JP7175803B2 - Method for producing olefin polymer and catalyst solution for olefin polymer - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for producing an olefin polymer and a catalyst solution for an olefin polymer.

As a method for producing an olefin polymer, a production method using a transition metal complex such as a metallocene compound or a post-metallocene compound as a catalyst is known, and many such production methods have been reported so far (Patent Document 1. ~5 etc.).

When an olefin is polymerized using such a transition metal complex, the presence of impurities such as polar substances in the polymerization system hinders the catalytic activity of the transition metal complex. Therefore, scavengers for such impurities are often used when transition metal complexes are used. AlR ₃ (eg, triisobutylaluminum, triethylaluminum), for example, is known as the scavenger (see Non-Patent Document 1, etc.).

In addition, it is known that when a transition metal complex comes into contact with moisture, it gradually deteriorates and becomes unable to exhibit catalytic activity. If it is left for a long period of time in such a state, the catalytic activity cannot be expressed due to the contamination of moisture from the outside. In other words, it has been difficult to stably store the transition metal complex for a long period of time in a solution state dissolved in a solvent. Therefore, in the case of olefin polymerization using a transition metal complex solution dissolved in a solvent, the olefin polymerization is performed in a short time after preparation of such a solution.

On the other hand, if a transition metal complex solution dissolved in a solvent can be used to produce an olefin polymer with high catalytic activity even after long-term storage, such a solution can be prepared immediately before olefin polymerization. For example, the degree of freedom in olefin polymerization (procurement planning, etc.) increases.
Patent Documents 6 to 8 disclose methods for producing an olefin polymer with high catalytic activity using a transition metal complex solution even after long-term storage.

WO2004/029062 WO2015/122414 WO2015/122415 JP-A-2003-73412 JP-A-2004-256602 JP 2018-165308 A JP-A-8-245714 JP-A-11-12313

Polypropylene Handbook, Industrial Research Institute, 1998, 61 pages

The method described in Patent Document 6 uses a transition metal complex such as [bis(4-methoxyphenyl)methylene(η ⁵ -cyclopentadienyl)(η ⁵ -tetramethyldodecahydrodibenzofluorenyl)]hafniumdimethyl. The method described in Patent Documents 7 and 8 was also effective when a predetermined transition metal compound was used. It was found that there is room for further improvement in terms of catalytic activity when a transition metal complex solution is used.

The present invention has been made in view of the above, and relates to a method for producing an olefin polymer using a solution containing a transition metal complex having an imine group. ) To provide a method capable of producing an olefin polymer with high catalytic activity even after storage, and a catalyst solution capable of producing an olefin polymer with high catalytic activity even after long-term storage. for the purpose.

As a result of the research conducted by the present inventors, it was found that the above problems can be solved by the following configuration example. A configuration example of the present invention is as follows.

[1] Step 1 of contacting a transition metal complex having an imine group, a modified methylaluminoxane (MMAO), and a solvent to prepare a catalyst solution;
Step 2 of polymerizing an olefin using the catalyst solution;
including
In the step 1, the MMAO and the transition metal complex are combined into a ratio (M _Al /M _M ) of the moles (M _Al ) of the aluminum atoms in the MMAO and the moles (M _M ) of the central metal of the transition metal complex. is used in an amount of 0.1 to 9.5,
A method for producing an olefin polymer.

[2] The method for producing an olefin polymer according to [1], wherein the MMAO is modified methylaluminoxane obtained using trimethylaluminum and triisobutylaluminum.

[3] The olefin according to [1] or [2], wherein the step 1 is a step of contacting the transition metal complex, the MMAO, and the solvent, and then storing the resulting solution for 1 hour or more. A method for producing a polymer.

[4] including a transition metal complex having an imine group, a modified methylaluminoxane (MMAO), and a solvent;
The ratio (M _Al /M _M ) between the moles (M _Al ) of aluminum atoms in the MMAO and the moles (M _M ) of the central metal of the transition metal complex is 0.1 to 9.5.
Catalyst solution for olefin polymerization.

