しており、さらに
Ｔは、ｊが１又は２であるとき、Ｃｐ環そしてＲ^Bに共有結合しているヘテロ原子であり、さらにｊが０のとき、ＴはＦ、Ｃｌ、Ｂｒ又はＩであり；ｊが１のとき、ＴはＯ又はＳ、又はＮ又はＰであり、そしてＲ^BはＴへの二重結合を有し；ｊが２のとき、ＴはＮ又はＰであり、さらに
Ｒ^Bは、それぞれの場合独立して、水素であるか、又はヒドロカルビル、ヒドロカルビルシリル、ハロゲン置換ヒドロカルビル、ヒドロカルビルオキシ置換ヒドロカルビル、ヒドロカルビルアミノ置換ヒドロカルビル、ヒドロカルビルシリルヒドロカルビル、ヒドロカルビルアミノ、ジ（ヒドロカルビル）アミノ、ヒドロカルビルオキシである１－８０個の非水素原子を有する基であり、各Ｒ^Bは任意にそれぞれの場合独立して１－２０個の非水素原子を有するヒドロカルビルオキシ、ヒドロカルビルシロキシ、ヒドロカルビルシリルアミノ、ジ（ヒドロカルビルシリル）アミノ、ヒドロカルビルアミノ、ジ（ヒドロカルビル）アミノ、ジ（ヒドロカルビル）ホスフィノ、ヒドロカルビルスルフィド、ヒドロカルビル、ハロゲン置換ヒドロカルビル、ヒドロカルビルオキシ置換ヒドロカルビル、ヒドロカルビルアミノ置換ヒドロカルビル、ヒドロカルビルシリル又はヒドロカルビルシリルヒドロカルビル又は１－２０個の非水素原子を有する非干渉基である１個以上の基により置換されていてもよく；そして
Ｒ^A、Ｒ^C及びＲ^Dのそれぞれは、水素であるか、又はヒドロカルビル、ハロゲン置換ヒドロカルビル、ヒドロカルビルオキシ置換ヒドロカルビル、ヒドロカルビルアミノ置換ヒドロカルビル、ヒドロカルビルシリル、ヒドロカルビルシリルヒドロカルビルである１－８０個の非水素原子を有する基であり、Ｒ^A、Ｒ^C及びＲ^Dのそれぞれは、任意にそれぞれの場合独立して１－２０個の非水素原子を有するヒドロカルビルオキシ、ヒドロカルビルシロキシ、ヒドロカルビルシリルアミノ、ジ（ヒドロカルビルシリル）アミノ、ヒドロカルビルアミノ、ジ（ヒドロカルビル）アミノ、ジ（ヒドロカルビル）ホスフィノ、ヒドロカルビルスルフィド、ヒドロカルビル、ハロゲン置換ヒドロカルビル、ヒドロカルビルオキシ置換ヒドロカルビル、ヒドロカルビルアミノ置換ヒドロカルビル、ヒドロカルビルシリル又はヒドロカルビルシリルヒドロカルビルであるか、又は１－２０個の非水素原子を有する非干渉基である１個以上の基により置換されていてもよく；又は任意に、Ｒ^A、Ｒ^B、Ｒ^C及びＲ^Dの２個以上は、互いに共有結合してそれぞれのＲ基について１－８０個の非水素原子を有する１個以上の縮合環又は環系を形成し、１個以上の縮合環又は環系は、置換されていないか、又はそれぞれの場合独立して１－２０個の非水素原子を有するヒドロカルビルオキシ、ヒドロカルビルシロキシ、ヒドロカルビルシリルアミノ、ジ（ヒドロカルビルシリル）アミノ、ヒドロカルビルアミノ、ジ（ヒドロカルビル）アミノ、ジ（ヒドロカルビル）ホスフィノ、ヒドロカルビルスルフィド、ヒドロカルビル、ハロゲン置換ヒドロカルビル、ヒドロカルビルオキシ置換ヒドロカルビル、ヒドロカルビルアミノ置換ヒドロカルビル、ヒドロカルビルシリル又はヒドロカルビルシリルヒドロカルビル、又は１－２０個の非水素原子を有する非干渉基である１個以上の基により置換されており；
Ｚはσ結合を介してＣｐ及びＭの両者に結合している２価の基であり、Ｚは硼素であるか又は元素の周期律表の１４族の一員であり、さらに窒素、燐、硫黄又は酸素からなり；
Ｘは、環状の非局在化π結合リガンド基であるリガンドの群を除く、６０個以内の原子を有するアニオン性又はジアニオン性リガンド基であり；
Ｘ'は、それぞれの場合独立して２０個以内の原子を有する中性のルイス塩基配位結合性化合物であり；
ｐは０、１又は２であり、そしてＸがアニオン性リガンドであるときＭの形式酸化状態より２少なく；Ｘがジアニオン性リガンドであるとき、ｐは１であり；そして
ｑは０、１又は２である。）
前記遷移金属錯体（５）の具体例としては、特表２０００－５１６２２８号公報の３５～９９頁に列挙された化合物が挙げられる。

(In the formula, M is a metal from 1, lanthanide or actinide, group 3-13 of the periodic table of elements, which is in a +2, +3 or +4 formal oxidation state and has five substituents, i.e. R. ^A , (RB) _j ^- T (where j is 0, 1 or 2), ^RC , ^RD and Z (where ^RA , RB, ^RC and ^RD are ^R groups). It is π-bonded to one cyclopentadienyl (Cp) group, which is a cyclic delocalized π-binding ligand group having, and T is Cp ring and R when j is 1 or 2. It is a hetero atom covalently bonded to ^B , and when j is 0, T is F, Cl, Br or I; when j is 1, T is O or S, or N or P. And RB has a double bond to ^T ; when j is 2, T is N or ^P , and RB is hydrogen in each case independently, or hydrocarbyl, hydrocarbylsilyl. , Halogen-substituted hydrocarbyl, hydrocarbyloxy-substituted hydrocarbyl, hydrocarbylamino-substituted hydrocarbyl, hydrocarbylsilylhydrocarbyl, hydrocarbylamino, di (hydrocarbyl) amino, hydrocarbyloxy, a group having 1-80 non ^- hydrogen atoms, each RB Hydrocarbyloxy, hydrocarbylsiloxy, hydrocarbylsilylamino, di (hydrocarbylsilyl) amino, hydrocarbylamino, di (hydrocarbyl) amino, di (hydrocarbyl) phosphino, optionally each independently having 1-20 non-hydrogen atoms, Hydrocarbylsulfide, hydrocarbyl, halogen-substituted hydrocarbyl, hydrocarbyloxy-substituted hydrocarbyl, hydrocarbylamino-substituted hydrocarbyl, hydrocarbylsilyl or hydrocarbylsilylhydrocarbyl or substituted with one or more groups that are non-interfering groups with 1-20 non-hydrogen atoms. And each of ^RA , ^RC and ^RD may be hydrogen or 1-80, hydrocarbyl, halogen-substituted hydrocarbyl, hydrocarbyloxy-substituted hydrocarbyl, hydrocarbylamino-substituted hydrocarbyl, hydrocarbylsilyl, hydrocarbylsilylhydrocarbyl. ^A group having 1 non-hydrogen atom, each of RA, ^RC and ^RD optionally independently having 1-20 non-hydrogen atoms in each case of hydrocarbyloxy, hydrocarbi. Luciloxy, hydrocarbylsilylamino, di (hydrocarbylsilyl) amino, hydrocarbylamino, di (hydrocarbyl) amino, di (hydrocarbyl) phosphino, hydrocarbyl sulfide, hydrocarbyl, halogen-substituted hydrocarbyl, hydrocarbyloxy-substituted hydrocarbyl, hydrocarbylamino-substituted hydrocarbyl, hydrocarbylsilyl or Hydrocarbyl Cyril Hydrocarbyl may be substituted with one or more groups which are non-interfering groups having 1-20 non ^- hydrogen atoms; or optionally ^RA , RB, ^RC and R. Two or more of ^D form a covalent bond with each other to form one or more fused rings or ring systems having 1-80 non-hydrogen atoms for each R group, and one or more fused rings or ring systems. Hydrocarbyloxy, hydrocarbylsiloxy, hydrocarbylsilylamino, di (hydrocarbylsilyl) amino, hydrocarbylamino, di (hydrocarbyl) amino, unsubstituted or in each case independently having 1-20 non-hydrogen atoms. Di (hydrocarbyl) phosphino, hydrocarbyl sulfide, hydrocarbyl, halogen-substituted hydrocarbyl, hydrocarbyloxy-substituted hydrocarbyl, hydrocarbylamino-substituted hydrocarbyl, hydrocarbylsilyl or hydrocarbylsilylhydrocarbyl, or one non-interfering group with 1-20 non-hydrogen atoms. It has been replaced by the above groups;
Z is a divalent group attached to both Cp and M via a σ bond, Z is a boron or a member of Group 14 of the Periodic Table of the Elements, and nitrogen, phosphorus, sulfur. Or consists of oxygen;
X is an anionic or dianionic ligand group having no more than 60 atoms, excluding the group of ligands that are cyclic delocalized π-bonded ligand groups;
X'is a neutral Lewis base-coordinating compound with up to 20 atoms independently in each case;
p is 0, 1 or 2 and 2 less than the formal oxidation state of M when X is an anionic ligand; p is 1 when X is a dianionic ligand; and q is 0, 1 or It is 2. )
Specific examples of the transition metal complex (5) include the compounds listed on pages 35 to 99 of JP-A-2000-516228.

(Transition metal complex (6))
The transition metal complex (6) is an ansabis (μ-substituted) periodic table group 4 metal and an aluminum compound corresponding to the following general formula [A6] described in JP-A-2002-522551.

（式中、Ｌ´はπ－結合した基であり、
Ｍは周期律表４族金属であり、
Ｊは窒素又は燐であり、
Ｚは２価の橋かけ結合基であり、
Ｒ´は不活性の１価のリガンドであり、
ｒは１又は２であり、
Ｘはそれぞれの場合独立してμ－橋かけ結合リガンド基を形成できるルイス塩基性リガンド基であり、所望により２個のＸ基は一緒に結合してもよく、そして
Ａ´はそれぞれの場合独立して水素を除いて５０個以内の原子のアルミニウム含有ルイス酸化合物であり、該化合物はμ－橋かけ結合基により金属錯体との付加物を形成し、所望により２個のＡ´基は一緒に結合しそれにより単一の２官能性ルイス酸含有化合物を形成してもよい。）
前記遷移金属錯体（６）の具体例としては、特表２００２－５２２５５１号公報の［００２５］～［００２７］に列挙された化合物が挙げられる。

(In the equation, L'is a π-bonded group,
M is a Group 4 metal of the Periodic Table,
J is nitrogen or phosphorus,
Z is a divalent bridging bond,
R'is an inactive monovalent ligand,
r is 1 or 2
X is a Lewis basic ligand group capable of independently forming a μ-bridge binding ligand group in each case, two X groups may optionally bind together, and A'is independent in each case. It is an aluminum-containing Lewis acid compound having up to 50 atoms excluding hydrogen, and the compound forms an adduct with a metal complex by a μ-bridge bond group, and optionally two A'groups together. It may bind to and thereby form a single bifunctional Lewis acid-containing compound. )
Specific examples of the transition metal complex (6) include the compounds listed in [0025] to [0027] of JP-A-2002-522551.

(Transition metal complex (7))
The transition metal complex (7) is a metal complex corresponding to the following general formula [A7-1], [A7-2] or [A7-3] described in JP-A-2003-501433.

（式中、Ｍは元素周期律表の３～１３族ランタニド又はアクチニドの１つから選ばれる金属である；
Ｚはホウ素、又は元素周期律表の１４族の１員をもち、且つ窒素、リン、硫黄又は酸素をもつ２価の基である；
Ｘは水素を算入せずに６０以下の原子をもつアニオン性リガンド基であり、所望により２個のＸ基はいっしょになって２価のアニオン性リガンド基を形成している；
Ｘ'はそれぞれの場合独立に２０以下の原子をもつ中性ルイス塩基リガンドである；
ｐは０～５の数であって、Ｍの形式酸化状態より２少ない；
ｑは０、１又は２である；
Ｅはケイ素又は炭素である；
Ｒ^A はそれぞれの場合独立に水素又はＲ^B である；
Ｒ^B はＢＲ^C ₂ であるか、又はヒドロカルビル、ヒドロカルビルシリル、ハロゲン置換ヒドロカルビル、ヒドロカルビルオキシ置換ヒドロカルビル、ジ（ヒドロカルビル）アミノ置換ヒドロカルビル、ＢＲ^C ₂ －置換ヒドロカルビル、ヒドロカルビルシリルヒドロカルビル、ジ（ヒドロカルビル）アミノ、ヒドロカルバジイルアミノ、又はヒドロカルビルオキシ基であり、各Ｒ^B は水素を算入せずに１～１８の原子をもち、そして所望により２個のＲ^B 基は共有結合して１以上の縮合環を形成していてもよい；
Ｒ^C はそれぞれの場合独立にヒドロカルビル、ハロゲン置換ヒドロカルビル、ヒドロカルビルオキシ置換ヒドロカルビル、ジヒドロカルビルアミノ置換ヒドロカルビル、ヒドロカルバジイルアミノ置換ヒドロカルビル、ヒドロカルビルシリル、ヒドロカルビルシリルヒドロカルビル、又はＲ^D である；
Ｒ^D はそれぞれの場合独立にジヒドロカルビルアミノ又はヒドロカルビルオキシ基で水素を算入せずに１～２０の原子をもち、そして所望により単一のホウ素上の２個のＲ^D 基はいっしょになってホウ素に結合した両原子価をもつヒドロカルバジイルアミノ－、ヒドロカルバジイルオキシ－、ヒドロカルバジイルジアミノ－、又はヒドロカルバジイルオキシ－基を形成している；
但し少なくとも１の場合においてＲ^A はＢＲ^C ₂ 、ＢＲ^C ₂ －置換ヒドロカルビル基、及びそれらが合体した誘導体から選ばれると共に、少なくとも１のＲ^CはＲ^D である；
Ｒ^F はそれぞれの場合独立に水素、又はシリル、ヒドロカルビル、ヒドロカルビルオキシ及びそれらの組合せから選ばれる基であって、該Ｒ^F は３０以下の炭素又はケイ素原子をもっている；そして ｘは１～８であるか、又は所望により（Ｒ^F ₂ Ｅ）_x が－Ｔ'Ｚ'－又は－（Ｔ'Ｚ'）₂ －であり、ここでＴ'はそれぞれの場合独立にホウ素又はアルミニウムであり、そしてＺ'はそれぞれの場合独立に

(In the formula, M is a metal selected from one of Group 3-13 lanthanides or actinides in the Periodic Table of the Elements;
Z is a divalent group having boron, or a member of Group 14 of the Periodic Table of the Elements, and having nitrogen, phosphorus, sulfur or oxygen;
X is an anionic ligand group having 60 or less atoms without the inclusion of hydrogen, and optionally the two X groups together form a divalent anionic ligand group;
X'is a neutral Lewis base ligand with 20 or less atoms independently in each case;
p is a number from 0 to 5 and is 2 less than the formal oxidation state of M;
q is 0, 1 or 2;
E is silicon or carbon;
^RA is hydrogen or ^RB independently in each case;
RB is ^{BR C} ₂ or hydrocarbyl, hydrocarbylsilyl, halogen-substituted hydrocarbyl, hydrocarbyloxy-substituted hydrocarbyl, di (hydrocarbyl) amino-substituted hydrocarbyl, BR ^C ₂ -substituted hydrocarbyl, hydrocarbylsilylhydrocarbyl, di (hydrocarbyl) amino, Hydrocarbaziylamino, or hydrocarbyloxy groups, each RB has ^1-18 atoms without inclusion of hydrogen, and optionally the two ^RB groups are covalently bonded to form one or more fused rings. May be formed;
^RC is independently hydrocarbyl, halogen-substituted hydrocarbyl, hydrocarbyloxy-substituted hydrocarbyl, dihydrocarbylamino-substituted hydrocarbyl, hydrocarbaziylamino-substituted hydrocarbyl, hydrocarbylsilyl, hydrocarbylsilylhydrocarbyl, or R ^D ;
The ^{RDs are each independently dihydrocarbylamino or hydrocarbyloxy group with 1 to 20 atoms without the inclusion of hydrogen, and optionally the two RD groups} on a single boron together. It forms a hydrocarbaziylamino-, hydrocarbaziyloxy-, hydrocarbaziyldiamino-, or hydrocarbaziyloxy-group with both valences bound to boron;
However, in the case of at least 1, ^RA is selected from BR ^C ₂ , BR ^C ₂ -substituted hydrocarbyl groups, and derivatives in which they are combined, and at least 1 ^RC is R ^D ;
^RF is each case independently a group selected from hydrogen, or silyl, hydrocarbyl, hydrocarbyloxy and combinations thereof, the ^RF having 30 or less carbon or silicon atoms; and x being 1-8. There, or optionally (RF ₂ E) _x is ^-T'Z' -or-(T'Z') _2- , where T'is independently boron or aluminum in each case, and Z'is independent in each case

であり；
Ｒ¹ はそれぞれの場合独立に水素、ヒドロカルビル基、トリヒドロカルビルシリル基、又はトリヒドロカルビルシリルヒドロカルビル基であり、該Ｒ¹ 基は炭素を算入せずに２０以下の原子をもち、そして２個のこれらＲ¹ 基は所望によりいっしょになって環構造を形成していてもよい；そして
Ｒ⁵ はＲ¹ 又はＮ（Ｒ¹ ）₂ である。）
前記遷移金属錯体（７）の具体例としては、特表２００３－５０１４３３号公報の［００３０］に列挙された化合物が挙げられる。

And;
R ¹ is an independently hydrogen, hydrocarbyl group, trihydrocarbylsilyl group, or trihydrocarbylsilylhydrocarbyl group, ^each of which has 20 or less atoms without carbon, and two of these. The R ¹ groups may optionally be together to form a ring structure; and R ⁵ is R ¹ or N (R ¹ ) ₂ . )
Specific examples of the transition metal complex (7) include the compounds listed in [0030] of JP-A-2003-501433.

(Transition metal complex (8))
The transition metal complex (8) is a compound represented by the following general formula [A8].

<M>
In the formula [A8], M represents a transition metal atom of Group 4 and 5 of the periodic table, and is preferably a transition metal atom of Group 4. Specifically, it is titanium, zirconium, hafnium, vanadium, niobium, tantalum and the like, more preferably titanium, zirconium and hafnium, and particularly preferably titanium or zirconium.
The dotted line connecting N and M in the formula [A8] generally indicates that N is coordinated to M, but in the present invention, it may or may not be coordinated.

<M>
In the formula [A8], m represents an integer of 1 to 4, preferably an integer of 2 to 4, and more preferably 2.

<R ¹ to R ⁵ >
In the formula [A8], R ¹ to R ⁵ may be the same or different from each other, and may be the same or different from each other, and are a hydrogen atom, a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, and a boron-containing group. , Sulfur-containing group, phosphorus-containing group, silicon-containing group, germanium-containing group, or tin-containing group, and two or more of these may be linked to each other to form a ring.

Examples of the halogen atom include fluorine, chlorine, bromine and iodine.
Examples of the hydrocarbon group include the hydrocarbon groups exemplified as R ¹ to R ¹⁴ in the above-mentioned formula [A3], and in particular, the hydrocarbon group.
1 to 30 carbon atoms such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, neopentyl group, n-hexyl group, preferably 1 to 20 linear or branched alkyl groups;
Aryl groups having 6 to 30, preferably 6 to 20 carbon atoms such as a phenyl group, a naphthyl group, a biphenyl group, a terphenyl group, a phenanthryl group, and an anthrasenyl group;
These aryl groups include a halogen atom, an alkyl group or an alkoxy group having 1 to 30 carbon atoms, preferably 1 to 20, and a substituent such as an aryl group or an aryloxy group having 6 to 30 carbon atoms, preferably 6 to 20. Substituted aryl groups substituted with 1 to 5 are preferable.

R ¹ is a linear or branched hydrocarbon group having 1 to 20 carbon atoms and 3 to 20 carbon atoms from the viewpoint of olefin polymerization catalytic activity and giving a high molecular weight olefin polymer. A group selected from an alicyclic hydrocarbon group or an aromatic hydrocarbon group having 6 to 20 carbon atoms is preferable.

Heterocyclic compound residues include nitrogen-containing compounds such as pyrrole, pyridine, pyrimidine, quinoline, and triazine, oxygen-containing compounds such as furan and pyran, and sulfur-containing compounds such as thiophene, and heterocyclic compounds thereof. Examples of the compound residue include an alkyl group having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, and a group further substituted with a substituent such as an alkoxy group.

Examples of the oxygen-containing group include an alcoholic group, an aryloxy group, an ester group, an ether group, an acyl group, a carboxyl group, a carbonate group, a hydroxy group, a peroxy group, and a carboxylic acid anhydride group.