According to the present invention, in a method for producing an olefin polymer using a solution containing a transition metal complex having an imine group, even after storing the solution for a long period of time (eg, 7 days or longer) after preparation, Olefin polymers can be produced with high catalytic activity.

<<Method for Producing Olefin Polymer and Catalyst Solution for Olefin Polymerization>>
The method for producing an olefin polymer according to the present invention (hereinafter also referred to as "this method") comprises:
Step 1 of contacting a transition metal complex having an imine group (hereinafter also referred to as "this complex"), modified methylaluminoxane (MMAO), and a solvent to prepare a catalyst solution;
Step 2 of polymerizing an olefin using the catalyst solution;
including
In the step 1, the MMAO and the transition metal complex are combined into a ratio (M _Al /M _M ) of the moles (M _Al ) of the aluminum atoms in the MMAO and the moles (M _M ) of the central metal of the transition metal complex. is used in an amount of 0.1 to 9.5.

Further, the catalyst solution for olefin polymerization according to the present invention (hereinafter also referred to as "this catalyst solution") is
comprising a transition metal complex having an imine group, a modified methylaluminoxane (MMAO), and a solvent;
The content ratio (M _Al /M _M ) between the moles (M _Al ) of aluminum atoms in the MMAO and the moles (M _M ) of the central metal of the transition metal complex is 0.1 to 9.5.
The method for preparing this catalyst solution is not particularly limited, but the same method as in step 1 of this method is preferred. That is, the catalyst solution obtained in step 1 of the present method is the present catalyst solution.

<Step 1>
The step 1 is a step of contacting a predetermined amount of the present complex, a predetermined amount of MMAO, and a solvent to prepare a catalyst solution.
Even if the catalyst solution obtained in step 1 is stored for a long period of time, it is possible to maintain high catalytic activity in olefin polymerization. In other words, step 1 allows the present complex to be stably stored for a long period of time in a solution state. Therefore, this step 1 can be said to be a method for producing a catalyst solution having excellent storage stability, and also a method for preserving the present complex.

The M _Al /M _M is 0.1 to 9.5, and even after long-term storage, a catalyst solution exhibiting higher catalytic activity can be easily obtained. 0.5 to 8.0, more preferably 1.0 to 7.0, still more preferably 1.5 to 6.0.
If the amount of MMAO is more than the above range, there is a possibility that the present complex will react with MMAO and change in quality, or the risk of ignition of MMAO will increase. In particular, when the present complex and MMAO are kept in contact for a long period of time, these problems become conspicuous.

<This complex>
The present complex used in Step 1 is not particularly limited as long as it has an imine group, and a transition metal complex having an imine group conventionally known as an olefin polymerization catalyst can be used.
Specific examples of this complex include the following complexes (1) to (7). Among these, the following complex (1) is preferable. The following complexes (1) to (7) can be synthesized, for example, by the methods described in the following publications that exemplify each of them.
The present complex used in step 1 may be of one type or two or more types.

[Complex (1)]
The complex (1) is a complex represented by the following formula (1). Examples of the complex (1) include the following complexes (1-1) to (1-3). Examples include the complexes described in JP-A-2004-256602.

The complex (1-1) is a complex in which each symbol in the formula (1) represents the following.
M is a transition of groups 3-11 of the periodic table (group 3 also includes lanthanides), preferably groups 3-9, more preferably groups 3, 4, 5 or 9, particularly preferably groups 4 or 5 indicates a metal atom,
m represents an integer of 1 to 6, preferably 1 to 4,
R ¹ to R ⁶ may be the same or different, and may be a hydrogen atom, a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, a sulfur-containing group, a phosphorus containing group, silicon-containing group, germanium-containing group, or tin-containing group, two or more of which may be linked together to form a ring, and when m is 2 or more, R Two groups among the groups represented by ¹ to R ⁶ may be linked (provided that R ¹ is not linked to each other), and R ⁶ is preferably a group other than hydrogen,
n is a number that satisfies the valence of M,
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, a heterocyclic compound residue, a silicon-containing group, germanium-containing group, or tin-containing group, and when n is 2 or more, the multiple groups represented by X may be the same or different, and the multiple groups represented by X may be bonded to each other. may form a ring,
N...M generally indicates coordination, but may or may not be coordination.