Examples of the nitrogen-containing group include an amino group, an imino group, an amide group, an imide group, a hydrazino group, a hydrazono group, a nitro group, a nitroso group, a cyano group, an isocyano group, a cyanate ester group, an amidino group, a diazo group and an amino group. Examples include those that have become ammonium salts.

Examples of the boron-containing group include a bolangyl group, a bolantriyl group, and a diboranyl group.
Examples of the sulfur-containing group include a mercapto group, a thioester group, a dithioester group, an alkylthio group, an arylthio group, a thioacyl group, a thioether group, a thiosian acid ester group, an isothian acid ester group, a sulfone ester group, a sulfonamide group and a thiocarboxyl group. Examples thereof include a dithiocarboxyl group, a sulfo group, a sulfonyl group, a sulfinyl group and a sulfenyl group.

Examples of the phosphorus-containing group include a phosphido group, a phosphoryl group, a thiophosphoryl group, a phosphat group and the like.
Examples of the silicon-containing group include a silyl group, a siloxy group, a hydrocarbon-substituted silyl group, a hydrocarbon-substituted siloxy group, and more specifically, a methylsilyl group, a dimethylsilyl group, a trimethylsilyl group, an ethylsilyl group, and a diethylsilyl group. , Triethylsilyl group, diphenylmethylsilyl group, triphenylsilyl group, dimethylphenylsilyl group, dimethyl-t-butylsilyl group, dimethyl (pentafluorophenyl) silyl group and the like. Examples of the hydrocarbon-substituted syroxy group include a trimethylsiloxy group.
Examples of the germanium-containing group and the tin-containing group include a group in which the silicon of the silicon-containing group is replaced with germanium or tin.

<R ⁶ >
In the formula [A8], R ⁶ is a hydrocarbon group having 1 to 4 carbon atoms consisting of only hydrogen atoms and primary or secondary carbons, an aliphatic hydrocarbon group having 4 or more carbon atoms, an aryl group substituted alkyl group, and a simple substance. It is selected from cyclic or bicyclic alicyclic hydrocarbon groups, aromatic hydrocarbon groups and halogen atoms. Of these, aliphatic hydrocarbon groups having 4 or more carbon atoms, aryl group-substituted alkyl groups, from the viewpoint of olefin polymerization catalytic activity, from the viewpoint of providing a high molecular weight olefin polymer, and from the viewpoint of hydrogen resistance during polymerization, It is preferably a group selected from a monocyclic or bicyclic alicyclic hydrocarbon group and an aromatic hydrocarbon group, more preferably a branched hydrocarbon group such as a t-butyl group; benzyl group, 1-. Aryl-substituted alkyl groups such as methyl-1-phenylethyl group (cumyl group), 1-methyl-1,1-diphenylethyl group, 1,1,1-triphenylmethyl group (trityl group); hydrocarbons at the 1-position Examples thereof include an alicyclic group having 6 to 15 carbon atoms such as a cyclohexyl group having a group, an adamantyl group, a norbornyl group, and a tetracyclododecyl group, or an alicyclic group hydrocarbon group having a compound ring structure.

<N>
In the formula [A8], n is a number satisfying the valence of M.

<X>
In the formula [A8], X is a hydrogen atom, a halogen atom, a hydrocarbon group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a boron-containing group, an aluminum-containing group, a phosphorus-containing group, a halogen-containing group, and a heterocyclic group. A compound residue, a silicon-containing group, a germanium-containing group, or a tin-containing group, and when n is 2 or more, the plurality of groups represented by X may be the same or different from each other, and the plurality of groups represented by X may be the same or different from each other. The groups of may combine with each other to form a ring.
Examples of each group such as a halogen atom and a hydrocarbon group include the same groups as those exemplified in the above description of R ¹ to R ⁵ . Of these, halogen atoms and hydrocarbon groups are preferable.

(Transition metal complex (9))
The transition metal complex (9) is a compound represented by the following general formula [A9].

<M>
In the formula [A9], M represents a transition metal atom of Group 4 to 11 of the periodic table, and specifically, titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, manganese, iron, cobalt, nickel, palladium, etc. It is preferably a metal atom of groups 4 to 7, 10 and specifically, titanium, zirconium, hafnium, vanadium, chromium, manganese and nickel, and more preferably titanium and nickel.
The dotted line connecting N and M in the formula [A9] generally indicates that N is coordinated to M, but in the present invention, it may or may not be coordinated.

<M>
In the formula [A9], m represents an integer of 1 to 4, and is preferably 2.

<R ¹ to R ⁵ >
In the formula [A9], R ¹ to R ⁵ may be the same as or different from each other, and are a hydrogen atom, a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, and a boron-containing group. , Sulfur-containing group, phosphorus-containing group, silicon-containing group, germanium-containing group, or tin-containing group, and two or more of these may be linked to each other to form a ring.

Examples of the halogen atom include fluorine, chlorine, bromine and iodine.
Hydrocarbon groups, heterocyclic compound residues, oxygen-containing groups, nitrogen-containing groups, boron-containing groups, sulfur-containing groups, phosphorus-containing groups, silicon-containing groups, germanium-containing groups, and tin-containing groups include the above-mentioned formulas [ Examples of R ¹ to R ⁵ in A8] can be mentioned.

A preferred embodiment of R ¹ is a group exhibiting aromaticity, and more preferably a pyrrole which may have an aryl group or a substituent represented by the following general formula [A9-1].

一般式［A9-1］において、Ｒ^1A～Ｒ^1Eは互いに同一でも異なっていても、また互いに結合して環を形成していてもよく、水素原子、炭化水素基、ヘテロ環式化合物残基、酸素含有基、窒素含有基、ホウ素含有基、イオウ含有基、リン含有基、ケイ素含有基、ゲルマニウム含有基またはスズ含有基である。炭化水素基、ヘテロ環式化合物残基、酸素含有基、窒素含有基、ホウ素含有基、イオウ含有基、リン含有基、ケイ素含有基、ゲルマニウム含有基、およびスズ含有基としては、上述した式［A9］におけるＲ¹～Ｒ⁵として例示したものが挙げられる。

In the general formula [A9-1], R ^1A to R ^1E may be the same or different from each other, or may be bonded to each other to form a ring, and may be a hydrogen atom, a hydrocarbon group, or a heterocyclic compound residue. , Oxygen-containing group, nitrogen-containing group, boron-containing group, sulfur-containing group, phosphorus-containing group, silicon-containing group, germanium-containing group or tin-containing group. Hydrocarbon groups, heterocyclic compound residues, oxygen-containing groups, nitrogen-containing groups, boron-containing groups, sulfur-containing groups, phosphorus-containing groups, silicon-containing groups, germanium-containing groups, and tin-containing groups include the above-mentioned formulas [ Examples are given as R ¹ to R ⁵ in A9].

<R ⁶ >
In the formula [A9], R ⁶ is a hydrocarbon group having 1 to 4 carbon atoms consisting of only hydrogen atoms and primary or secondary carbons, an aliphatic hydrocarbon group having 5 or more carbon atoms, an aryl group substituted alkyl group, and a simple substance. It is selected from cyclic or bicyclic alicyclic hydrocarbon groups, aromatic hydrocarbon groups and halogen atoms.

As R ⁶ , an aryl group having 6 to 30 carbon atoms, preferably 6 to 20 carbon atoms such as phenyl, benzyl, naphthyl, and anthranil;
A linear or branched (secondary) alkyl group having 1 to 30, preferably 1 to 20 carbon atoms such as methyl, ethyl, isopropyl, isobutyl, sec-butyl, and neopentyl;
Cyclobutyl, cyclopentyl, cyclohexyl, 2-methylcyclohexyl, 2,6-dimethylcyclohexyl, 3,5-dimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, cyclooctyl, cyclododecyl, etc. have 3 to 30 carbon atoms. , Preferably 3 to 20 cyclic saturated hydrocarbon groups, and R ⁶ is an aromatic group such as phenyl, benzyl, naphthyl, and 3,5-difluorophenyl, 3,5 in which these hydrogen atoms are substituted. -Bistrifluoromethylphenyl and the like are particularly preferred.

<N>
In the formula [A9], n is a number satisfying the valence of M, specifically 0 to 5, preferably 1 to 4, and more preferably 2.

<X>
In the formula [A9], X is a hydrogen atom, a halogen atom, a hydrocarbon group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a boron-containing group, an aluminum-containing group, a phosphorus-containing group, a halogen-containing group, and a heterocyclic group. A compound residue, a silicon-containing group, a germanium-containing group, or a tin-containing group, and when n is 2 or more, the plurality of groups represented by X may be the same or different from each other, and the plurality of groups represented by X may be the same or different from each other. The groups of may combine with each other to form a ring.

Examples of each group such as a halogen atom and a hydrocarbon group include the same groups as those exemplified in the above description of R ¹ to R ⁵ .
Specific examples of the transition metal complex (9) include the compounds listed in [0079] to [0088] of JP-A-2011-231291.

The transition metal complex is not limited to the above-mentioned transition metal complexes (1) to (9), and other than these, for example, Japanese Patent Application Laid-Open No. 2008-163140 [0007] and International Publication No. 2010/50256. [0030] to [0051], JP-A-2010-150246 [0016], International Publication No. 2013/184579 [0133], Japanese Patent Application Laid-Open No. 2013-534934 [0006], Japanese Patent Application Laid-Open No. 2009-534517. [0001], the transition metal complex described in [0009] to [0017] of JP-A-2001-516767 can be exemplified.

<Organoaluminum>
Examples of the organoaluminum include the general formula:
R ^a _m Al (OR ^b ) _n H _p X _q
^{(In the formula, Ra and R b may} be the same or different from each other and represent hydrocarbon groups having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms.
X indicates a halogen atom,
m is 0 <m ≦ 3, n is 0 ≦ n <3, p is 0 ≦ p <3, q is a number of 0 ≦ q <3, and m + n + p + q = 3).
Examples thereof include organoaluminum compounds represented by.

Such compounds include tri-n-alkylaluminum, such as trimethylaluminum, triethylaluminum, tri-n-butylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, etc.
Tri-branched alkyl aluminum such as triisopropyl aluminum, triisobutylaluminum, trisec-butylaluminum, tri-t-butylaluminum, tri-2-methylbutylaluminum, tri-3-methylhexylaluminum, tri-2-ethylhexylaluminum, etc. ,
Tricycloalkylaluminum, such as tricyclohexylaluminum, tricyclooctylaluminum,
Triarylaluminum, triarylaluminum such as triphenylaluminum, tri (4-methylphenyl) aluminum,
Dialkylaluminum hydrides such as diethylaluminum hydride, diisopropylaluminum hydride, diisobutylaluminum hydride, etc.
For example, isoprenyl aluminum represented by the general formula (iC ₄ H ₉ ) _x Al _y (C ₅ H ₁₀ ) _z (where x, y, z are positive numbers and z ≤ 2x). Alkenyl aluminum,
Alkoxides such as isobutylaluminum methoxydo and isobutylaluminum ethoxyoxide,
Dialkylaluminum alkoxides such as dimethylaluminum methoxyd, diethylaluminum ethoxide, dibutylaluminum butoxide,
Alkyl aluminum sesquialkoxides such as ethyl aluminum sesquiethoxydo, butylaluminum sesquibutoxide,
Partially alkoxylated alkylaluminum with an average composition represented by the general formula R ^a _2.5 Al (OR ^b ) _0.5 etc.
Alkylaluminum allyloxides, such as diethylaluminum phenoxide, diethylaluminum (2,6-di-t-butyl-4-methylphenoxide),
Dialkylaluminum halides such as dimethylaluminum chloride, diethylaluminum chloride, dibutylaluminum chloride, diethylaluminum bromide, diisobutylaluminum chloride,
Alkylaluminum sesquihalides such as ethylaluminum sesquichloride, butylaluminum sesquichloride, ethylaluminum sesquibramide,
Partially halogenated alkylaluminum, such as alkylaluminum dihalide, such as ethylaluminum dichloride,
Alkylaluminum dihydrides such as ethylaluminum dihydrides, propylaluminum dihydrides and other partially hydrogenated alkylaluminum,
Examples thereof include partially alkoxylated and halogenated alkylaluminum such as ethylaluminum ethoxychloride, butylaluminum butycyclolide, ethylaluminum ethoxybromid and the like. Further, a compound similar to the compound represented by the above general formula ^{Ram Al (OR b} _{) n H p X q} ^can _{also be used} , for example, organoaluminum in which two or more aluminum compounds are bonded via a nitrogen atom. Compounds can be mentioned. Specific examples of such a compound include (C ₂ H ₅ ) ₂ AlN (C ₂ H ₅ ) Al (C ₂ H ₅ ) ₂ .

Among these, from the viewpoint of ease of procurement and low cost, tri-n-alkylaluminum, tri-branched alkylaluminum, tricycloalkylaluminum, triarylaluminum, dialkylaluminum hydride, dialkylaluminum halide, alkylaluminum dihydride, Alkyl-aluminum dihalides are preferred, tri-n-alkylaluminum, tri-branched alkylaluminum are more preferred, and tri-branched alkylaluminum is even more preferred.

Further, among the tri-branched alkylaluminum, triisobutylaluminum is particularly preferable from the viewpoint of the stability of the aluminum compound and the low alteration property to the metallocene compound.

<Solvent>
As the solvent, a solvent in which the transition metal complex and the organoaluminum are soluble is preferable. Further, as the solvent, a solvent to be used in the polymerization step is preferable.

Specific examples of the solvent include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane and kerosene, and alicyclic hydrocarbons such as cyclopentane, cyclohexane, methylcyclopentane and methylcyclohexane. Aromatic hydrocarbons such as toluene and xylene are mentioned, with particular preference being hexane, heptane, octane, decane, cyclohexane and toluene.

From the viewpoint of stably storing the transition metal complex in a solution state for a long period of time and thus producing an olefin polymer with high catalytic activity, activated alumina or the like is previously contacted with a solvent before storing the transition metal complex. It is preferable to remove some or all of the impurities in the solvent.

<Contact of each component>
In the contacting step, the transition metal complex, the organoaluminum, and the solvent are brought into contact with each other.

In the contacting step, an operation of bringing the transition metal complex into contact with organoaluminum in a solvent (contacting operation) is usually performed, and then the obtained solution is stored until it is subjected to the next polymerization step. Will be done.

The operation of contacting the components can be carried out by adding the components to the container in any order, for example adding the transition metal complex and solvent to the container, then adding organoaluminum, and further solvent if necessary. Can be carried out by adding. Each component may be added in a plurality of times.

The atmosphere inside the container is preferably replaced with an inert gas such as nitrogen before adding each component.
In the transition metal complex, the concentration in the solution obtained by contacting the transition metal complex, the organic aluminum and the solvent is usually 1 × 10 in terms of the concentration of the transition metal atom in the transition metal complex. It is used in an amount of ^-10 to 1 × 10 ^-1 mol / L, preferably 1 × 10 ^-8 to 1 × 10 ⁻² mol / L.

Further, the organic aluminum is 10,000 mol or less, preferably 1,000 mol or less, more preferably 200 mol or less, relative to 1 mol of the transition metal atom in the transition metal complex in terms of the amount of aluminum atoms in the organic aluminum. It is used in an amount of mol or less, more preferably 199 mol or less, and particularly preferably 20 mol or less.

If the amount of the organoaluminum is more than the above range, there is a problem that the transition metal complex may react with the organoaluminum to be denatured or the risk of ignition of the organoaluminum may be increased. Polymerization of olefins may occur in the presence of the transition metal complex and organoaluminum, but in the contact step, the transition metal complex and organoaluminum may be maintained in contact for a long period of time as compared with the polymerization step. Therefore, these problems become remarkable. In the present invention, maintaining the transition metal complex in contact with organic aluminum after performing an operation of bringing the transition metal complex into contact with organic aluminum is also referred to as "preserving (transition metal complex)". ..

The lower limit of the amount of organoaluminum is preferably 1.0 mol or more according to the above criteria from the viewpoint of exerting the effect of stably preserving the transition metal complex.
The solution obtained by the contact operation can be stably stored for a long period of time. In other words, the contact step allows the transition metal complex to be stably stored in solution for a long period of time. This effect is confirmed by the fact that even if the transition metal complex is stored in a solution state for a long period of time and then used as a catalyst for olefin polymerization in the contact step, the catalytic activity in olefin polymerization does not decrease or the decrease is suppressed. be able to.

The period for storing the solution obtained by the contact operation is not particularly limited, but is preferably 1 hour from the viewpoint of enjoying the advantage that the transition metal complex does not need to be adjusted to the solution state immediately before the olefin polymerization. The above is more preferably 12 hours or more, still more preferably 1 day or more. The upper limit is, for example, 5 years.

[Polymerization process]
In the polymerization step, the olefin is polymerized in the presence of a solution containing the transition metal complex that has undergone the contact step and containing organoaluminum at a concentration of 0.005 mmol / L or more in terms of aluminum atom.

The organic aluminum concentration of the solution is 0.005 mmol / L or more, preferably 0.01 mmol / L or more (upper limit is, for example, 1,000 mmol / L) in terms of aluminum atoms.

In the polymerization step, preferably, a solution containing the transition metal complex and organoaluminum that has undergone the contact step and further organoaluminum (hereinafter, also referred to as “additional organoaluminum”) are added to the solution. Is prepared. At this time, a solvent may be further added. By adding additional organoaluminum in the polymerization step, in other words, by performing the addition of organoaluminum in two steps, the contact step and the polymerization step, it is necessary to prepare the transition metal complex into a solution state immediately before the olefin polymerization. It is possible to produce an olefin polymer with high catalytic activity while enjoying the advantage of not being present.

As the additional organoaluminum, those mentioned as specific examples of the organoaluminum used in the above-mentioned contact step can be used. As the organoaluminum, trimethylaluminum, triethylaluminum and triisobutylaluminum, which are easily available because of commercial products, are preferable. Of these, triisobutylaluminum, which is easy to handle, is particularly preferable.

The additional organoaluminum may be the same as or different from the organoaluminum used in the contacting step described above.
If necessary, the solution contains a transition metal complex other than the transition metal complex that has undergone the contact step (hereinafter, also referred to as “additional transition metal complex”; a transition metal complex that has undergone the contact step and an additional transition metal complex. Are collectively referred to as "transition metal complex (A)"),
From a complex alkyl compound (B-1b), a dialkyl compound (B-1c), an organoaluminum oxy compound (B-2), and a compound (B-3) that reacts with a transition metal complex (A) to form an ion pair. At least one compound selected (in the following description, these components and the organoaluminum are collectively referred to as "compound (B)").
Carrier (C) or organic compound component (D)
May be added.
Hereinafter, each optional component will be described.

(Additional transition metal complex)
When used, the additional transition metal complex is used in an amount of, for example, 50% by mass or less, 10% by mass or less, or 1% by mass or less, assuming that the total amount of the transition metal complex (A) is 100% by mass. Will be done.

(Compound (B))
<< Complex alkylated product (B-1b) >>
The complex alkylated product (B-1b) is a general formula M ² AlR ^a ₄
(In the formula, M ² represents Li, Na or K, and Ra represents ^a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms.)
It is a complex alkylated product of aluminum and Group 1 metal of the periodic table represented by.
Examples of such compounds include LiAl (C ₂ H ₅ ) ₄ , LiAl (C ₇ H ₁₅ ) ₄ , and the like.

<< Dialkyl compound (B-1c) >>
The dialkyl compound (B-1c) has the general formula R ^a R ^b M ^{3
(In the formula, Ra and R b may} be the same or different from each other, and represent hydrocarbon groups having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, and M ³ is Mg, Zn or Cd.)
It is a dialkyl compound of a group 2 or 12 metal of the periodic table represented by.

In the following description, the organoaluminum, the complex alkylated product (B-1b), and the dialkyl compound (B-1c) are collectively referred to as "organic metal compound (B-1)" or "component (B-). Also called "1)".