The complex (1-2) is a complex in which each symbol in the formula (1) represents the following.
M represents a transition metal atom of groups 4 to 5 of the periodic table, preferably group 4,
m is an integer of 1 to 4, preferably 1 to 2, particularly preferably 2,
R ¹ is (i) a linear hydrocarbon group having 1 to 5 carbon atoms or a hydrogen atom, (ii) a 3- to 5-membered alicyclic hydrocarbon optionally having one or more substituents. or (iii) a bicyclic hydrocarbon group having 4 to 20 carbon atoms and sharing at least one or more carbon atoms, which may have one or more substituents;
R ² to R ⁶ may be the same or different, and may be hydrogen atoms, halogen atoms, hydrocarbon groups, heterocyclic compound residues, oxygen-containing groups, nitrogen-containing groups, boron-containing groups, sulfur-containing groups, phosphorus containing group, silicon-containing group, germanium-containing group, or tin-containing group, two or more of which may be linked together to form a ring, and when m is 2 or more, R two of the groups represented by ² to R ⁶ may be linked,
n is a number that satisfies the valence of M,
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, a heterocyclic compound residue, a silicon-containing group, germanium-containing group, or tin-containing group, and when n is 2 or more, the multiple groups represented by X may be the same or different, and the multiple groups represented by X may be bonded to each other. may form a ring,
N...M generally indicates coordination, but may or may not be coordination.

The complex (1-3) is a complex in which each symbol in the formula (1) represents the following.
M represents a transition metal atom of groups 4 to 5 of the periodic table, preferably group 4,
m is an integer of 1 to 2, preferably 2,
R ¹ is an aliphatic or alicyclic hydrocarbon group,
R ² to R ⁵ , which may be the same or different, represent a hydrocarbon group, a hydrogen atom, a hydrocarbon-substituted silyl group, an oxygen-containing group, a nitrogen-containing group or a sulfur-containing group;
R ⁶ represents an aliphatic hydrocarbon group, an alicyclic hydrocarbon group or an aromatic group,
n is a number that satisfies the valence of M,
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, a heterocyclic compound residue, a silicon-containing group, germanium-containing group, or tin-containing group, and when n is 2 or more, the multiple groups represented by X may be the same or different, and the multiple groups represented by X may be bonded to each other. may form a ring,
N...M generally indicates coordination, but may or may not be coordination.

[Complex (2)]
The complex (2) is a complex represented by the following formula (2). Specific examples of the complex (2) include the complexes described in International Publication No. 2009/005003.

In formula (2),
R ¹ to R ⁶ may be the same or different, and are hydrogen atoms, halogen atoms, hydrocarbon groups, heterocyclic compound residues, oxygen-containing groups, nitrogen-containing groups, boron-containing groups, aluminum-containing groups, sulfur containing group, phosphorus-containing group, silicon-containing group, germanium-containing group, or tin-containing group, two or more of which may be linked to each other, and R ¹ may be linked to Z ,
M represents a transition metal atom of groups 3 to 10 of the periodic table, preferably group 4,
n represents the valence of M,
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, a heterocyclic compound residue, a silicon-containing group, germanium-containing group, or tin-containing group, the atoms and groups represented by X may be the same or different, and the groups represented by X may be combined to form a ring,
Y represents an oxygen atom, a nitrogen atom, a phosphorus atom or a sulfur atom,
m represents 1 when Y is an oxygen atom or a sulfur atom, and represents 2 when Y is a nitrogen atom or a phosphorus atom,
Z represents an optionally substituted hydrocarbon group or heterocyclic compound residue, the shortest number of bonds connecting Y and N is 4 to 6,
The bond connecting Y and Z may be a double bond or a triple bond, the bond connecting Y and R ¹ may be a double bond or a triple bond,
Dotted lines indicate coordinate bonds.