<< Organoaluminium oxy compound (B-2) >>
As the organoaluminum oxy compound (B-2), conventionally known aluminoxane can be used as it is. Specifically, the following general formula [B2-1]

および／または下記一般式［B2-2］

And / or the following general formula [B2-2]

（式中、Ｒは炭素数１から１０の炭化水素基、ｎは2以上の整数を示す）
で表わされる化合物を挙げることができ、特にＲがメチル基であるメチルアルミノキサンであってｎが３以上、好ましくは１０以上のものが利用される。これらアルミノキサン類に若干の有機アルミニウム化合物が混入していても差し支えない。本発明においてエチレンと炭素数が３以上のα－オレフィンとの共重合を高温で行う場合には、特開平2-78687号公報に例示されているようなベンゼン不溶性の有機アルミニウムオキシ化合物も適用することができる。また、特開平2-167305号公報に記載されている有機アルミニウムオキシ化合物、特開平2-24701号公報、特開平3-103407号公報に記載されている二種類以上のアルキル基を有するアルミノキサンなども好適に利用できる。なお、本発明で用いられることのある「ベンゼン不溶性の有機アルミニウムオキシ化合物」とは、６０℃のベンゼンに溶解するＡｌ成分がＡｌ原子換算で通常１０％以下、好ましくは５％以下、特に好ましくは２％以下であり、ベンゼンに対して不溶性または難溶性である化合物である。

(In the formula, R is a hydrocarbon group having 1 to 10 carbon atoms, and n is an integer of 2 or more).
The compound represented by the above can be mentioned, and in particular, a methylaluminoxane having R as a methyl group and having n of 3 or more, preferably 10 or more is used. It does not matter if some organoaluminum compounds are mixed in these aluminoxans. In the present invention, when copolymerization of ethylene with an α-olefin having 3 or more carbon atoms is carried out at a high temperature, a benzene-insoluble organoaluminum oxy compound as exemplified in JP-A-2-78687 is also applied. be able to. In addition, organoaluminum oxy compounds described in JP-A No. 2-167305, and aluminoxane having two or more types of alkyl groups described in JP-A-2-24701 and JP-A-3-103407 are also available. It can be suitably used. The "benzene-insoluble organic aluminum oxy compound" that may be used in the present invention means that the Al component dissolved in benzene at 60 ° C. is usually 10% or less, preferably 5% or less, particularly preferably 5% or less in terms of Al atoms. It is a compound having 2% or less and being insoluble or sparingly soluble in benzene.

Further, as the organoaluminum oxy compound (B-2), modified methylaluminoxane as represented by the following general formula [B2-3] can also be mentioned.

（式中、Ｒは炭素数１から１０の炭化水素基、ｍおよびｎはそれぞれ独立に２以上の整数を示す。）

(In the formula, R is a hydrocarbon group having 1 to 10 carbon atoms, and m and n are independently integers of 2 or more.)

This modified methylaluminoxane is prepared using trimethylaluminum and alkylaluminum other than trimethylaluminum. Such compounds are commonly referred to as MMAO. Such MMAOs can be prepared by the methods set forth in US Pat. No. 4,960,878 and US Pat. No. 5,541,584. Further, those prepared by using trimethylaluminum and triisobutylaluminum and having R as an isobutyl group are commercially available from Toso Finechem Co., Ltd. under the names of MMAO and TMAO. Such MMAO is an aluminoxane having improved solubility in various solvents and storage stability, and specifically, with respect to benzene among the compounds represented by the above formulas [B2-1] and [B2-2]. Unlike insoluble or sparingly soluble compounds, it dissolves in aliphatic or alicyclic hydrocarbons.

Further, as the organoaluminum oxy compound (B-2), an organoaluminum oxy compound containing boron represented by the following general formula [B2-4] can also be mentioned.

（式中、Ｒ^cは炭素数１から１０の炭化水素基を示す。Ｒ^dは、互いに同一でも異なっていてもよく、水素原子、ハロゲン原子または炭素数１から１０の炭化水素基を示す。）

(In the formula, R ^c represents a hydrocarbon group having 1 to 10 carbon atoms. R ^d may be the same as or different from each other, and represents a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 10 carbon atoms. )

As the organoaluminum oxy compound (B-2), methylaluminoxane, which is easily available for commercial products, and MMAO prepared using trimethylaluminum and triisobutylaluminum are preferable. Of these, MMAO having improved solubility in various solvents and storage stability is particularly preferable.

<< Compound (B-3) that reacts with the transition metal complex (A) to form an ion pair >>
Examples of the compound (B-3) (hereinafter, also referred to as “ionic compound (B-3)”) that reacts with the transition metal complex (A) to form an ion pair include JP-A No. 1-501950 and JP-A. Lewis acid and ionicity described in JP-A-1-502036, JP-A-3-179005, JP-A-3-179006, JP-A-3-207703, JP-A-3-207704, USP5321106, etc. Examples thereof include compounds, borane compounds and carborane compounds. Further, heteropoly compounds and isopoly compounds can also be mentioned. However, the above-mentioned (B-2) organoaluminum oxy compound is not included.

The ionic compound (B-3) preferably includes a boron compound represented by the following general formula [B3-1].

式中、Ｒ^e+としては、Ｈ⁺、カルベニウムカチオン、オキソニウムカチオン、アンモニウムカチオン、ホスホニウムカチオン、シクロヘプチルトリエニルカチオン、遷移金属を有するフェロセニウムカチオンなどが挙げられる。Ｒ^fからＲⁱは、互いに同一でも異なっていてもよく、炭素数１から２０の炭化水素基、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選ばれる置換基であり、好ましくは置換アリール基である。

In the formula, Examples of R ^{e +} include H ⁺ , carbenium cation, oxonium cation, ammonium cation, phosphonium cation, cycloheptyllienyl cation, ferrosenium cation having a transition metal, and the like. R ^f to R ⁱ may be the same or different from each other, and are substituents selected from hydrocarbon groups having 1 to 20 carbon atoms, silicon-containing groups, nitrogen-containing groups, oxygen-containing groups, halogen atoms and halogen-containing groups. Yes, preferably a substituted aryl group.

Specific examples of the ionic compound (B-3) include those described in International Publication No. 2015/122414 [0133] to [0144].
In addition, the ionic compounds disclosed in JP-A-2004-51676 can also be used without limitation.

The ionic compound (B-3) may be used alone or in combination of two or more.
As the compound (B-3) that reacts with the transition metal complex (A) to form an ion pair, it is easily available as a commercial product and contributes greatly to the improvement of polymerization activity. Therefore, triphenylcarbenium tetrakis. (Pentafluorophenyl) borate and N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate are preferred.

(Carrier (C))
A carrier (C) may be used as a constituent component of the olefin polymerization catalyst, if necessary. The carrier (C) is an inorganic or organic compound and is a solid in the form of granules or fine particles. Specifically, it is described in, for example, International Publication No. 2006/123759 [0205] to [0218]. I can mention things.

(Organic compound component (D))
If necessary, the organic compound component (D) may be used as a constituent component of the olefin polymerization catalyst. The organic compound component (D) is used for the purpose of improving the polymerization performance and the physical properties of the produced polymer. Examples of the organic compound component (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 usage and the order of addition of each catalyst component are arbitrarily selected, and the following methods are exemplified.
(1) A method of adding a transition metal complex and organoaluminum that have undergone a contact step and additional organoaluminum to a polymerizer in an arbitrary order.
(2) A method of adding a transition metal complex and organoaluminum that have undergone a contact step, additional organoaluminum, and compound (B) (other than organoaluminum) to a polymerizer in any order.
(3) A method in which a catalyst component in which a transition metal complex and organoaluminum that have undergone a contact step are supported on a carrier (C) and additional organoaluminum are added to a polymerizer in an arbitrary order.
(4) A method of adding a catalyst component in which additional organoaluminum is supported on a carrier (C), a transition metal complex that has undergone a contact step, and organoaluminum to a polymerizer in an arbitrary order.
The transition metal complex and organoaluminum that have undergone the contact step are usually added in the form of a solution.

In each of the above methods, the organic compound component (D) may be added in any order.
In each of the above methods (3) and (4), the unsupported compound (B) may be added in any order, if necessary.
Further, in the solid catalyst component in which the transition metal complex and the organic aluminum (1) are supported on the carrier (C), the olefin may be prepolymerized, and the catalyst component is further supported on the prepolymerized solid catalyst component. It may have been done.

Examples of the olefins to be subjected to polymerization are ethylene, propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-. Linear or branched α-olefins with 3 to 20 carbon atoms such as pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, vinylcyclohexane, etc. Can be mentioned.

These α-olefins can be used alone or in combination of two or more. Therefore, for example, ethylene may be used alone, or ethylene and propylene may be used.

Further, at least one monomer selected from a polar group-containing monomer, an aromatic vinyl compound, and a cyclic olefin may be allowed to coexist in the reaction system to proceed with the polymerization. Therefore, for example, 5-ethylidene-2-norbornene, which is a cyclic olefin, may be used together with ethylene and propylene. The amount of these monomers is, for example, 20 parts by mass or less, preferably 10 parts by mass or less, based on 100 parts by mass of the α-olefin.

Examples of the polar group-containing monomer include α, β-unsaturated carboxylic acids such as acrylic acid, methacrylic acid, fumaric acid, and maleic anhydride, metal salts such as sodium salts thereof, methyl acrylate, ethyl acrylate, and acrylic acid. Α, β-Unsaturated carboxylic acid esters such as n-propyl, methyl methacrylate and ethyl methacrylate, vinyl esters such as vinyl acetate and vinyl propionate, unsaturated glycidyls such as glycidyl acrylate and glycidyl methacrylate, etc. Can be exemplified.

Examples of aromatic vinyl compounds include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, o, p-dimethylstyrene, methoxystyrene, vinylbenzoic acid, methyl vinylbenzoate, vinylbenzylacetate, and hydroxystyrene. Examples thereof include p-chlorostyrene, divinylbenzene, α-methylstyrene, and allylbenzene.

Examples of the cyclic olefin include cyclic olefins having 3 to 30 carbon atoms, preferably 3 to 20 carbon atoms such as cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, 5-ethylidene-2-norbornene, and tetracyclododecene. can do.

The polymerization can be carried out by any of a liquid phase polymerization method such as solution polymerization and suspension polymerization or a gas phase polymerization method. Examples of the inert hydrocarbon medium used in the liquid phase polymerization method include those mentioned as specific examples of the solvent usually used in the above-mentioned contact step.

As the inert hydrocarbon medium, the solvent used in the contact step may be used as it is, or a new inert hydrocarbon medium may be added to the solvent used in the contact step. The newly added inert hydrocarbon medium may be the same as or different from the solvent used in the contacting step.

The amount of each component that can constitute a catalyst for olefin polymerization in the polymerization step is as follows. Further, in the catalyst for olefin polymerization, the content of each component can be set as follows.

The component (A) is usually used in an amount of 10 ^-10 to ^10-2 mol, preferably 10 ^-8 to 10 ^-3 mol, per liter of the reaction volume.
The molar ratio [(B-1) / M] of the component (B-1) to the total transition metal atom (M) in the component (B-1) is usually 1 to 50,000, preferably 1 to 50,000. Can be used in an amount of 10 to 20,000, particularly preferably 50 to 10,000.

The molar ratio [Al / M] of the aluminum atom in the component (B-2) to the total transition metal atom (M) in the component (A) is usually 10 to 5,000, preferably 10 to 5,000. Can be used in an amount of 20 to 2,000.

The molar ratio [(B-3) / M] of the component (B-3) to the total transition metal atom (M) in the component (A) is usually 1 to 1000, preferably 1. It can be used in an amount of up to 200.

When the component (C) is used, the weight ratio of the component (A) to the 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 such that it is 0.001 to 0.1.

The polymerization temperature of the olefin in the polymerization step is usually −50 to + 200 ° C., preferably 0 to 180 ° C.; 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 by any of a batch type, a semi-continuous type and a continuous type. Further, the polymerization can be carried out in two or more stages having different reaction conditions. The molecular weight of the obtained olefin polymer can be adjusted by allowing hydrogen or the like to be present in the polymerization system, changing the polymerization temperature, or adjusting the amount of the component (B) used.

[Preservation method of transition metal complex]
The method for preserving a transition metal complex of the present invention comprises a preservation step of preserving the transition metal complex in a solution containing organic aluminum, wherein the solution converts organic aluminum into the amount of aluminum atoms in the organic aluminum. The transition metal atom in the transition metal complex is 10,000 mol or less, preferably 1,000 mol or less, more preferably 200 mol or less, still more preferably 199 mol or less, and particularly preferably 20 mol or less. Included in quantity. The lower limit of the amount of organoaluminum is preferably 1.0 mol or more according to the above criteria from the viewpoint of exerting the effect of stably preserving the transition metal complex.

In the storage step, an operation of contacting the transition metal complex with organoaluminum in a solvent (contact operation) is performed, and then the obtained solution is stored.
The transition metal complex is not particularly limited, and examples thereof include conventionally known transition metal complexes. Among the transition metal complexes, the preservation method of the present invention can be particularly preferably applied to the preservation of the transition metal complex used as a catalyst for olefin polymerization. Specific embodiments (type, ratio, preferred embodiments, etc.) of the transition metal complex used in the catalyst for olefin polymerization are as described in the above description of the contact step in the method for producing an olefin polymer of the present invention.

Specific embodiments (type, ratio, preferred embodiments, etc.) of the organoaluminum and the solvent are as described in the above description of the contact step in the method for producing the olefin polymer of the present invention.

From the viewpoint of enhancing the preservation effect of the transition metal complex, it is preferable to contact activated alumina or the like with the solvent in advance to remove some or all of the impurities in the solvent before preserving the transition metal complex.

The period for storing the solution obtained by the contact operation is not particularly limited, but is preferably 1 hour or longer, more preferably 12 hours or longer, still more preferably 1 day or longer. The upper limit is, for example, 5 years.

Hereinafter, the present invention will be described in more detail based on Examples, but the present invention is not limited to these Examples.
[Synthesis Example 1]
[Bis (4-methoxyphenyl) methylene (η ⁵ -cyclopentadienyl) (η ⁵ -tetramethyldodecahydrodibenzofluorenyl)] Hafnium dimethyl (hereinafter also referred to as “transition metal complex a”) is WO2015 / After synthesizing [bis (4-methoxyphenyl) methylene (η ⁵ -cyclopentadienyl) (η ⁵ -tetramethyldodecahydrodibenzofluorenyl)] hafnium dichloride according to the method described in 122414, JP-A-7 Methyllithium was reacted according to the method described in Example 86 of the publication No. 53618, and [bis (4-methoxyphenyl) methylene (η ⁵ -cyclopentadienyl) (η ⁵ -tetramethyldodecahydrodibenzofluorenyl). ] Hafnium dimethyl was synthesized.

[Synthesis Example 2]
[Bis (4-methoxyphenyl) methylene (η ⁵ -cyclopentadienyl) (η ⁵ -2,3,6,7-tetramethylfluorenyl)] Hafnium dimethyl (hereinafter also referred to as "transition metal complex b". ) Is [bis (4-methoxyphenyl) methylene (η ⁵ -cyclopentadienyl) (η ⁵ -2,3,6,7-tetramethylfluorenyl)] hafnium dichloride according to the method described in WO2015 / 122415. Is then reacted with methyllithium according to the method described in Example 86 of JP-A-7-53618 to [bis (4-methoxyphenyl) methylene (η ⁵ -cyclopentadienyl) (η ⁵ ). -2,3,6,7-Tetramethylfluorenyl)] Hafnium dimethyl was synthesized.

[Synthesis Example 3]
[Methyl (4-methylphenyl) methylene (η ⁵ -cyclopentadienyl) (η ⁵ -octamethyloctahydrodibenzofluorenyl)] Zirconium dimethyl (hereinafter also referred to as “transition metal complex c”) is WO2004 / After synthesizing [methyl (4-methylphenyl) methylene (η ⁵ -cyclopentadienyl) (η ⁵ -octamethyloctahydrodibenzofluorenyl)] zirconium dichloride according to the method described in 029062, JP-A-7 Methyllithium was reacted according to the method described in Example 86 of the publication No. 53618, and [Methyl (4-methylphenyl) methylene (η ⁵ -cyclopentadienyl) (η ⁵ -octamethyloctahydrodibenzofluorenyl). ] Zirconium dimethyl was synthesized.

[Examples 1-1 to 1-5]
[Contact step or storage step (containing 20 equivalents of triisobutylaluminum [bis (4-methoxyphenyl) methylene (η ⁵ -cyclopentadienyl) (η ⁵ -tetramethyldodecahydrodibenzofluorenyl)] hafnium dimethyl Preparation of hexane solution)]
(Contact operation 1)
[Bis (4-methoxyphenyl) methylene (η ⁵ -cyclopentadienyl) (η ⁵ -tetramethyldodecahydro) immediately after the synthesis in Synthesis Example 1 was placed in a glass two-port flask having an internal volume of 100 ml sufficiently substituted with nitrogen. Dibenzofluorenyl)] 8.27 mg of hafnium dimethyl (transition metal complex a) and n-hexane from which impurities have been removed with active alumina are charged at 25 ° C., and then 1 mol of triisobutylaluminum is added to the transition metal complex a. A solution (A) having a transition metal complex a concentration of 0.1 mmol / l was prepared by adding 20 mol to the amount and further adding n-hexane to make the total volume 100 ml.
Then, immediately, this solution (A) was subdivided into five glass two-necked flasks having an internal volume of 25 ml and sufficiently nitrogen-substituted to obtain solutions (A-1) to (A-5).

(Preservation of solution)
In Example 1-1, the solution (A-1) containing the transition metal complex a obtained in the contact operation 1 was stored for 1 hour in a cool and dark place at a temperature of 2 ° C. under a nitrogen atmosphere.
Similarly, in Examples 1-2 to 1-5, the solutions (A-2) to (A-5) containing the transition metal complex a obtained in the contact operation 1 are placed in a cool and dark place at a temperature of 2 ° C. under a nitrogen atmosphere. Saved in. The storage period of each solution is shown in Table 1.

[Polymerization process (production of ethylene / propylene copolymer)]
(Example 1-1)
680 ml of heptane and 160 g of propylene were charged into a stainless steel autoclave having an internal volume of 2 L sufficiently substituted with nitrogen, the temperature in the system was raised to 111 ° C., and then ethylene was supplied to bring the total pressure to 3 MPa-G. .. Next, here, 0.3 mmol of triisobutylaluminum, 1.5 ml of the solution (A-1) immediately after storage (this solution contains 0.00015 mmol of the transition metal complex a) and triphenylcarbenium tetrakis (this solution contains 0.00015 mmol). Polymerization was started by press-fitting 0.00075 mmol of pentafluorophenyl) borate with nitrogen and setting the stirring speed to 250 rpm. Then, by continuously supplying only ethylene, the total pressure was maintained at 3 MPa-G, and polymerization was carried out at 115 ° C. for 10 minutes. After terminating the polymerization by adding a small amount of ethanol into the system, unreacted ethylene was purged. The polymer was precipitated by pouring the obtained polymer solution into a large excess of methanol. The polymer was collected by filtration and dried under reduced pressure at 120 ° C. overnight.

As a result, 45.3 g of an ethylene / propylene copolymer was obtained. The mileage per 1 mmol of hafnium atom in the transition metal complex a was 302 kg. The results are shown in Table 1.

(Examples 1-2 to 1-5)
In Examples 1-2 to 1-5, the solution (A-1) is 1.5 ml of the solution (A-2) immediately after the storage is completed, and 1.5 ml of the solution (A-) immediately after the storage is completed. 3), 1.5 ml of solution (A-4) immediately after storage, or 1.5 ml of solution (A-5) immediately after storage (these solutions each have 0 transition metal complex a. An ethylene / propylene copolymer was produced under the same procedure and conditions as in Example 1-1 except that the mixture was changed to .00015 mmol.
Table 1 shows the yield of the obtained ethylene / propylene copolymer and the mileage per 1 mmol of hafnium atom in the transition metal complex a.

[Comparative Examples 1-1 to 1-5]
[Preparation of hexane solution of hafnium dimethyl [bis (4-methoxyphenyl) methylene (η ⁵ -cyclopentadienyl) (η ⁵ -tetramethyldodecahydrodibenzofluorenyl)] containing no triisobutylaluminum]
(Comparative contact operation 1)
The same operation as in contact operation 1 was performed except that triisobutylaluminum was not used, a solution (A') having a transition metal complex a concentration of 0.1 mmol / l was prepared, and this solution (A') was immediately prepared. Solutions (A'-1) to (A'-5) were obtained by subdividing into five glass two-necked flasks having an internal volume of 25 ml and sufficiently substituted with nitrogen.

(Preservation of solution)
The solutions (A'-1) to (A'-5) containing the transition metal complex a obtained in Comparative Contact Operation 1 were stored in a cool and dark place at a temperature of 2 ° C. under a nitrogen atmosphere. The storage period of each solution is shown in Table 2.

[Polymerization process (production of ethylene / propylene copolymer)]
In Comparative Examples 1-1 to 1-5, the solution (A-1) was the 1.5 ml solution (A'-1) immediately after the storage and the 1.5 ml solution (A) immediately after the storage. '-2), 1.5 ml solution immediately after storage (A'-3), 1.5 ml solution immediately after storage (A'-4), or 1. immediately after storage. Ethylene / propylene co-weight under the same procedures and conditions as in Example 1-1, except that they were each changed to 5 ml solutions (A'-5) (each of which contained 0.00015 mmol of the transition metal complex a). Manufactured a coalescence.
Table 2 shows the yield of the obtained ethylene / propylene copolymer and the mileage per 1 mmol of hafnium atom in the transition metal complex a.