[Complex (3)]
The complex (3) is a complex represented by the following formula (3). Specific examples of the complex (3) include complexes described in JP-A-2001-72706.

In formula (3),
M represents a transition metal atom selected from groups 3 to 11 of the periodic table, preferably groups 3 to 9, more preferably groups 3 to 5 and 9, particularly preferably groups 4 and 5,
U represents a carbon atom bearing a substituent ^R2 ,
A represents a nitrogen atom or a phosphorus atom, preferably a nitrogen atom,
Q represents a carbon atom, a nitrogen atom or a phosphorus atom having a substituent R3 ^, preferably a carbon atom having a substituent R3 ^,
S represents a carbon atom, a nitrogen atom or a phosphorus atom with a substituent ^R4 , preferably a carbon atom with a substituent ^R4 ,
T represents a carbon atom, a nitrogen atom or a phosphorus atom with a substituent ^R5 , preferably a carbon atom with a substituent ^R5 ,
m is an integer of 2 to 6, preferably 2 to 4, more preferably 2,
R ¹ to R ⁵ may be the same or different, and when M is a transition metal atom selected from Groups 3 to 5 and Groups 7 to 11 of the periodic table, a hydrogen atom, a halogen atom, a hydrocarbon group, represents a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group or a tin-containing group, and M is selected from Group 6 of the periodic table; When the transition metal atom is ^a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, a sulfur-containing group, phosphorus-containing group, silicon-containing group, germanium-containing group or tin-containing group, and R ² to R ⁵ are hydrogen atom, halogen atom, hydrocarbon group, 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, and two or more of R ¹ to R ⁵ are linked together to form a ring. one group of R ¹ to R ⁵ contained in any one ligand and one group of R ¹ to R ⁵ contained in the other ligand may form a linking group or a single bond with
n is a number that satisfies the valence of M,
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, a heterocyclic compound residue, a silicon-containing group, germanium-containing group or tin-containing group, and when n is 2 or more, the plurality of groups represented by X may be the same or different, and the plurality of groups represented by X may be linked to each other may form a ring,
N...M generally indicates that it is coordinated, but may or may not be coordinated,
AM usually represents a bond between A and M, but when A is nitrogen, it also includes a case where M and η bond.

[Complex (4)]
The complex (4) is a complex represented by the following formula (4). Specific examples of the complex (4) include complexes described in JP-A-2009-72665.

In formula (4),
R ¹ to R ⁵ may be the same or different, and may be hydrogen atoms, halogen atoms, hydrocarbon groups, heterocyclic compound residues, oxygen-containing groups, nitrogen-containing groups, boron-containing groups, aluminum-containing groups, sulfur containing group, phosphorus-containing group, silicon-containing group, germanium-containing group, or tin-containing group, two or more of which may be linked to each other, R ¹ may be linked to Z, and R ⁵ is optionally linked to Z,
M represents a transition metal atom of Group 4 of the periodic table,
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, a heterocyclic compound residue, a silicon-containing group, a germanium-containing group, or a tin-containing group, the groups represented by X may be the same or different, and the groups represented by X may be combined to form a ring,
Y represents an oxygen atom, a nitrogen atom, a phosphorus atom or a sulfur atom,
Z represents an optionally substituted hydrocarbon group or heterocyclic compound residue,
The bond connecting Y and Z may be a double bond or a triple bond, the bond connecting Y and R ¹ may be a double bond or a triple bond, and dotted lines indicate coordinate bonds.

[Complex (5)]
The complex (5) is a complex represented by the following formula (5). Specific examples of the complex (5) include complexes described in JP-A-10-324710.