[Examples 2-1 to 2-5]
[Contact step or storage step (5.0 mmol / l [bis (4-methoxyphenyl) methylene (η ⁵ -cyclopentadienyl) containing 50 equivalents of triisobutylaluminum) (η ^5-2,3,6,7 ) -Tetramethylfluorenyl)] Preparation of hexane solution of hafnium dimethyl)]
(Contact operation 2)
[Bis (4-methoxyphenyl) methylene (η ⁵ -cyclopentadienyl) (η ^5-2,3 , 6,7-Tetramethylfluorenyl)] Hafnium dimethyl (transition metal complex b) 360 mg and n-hexane from which impurities have been removed with active alumina are charged at 25 ° C., and then 1 mol of triisobutylaluminum is transferred. A solution (B) having a transition metal complex b having a concentration of 5.0 mmol / l was prepared by adding 50 mol to the metal complex b and further adding n-hexane to make the total volume 100 ml.
Then, immediately, this solution (B) was subdivided into five glass two-necked flasks having an internal volume of 25 ml and sufficiently nitrogen-substituted to obtain solutions (B-1) to (B-5).

(Preservation of solution)
In Example 2-1 the solution (B-1) containing the transition metal complex b obtained in the contact operation 2 was stored for 1 hour in a cool and dark place at a temperature of 2 ° C. under a nitrogen atmosphere.
Similarly, in Examples 2-2 to 2-5, the solutions (B-2) to (B-5) containing the transition metal complex b obtained in the contact operation 2 are placed in a cool and dark place at a temperature of 2 ° C. under a nitrogen atmosphere. Saved in. The storage period of each solution is shown in Table 3.

[Polymerization process (production of ethylene / propylene / ENB copolymer)]
(Example 2-1)
Hexane (1030 ml) and ethylidene norbornene (ENB) (12 ml) were charged into a stainless steel autoclave having an internal volume of 2 L sufficiently substituted with nitrogen, the temperature in the system was raised to 92 ° C., and then propylene was divided into 0.45 MPa by partial pressure. The total pressure was adjusted to 1.6 MPa-G by supplying ethylene. Next, here, 0.3 mmol of triisobutylaluminum, 0.03 ml of the solution (B-1) immediately after storage (this solution contains 0.00015 mmol of the transition metal complex b) and triphenylcarbenium tetrakis (this solution contains 0.00015 mmol). Polymerization was started by press-fitting 0.0015 mmol of pentafluorophenyl) borate with nitrogen and setting the stirring speed to 250 rpm. Then, by continuously supplying only ethylene, the total pressure was maintained at 1.6 MPa-G, and polymerization was carried out at 95 ° C. for 15 minutes. After terminating the polymerization by adding a small amount of ethanol into the system, unreacted ethylene was purged. The obtained polymer solution was put into a large excess of methanol / acetone mixed solution to precipitate the polymer. The polymer was collected by filtration and dried under reduced pressure at 120 ° C. overnight.

As a result, 10.69 g of an ethylene / propylene / ENB copolymer was obtained. The mileage per 1 mmol of hafnium atom in the transition metal complex b was 71.3 kg. The results are shown in Table 3.

(Examples 2-2-2-5)
In Examples 2-2-2-5, the solution (B-1) is 0.03 ml of the solution (B-2) immediately after the storage is completed, and 0.03 ml of the solution (B-2) immediately after the storage is completed. 3) 0.03 ml solution (B-4) immediately after storage, or 0.03 ml solution (B-5) immediately after storage (these solutions each have 0 transition metal complex b). An ethylene / propylene / ENB copolymer was produced under the same procedure and conditions as in Example 2-1 except that the mixture was changed to .00015 mmol.

Table 3 shows the yield of the obtained ethylene / propylene / ENB copolymer and the mileage per 1 mmol of hafnium atom in the transition metal complex b.

[Comparative Examples 2-1 to 2-5]
[5.0 mmol / l [bis (4-methoxyphenyl) methylene (η ⁵ -cyclopentadienyl) (η ⁵ -2,3,6,7-tetramethylfluorenyl)] containing no triisobutylaluminum] Preparation of hexane solution of hafnium dimethyl]
(Comparative contact operation 2)
The same operation as in contact operation 2 was performed except that triisobutylaluminum was not used, a solution (B') having a transition metal complex b concentration of 5.0 mmol / l was prepared, and this solution (B') was immediately prepared. Solutions (B'-1) to (B'-5) were obtained by subdividing into five glass two-necked flasks having an internal volume of 25 ml and sufficiently substituted with nitrogen.

(Preservation of solution)
The solutions (B'-1) to (B'-5) containing the transition metal complex b obtained in the comparative contact operation 2 were stored in a cool and dark place at a temperature of 2 ° C. under a nitrogen atmosphere. The storage period of each solution is shown in Table 4.

[Polymerization process (production of ethylene / propylene / ENB copolymer)]
In Comparative Examples 2-1 to 2-5, the solution (B-1) was 0.03 ml of the solution (B'-1) immediately after the storage and 0.03 ml of the solution (B) immediately after the storage. '-2), 0.03 ml solution immediately after storage (B'-3), 0.03 ml solution immediately after storage (B'-4), or 0. immediately after storage. Ethylene / propylene / ENB under the same procedures and conditions as in Example 2-1 except that they were each changed to 03 ml of solution (B'-5) (each of which contained 0.00015 mmol of the transition metal complex b). A copolymer was produced.

Table 4 shows the yield of the obtained ethylene / propylene / ENB copolymer and the mileage per 1 mmol of hafnium atom in the transition metal complex b.

[Examples 3-1 to 3-4]
Contact step or solution storage (1.0 mmol / l [bis (4-methoxyphenyl) methylene (η ⁵ -cyclopentadienyl) containing 20 eq triisobutylaluminum) (η ^5-2,3,6 , 7-Tetramethylfluorenyl)] Preparation of hexane solution of hafnium dimethyl)]
(Contact operation 3)
[Bis (4-methoxyphenyl) methylene (η ⁵ -cyclopentadienyl) (η ^5-2,3 , 6,7-Tetramethylfluorenyl)] Hafnium dimethyl (transition metal complex b) 72 mg and n-hexane from which impurities have been removed with active alumina are charged at 25 ° C., and then 1 mol of triisobutylaluminum is transferred. A solution (C) having a transition metal complex b having a concentration of 1.0 mmol / l was prepared by adding 20 mol to the metal complex b and further adding n-hexane to make the total volume 100 ml.
Then, immediately, this solution (C) was subdivided into four glass two-necked flasks having an internal volume of 25 ml and sufficiently nitrogen-substituted to obtain solutions (C-1) to (C-4).

(Preservation of solution)
In Example 3-1 the solution (C-1) containing the transition metal complex b obtained in the contact operation 3 was stored for 1 hour in a cool and dark place at a temperature of 2 ° C. under a nitrogen atmosphere.
Similarly, in Examples 3-2 to 3-4, the solutions (C-2) to (C-4) containing the transition metal complex b obtained in the contact operation 3 are placed in a cool and dark place at a temperature of 2 ° C. under a nitrogen atmosphere. Saved in. The storage period of each solution is shown in Table 5.

[Polymerization process (production of ethylene / propylene / ENB copolymer)]
(Example 3-1)
Hexane (1030 ml) and ethylidene norbornene (ENB) (12 ml) were charged into a stainless steel autoclave having an internal volume of 2 L sufficiently substituted with nitrogen, the temperature in the system was raised to 92 ° C., and then propylene was divided into 0.45 MPa by partial pressure. The total pressure was adjusted to 1.6 MPa-G by supplying ethylene. Next, here, 0.30 mmol of triisobutylaluminum, 0.15 ml of the solution (C-1) immediately after storage (this solution contains 0.00015 mmol of the transition metal complex b) and triphenylcarbenium tetrakis (this solution contains 0.00015 mmol). Polymerization was started by press-fitting 0.0015 mmol of pentafluorophenyl) borate with nitrogen and setting the stirring speed to 250 rpm. Then, by continuously supplying only ethylene, the total pressure was maintained at 1.6 MPa-G, and polymerization was carried out at 95 ° C. for 15 minutes. After terminating the polymerization by adding a small amount of ethanol into the system, unreacted ethylene was purged. The obtained polymer solution was put into a large excess of methanol / acetone mixed solution to precipitate the polymer. The polymer was collected by filtration and dried under reduced pressure at 120 ° C. overnight.

As a result, 9.09 g of an ethylene / propylene / ENB copolymer was obtained. The mileage per 1 mmol of hafnium atom in the transition metal complex b was 60.6 kg. The results are shown in Table 5.

(Examples 3-2 to 3-4)
In Examples 3-2 to 3-4, the solution (C-1) is a 0.15 ml solution (C-2) immediately after the storage is completed, and a 0.15 ml solution (C-) immediately after the storage is completed. 3) or 0.15 ml of the solution (C-4) immediately after the storage was completed (these solutions each contain 0.00015 mmol of the transition metal complex b), except that the solution was changed to Example 3-1. Ethylene / propylene / ENB copolymers were produced under the same procedure and conditions.

Table 5 shows the yield of the obtained ethylene / propylene / ENB copolymer and the mileage per 1 mmol of hafnium atom in the transition metal complex b.

[Comparative Examples 3-1 to 3-4]
[1.0 mmol / l [bis (4-methoxyphenyl) methylene (η ⁵ -cyclopentadienyl) (η ⁵ -2,3,6,7-tetramethylfluorenyl)] containing no triisobutylaluminum] Preparation of hexane solution of hafnium dimethyl]
(Comparative contact operation 3)
The same operation as in contact operation 3 was performed except that triisobutylaluminum was not used, a solution (C') having a transition metal complex b concentration of 1.0 mmol / l was prepared, and this solution (C') was immediately prepared. Solutions (C'-1) to (C'-4) were obtained by subdividing into four glass two-necked flasks having an internal volume of 25 ml sufficiently substituted with nitrogen.

(Preservation of solution)
The solutions (C'-1) to (C'-4) containing the transition metal complex b obtained in Comparative Contact Operation 3 were stored in a cool and dark place at a temperature of 2 ° C. under a nitrogen atmosphere. The storage period of each solution is shown in Table 6.

[Polymerization process (production of ethylene / propylene / ENB copolymer)]
In Comparative Examples 3-1 to 3-4, the solution (C-1) was a 0.15 ml solution (C'-1) immediately after the storage, and a 0.15 ml solution (C) immediately after the storage. '-2), 0.15 ml solution immediately after storage (C'-3), or 0.15 ml solution immediately after storage (C'-4) (these solutions are transition metals, respectively. An ethylene / propylene / ENB copolymer was produced under the same procedure and conditions as in Example 3-1 except that the complex b was changed to 0.00015 mmol.
Table 6 shows the yield of the obtained ethylene / propylene / ENB copolymer and the mileage per 1 mmol of hafnium atom in the transition metal complex b.

[Examples 4-1 to 4-6]
Contact step or solution storage (0.06 mmol / l [methyl (4-methylphenyl) methylene (η ⁵ -cyclopentadienyl) containing 200 eq triisobutylaluminum) (η ⁵ -octamethyl octahydrodibenzoful) Olenyl)] Preparation of hexane solution of zirconiumdimethyl)]
(Contact operation 4)
[Methyl (4-methylphenyl) methylene (η ⁵ -cyclopentadienyl) (η ⁵ -octamethyl octahydro) immediately after synthesis in Synthesis Example 3 in a glass two-port flask with an internal volume of 100 ml sufficiently substituted with nitrogen Dibenzofluorenyl)] 4.13 mg of zirconium dimethyl (transition metal complex c) and n-hexane from which impurities have been removed with active alumina are charged at 25 ° C., and then 1 mol of triisobutylaluminum is added to the transition metal complex c. A solution (D) having a transition metal complex c concentration of 0.06 mmol / l was prepared by adding 200 mol to the amount and further adding n-hexane to make the total volume 100 ml.
Then, immediately, this solution (D) was subdivided into 6 glass two-necked flasks having an internal volume of 25 ml and sufficiently nitrogen-substituted to obtain solutions (D-1) to (D-6).

(Preservation of solution)
In Example 4-1 the solution (D-1) containing the transition metal complex c obtained in the contact operation 4 was stored for 1 hour in a cool and dark place at a temperature of 5 ° C. under a nitrogen atmosphere.
Similarly, in Examples 4-2 to 4-6, the solutions (D-2) to (D-6) containing the transition metal complex c obtained in the contact operation 4 were subjected to a nitrogen atmosphere at a temperature of 5 ° C. Stored in a cool and dark place. The storage period of each solution is shown in Table 7.

[Polymerization process (manufacturing of polyethylene)]
(Example 4-1)
250 mL of decan is charged into a glass polymerizer having an internal volume of 1 L sufficiently substituted with nitrogen, the temperature in the system is raised to 130 ° C., and then ethylene is continuously supplied into the polymerizer at a flow rate of 100 L / hr. Then, the mixture was stirred at a stirring rotation speed of 600 rpm. Next, 0.2 mmol of triisobutylaluminum was charged into the polymerizer, and then 2.5 ml of the solution (D-1) immediately after the storage was completed (this solution contains 0.00015 mmol of the transition metal complex c) was added. Further, the polymerization was started by charging the polymerizer with N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate at a ratio of 5 mol to 1 mol of the transition metal complex c. Then, continuous supply of ethylene was continued, and polymerization was carried out at 130 ° C. for 10 minutes. After terminating the polymerization by adding a small amount of isobutyl alcohol into the system, the unreacted monomer was purged. The obtained polymer solution was poured into 1 L of methanol containing 2 mL of hydrochloric acid to precipitate the polymer. The precipitated polymer was collected by filtration and dried under reduced pressure at 80 ° C. overnight.
As a result, 2.76 g of polyethylene was obtained. The mileage per 1 mmol of zirconium atom in the transition metal complex c was 18.4 kg. The results are shown in Table 7.

(Examples 4-2 to 4-6)
In Examples 4-2 to 4-6, the solution (D-1) is a 2.5 ml solution (D-2) immediately after the storage is completed, and a 2.5 ml solution (D-) immediately after the storage is completed. 3), 2.5 ml solution immediately after storage (D-4), 2.5 ml solution immediately after storage (D-5), or 2.5 ml solution immediately after storage (D-4). Polyethylene was produced under the same procedures and conditions as in Example 4-1 except that D-6) (each of these solutions contained 0.00015 mmol of the transition metal complex c).
The yield of the obtained polyethylene and the mileage per 1 mmol of zirconium atom in the transition metal complex c are shown in Table 7.

[Comparative Examples 4-1 to 4-4]
[Methyl (4-methylphenyl) methylene (η ⁵ -cyclopentadienyl) (η ⁵ -octamethyloctahydrodibenzofluorenyl)] zirconium dimethyl hexane solution containing 0.06 mmol / l without triisobutylaluminum Preparation]
(Comparative contact operation 4)
The same operation as in contact operation 4 was performed except that triisobutylaluminum was not used, a solution (D') having a transition metal complex c concentration of 0.06 mmol / l was prepared, and this solution (D') was immediately prepared. Solutions (D'-1) to (D'-4) were obtained by subdividing into four glass two-necked flasks having an internal volume of 25 ml and sufficiently substituted with nitrogen.

(Preservation of solution)
The solutions (D'-1) to (D'-4) containing the transition metal complex b obtained in Comparative Contact Operation 4 were stored in a cool and dark place at a temperature of 5 ° C. under a nitrogen atmosphere. The storage period of each solution is shown in Table 8.

[Polymerization process (manufacturing of polyethylene)]
In Comparative Examples 4-1 to 4-4, the solution (D-1) was a 2.5 ml solution (D'-1) immediately after the storage was completed, and a 2.5 ml solution (D) immediately after the storage was completed. '-2), 2.5 ml of solution immediately after storage (D'-3), or 2.5 ml of solution immediately after storage (D'-4) (these solutions are transition metals, respectively. Polyethylene was produced under the same procedure and conditions as in Example 4-1 except that the complex c was changed to 0.00015 mmol.
The yield of the obtained polyethylene and the mileage per 1 mmol of zirconium atom in the transition metal complex c are shown in Table 8.

Claims (4)

Impurity removal step, which removes some or all of the impurities in the solvent by contacting activated alumina with the solvent.
A contacting step of contacting a transition metal complex, organic aluminum having a ratio of 20 mol or less with respect to 1 mol of the transition metal atom in the transition metal complex in terms of the amount of aluminum atoms, and a solvent that has undergone the impurity removing step. And a polymerization step of polymerizing the olefin in the presence of a solution containing the transition metal complex that has undergone the contact step and containing organic aluminum at a concentration of 0.005 mmol / L or more in terms of aluminum atom .
The transition metal complex is selected from the transition metal complex (2), the transition metal complex (3) and the transition metal complex (4).
The transition metal complex (2) is a compound represented by the following general formula [A2].

[In the formula [A2], R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are independently hydrogen atoms. , Hydrocarbon group, halogen-containing group, oxygen-containing group, nitrogen-containing group, boron-containing group, sulfur-containing group, phosphorus-containing group, silicon-containing group, germanium-containing group and tin-containing group. Alternatively, two adjacent groups may be linked to each other to form a ring.
Y is a divalent group and is a group selected from a hydrocarbon group having 1 to 20 carbon atoms and a silicon-containing group.
M is Zr or Hf.
X is independently a halogen atom or a hydrocarbon group. ]
The transition metal complex (3) is a compound represented by the following general formula [A3].

[In the formula [A3], R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ and R ¹⁴ , respectively. It is independently a hydrogen atom, a hydrocarbon group, a heteroatom-containing hydrocarbon group or a silicon-containing group, and any two of the substituents R ¹ to R ⁴ are bonded to each other to form a ring. Alternatively, any two of the substituents from R ⁵ to R ¹² may be bonded to each other to form a ring, and R ¹³ and R ¹⁴ may be bonded to each other to form a ring. You may be doing it.
Y is a carbon atom or a silicon atom.
M is Zr or Hf.
j is an integer of 1 to 4.
Q is a halogen atom or a hydrocarbon group. When j is an integer of 2 or more, Q may be selected in the same or different combinations. ]
The transition metal complex (4) is a compound represented by the following general formula [A4].

[In the formula [A4], R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are each independently a hydrogen atom, a hydrocarbon group, a heteroatom-containing hydrocarbon group or a silicon-containing group, and any two substituents from R ¹ to R ¹⁶ are bonded to each other. May form a ring.
M is Zr or Hf.
j is an integer of 1 to 4.
Q is a halogen atom or a hydrocarbon group. When j is an integer of 2 or more, Q may be selected in the same or different combinations. ]
A method for producing an olefin polymer. The method for producing an olefin polymer according to claim 1, wherein in the contacting step, the transition metal complex, the organoaluminum, and the solvent are brought into contact with each other, and then the obtained solution is stored for 1 hour or more. The olefin polymer according to claim 1 or 2, wherein in the polymerization step, a solution containing the transition metal complex and organoaluminum that has undergone the contact step and further organoaluminum are added to the polymer to prepare the solution. Manufacturing method. The impurity removal step of contacting the solvent with active alumina to remove some or all of the impurities in the solvent, and the transition metal complex are converted into 1 mol of the transition metal atom in the transition metal complex in terms of the amount of aluminum atoms. It comprises a storage step of storing in a solution containing 20 mol or less of organic aluminum and the solvent which has undergone the impurity removal step.
The transition metal complex is selected from the transition metal complex (2), the transition metal complex (3) and the transition metal complex (4).
The transition metal complex (2) is a compound represented by the following general formula [A2].

[In the formula [A2], R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are independently hydrogen atoms. , Hydrocarbon group, halogen-containing group, oxygen-containing group, nitrogen-containing group, boron-containing group, sulfur-containing group, phosphorus-containing group, silicon-containing group, germanium-containing group and tin-containing group. Alternatively, two adjacent groups may be linked to each other to form a ring.
Y is a divalent group and is a group selected from a hydrocarbon group having 1 to 20 carbon atoms and a silicon-containing group.
M is Zr or Hf.
X is independently a halogen atom or a hydrocarbon group. ]
The transition metal complex (3) is a compound represented by the following general formula [A3].

[In the formula [A3], R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ and R ¹⁴ , respectively. It is independently a hydrogen atom, a hydrocarbon group, a heteroatom-containing hydrocarbon group or a silicon-containing group, and any two of the substituents R ¹ to R ⁴ are bonded to each other to form a ring. Alternatively, any two of the substituents from R ⁵ to R ¹² may be bonded to each other to form a ring, and R ¹³ and R ¹⁴ may be bonded to each other to form a ring. You may be doing it.
Y is a carbon atom or a silicon atom.
M is Zr or Hf.
j is an integer of 1 to 4.
Q is a halogen atom or a hydrocarbon group. When j is an integer of 2 or more, Q may be selected in the same or different combinations. ]
The transition metal complex (4) is a compound represented by the following general formula [A4].

[In the formula [A4], R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are each independently a hydrogen atom, a hydrocarbon group, a heteroatom-containing hydrocarbon group or a silicon-containing group, and any two substituents from R ¹ to R ¹⁶ are bonded to each other. May form a ring.
M is Zr or Hf.
j is an integer of 1 to 4.
Q is a halogen atom or a hydrocarbon group. When j is an integer of 2 or more, Q may be selected in the same or different combinations. ]
How to preserve transition metal complexes.