In formula (5),
M represents a transition metal atom of groups 8 to 11 of the periodic table, preferably nickel, palladium, cobalt, rhodium,
R ¹ to R ⁶ may be the same or different and represent a hydrogen atom, a hydrocarbon group, an organic silyl group, an alkoxy group or an aryloxy group, two or more of which are linked together to form a ring. may be
n represents the valence of M,
X may be the same or different, and may be a hydrogen atom, a halogen atom, a hydrocarbon group, —OR ⁷ , —SR ⁸ , —N(R ⁹ ) ₂ or —P(R ¹⁰ ) ₂ (with the proviso that R ⁷ to R ¹⁰ each represent an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an organic silyl group, and R ⁹ or R ¹⁰ may be linked together to form a ring), and n When is 2 or more, X may be linked together to form a ring.

[Complex (6)]
The complex (6) is a complex represented by the following formula (6). Specific examples of the complex (6) include complexes described in JP-A-2000-281710.

In formula (6),
M represents a transition metal atom selected from Groups 3 to 11, preferably Groups 3 to 7, more preferably Group 4 of the periodic table,
m represents an integer of 1 to 6,
A is an oxygen atom or a sulfur atom, or a nitrogen atom having R ¹² as a substituent,
R ¹ to R ⁹ and R ¹² , which may be the same or different, are a hydrogen atom, a halogen atom, a hydrocarbon group, a heterocyclic compound residue, a nitrogen-containing group, an oxygen-containing group, a boron-containing group, a sulfur-containing group, phosphorus-containing group, silicon-containing group, germanium-containing group or tin-containing group, and two or more of the groups represented by R ¹ to R ⁹ and R ¹² may be linked together to form a ring. Well, when m is 2 or more, A, R ¹ to R ⁹ and R ¹¹ may be the same or different, and each of A, R ¹ , R ² , R ³ , R ⁴ may be connected to each other, R ⁵ to R ⁶ , R ⁷ to R ⁸ , R ⁹ to R ¹² , and R 12 to each other,
n is a number that satisfies the valence of M,
X is a hydrogen atom, a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, a sulfur-containing group, a phosphorus-containing group, a halogen-containing group, an aluminum-containing group, a silicon-containing group group, germanium-containing group or tin-containing group, and when n is 2 or more, the plurality of groups represented by X may be the same or different, and the plurality of groups represented by X may be bonded to each other A ring may be formed.

[Complex (7)]
The complex (7) is a complex represented by the following formula (7). Specific examples of the complex (7) include complexes described in JP-A-2005-132731.

In formula (7),
M represents a transition metal atom of Group 4 of the periodic table,
R ¹ to R ¹¹ , which may be the same or different, are a hydrogen atom, a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, an aluminum-containing group, and a sulfur-containing group. group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group, two or more of which may be linked together.
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, a heterocyclic compound residue, a silicon-containing group, germanium-containing group, or tin-containing group, the groups represented by X may be the same or different, and the groups represented by X may be combined to form a ring.

Examples of the transition metal atoms include scandium, titanium, zirconium, hafnium, vanadium, niobium, tantalum, cobalt, rhodium, yttrium, chromium, molybdenum, tungsten, manganese, rhenium, iron, ruthenium, lanthanum, samarium, nickel, and palladium. , copper.

The hydrocarbon group has 1 to 30 carbon atoms, preferably 1, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, neopentyl and n-hexyl. A linear or branched alkyl group of up to 20; a linear or branched alkenyl group of 2 to 30, preferably 2 to 20 carbon atoms such as vinyl, allyl and isopropenyl; a linear or branched alkenyl group of 2 to 20 carbon atoms such as ethynyl and propargyl to 30, preferably 2 to 20 linear or branched alkynyl groups; cyclic saturated hydrocarbon groups (cyclo alkyl group); cyclic unsaturated hydrocarbon groups having 5 to 30 carbon atoms such as cyclopentadienyl, indenyl and fluorenyl; phenyl, benzyl, cumyl, naphthyl, biphenyl, terphenyl, phenanthryl, anthracenyl and other , preferably 6 to 20 aryl or aralkyl groups; and alkyl-substituted aryl groups such as tolyl, iso-propylphenyl, tert-butylphenyl, dimethylphenyl and di-tert-butylphenyl.
Among these, in particular, linear or branched alkyl groups having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms; aryl groups having 6 to 30 carbon atoms, preferably 6 to 20 carbon atoms; A substituted aryl substituted with 1 to 5 substituents such as an atom, an alkyl group or an alkoxy group having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, an aryl group or an aryloxy group having 6 to 30 carbon atoms, preferably 6 to 20 carbon atoms Groups and the like are preferred.

A hydrogen atom of the hydrocarbon group may be substituted with a halogen atom, and such substituted groups include, for example, trifluoromethyl, pentafluorophenyl, chlorophenyl and the like having 1 to 30 carbon atoms, preferably 1 to 20 halogenated hydrocarbon groups are included.

The hydrocarbon groups may also be substituted with 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/or tin-containing groups. may have been

Heterocyclic compound residues include residues of 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 thereof include groups in which a compound residue is further substituted with a substituent such as an alkyl group or an alkoxy group having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms.

Oxygen-containing groups include alkoxy groups such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy and tert-butoxy; aryloxy groups such as phenoxy, methylphenoxy, dimethylphenoxy, trimethylphenoxy and naphthoxy; , arylalkoxy groups such as phenylethoxy; ester groups such as acetyloxy, benzoyloxy, methoxycarbonyl, phenoxycarbonyl, p-chlorophenoxycarbonyl; ether groups; formyl groups, acetyl groups, benzoyl groups, p-chlorobenzoyl groups, p carboxyl group; acetoxy group; carbonyl group; carbonate group; hydroxy group; peroxy group;

Nitrogen-containing groups include amino groups; alkylamino groups such as methylamino, dimethylamino, diethylamino, dipropylamino, dibutylamino and dicyclohexylamino; aryl groups such as phenylamino, diphenylamino, ditolylamino, dinaphthylamino and methylphenylamino; amino group; imino group such as methylimino, ethylimino, propylimino, butylimino, phenylimino; amide group such as acetamide, N-methylacetamide, N-methylbenzamide; imido group such as acetimide, benzimide; hydrazino group; cyano group; isocyano group; cyanate ester group; amidino group; diazo group;

Boron-containing groups include boranediyl group, boranetriyl group, diboranyl group, alkyl group-substituted boron, aryl group-substituted boron, halogenated boron, and alkyl group-substituted boron halide.

Sulfur-containing groups include mercapto groups; thioester groups such as acetylthio, benzoylthio, methylthiocarbonyl, and phenylthiocarbonyl; dithioester groups; thioacyl groups; thioether groups; thiocyanate groups; sulfone ester groups such as ethyl acid and phenyl sulfonate; sulfonamide groups such as phenylsulfonamide, N-methylsulfonamide and N-methyl-p-toluenesulfonamide; thiocarboxyl group; dithiocarboxyl group; sulfo group; sulfonyl group sulfinyl group; sulfenyl group; methylsulfonate, trifluoromethanesulfonate, phenylsulfonate, benzylsulfonate, p-toluenesulfonate, trimethylbenzenesulfonate, triisobutylbenzenesulfonate, p-chlorobenzenesulfonate, sulfonate groups such as pentafluorobenzenesulfonate; methyl sulfinate groups such as sulfinate, phenylsulfinate, benzylsulfinate, p-toluenesulfinate, trimethylbenzenesulfinate and pentafluorobenzenesulfinate; alkylthio groups such as methylthio and ethylthio; phenylthio and methylphenyl arylthio groups such as thio and naphthylthio;

Phosphorus-containing groups include trialkylphosphine groups such as trimethylphosphine, tributylphosphine and tricyclohexylphosphine; triarylphosphine groups such as triphenylphosphine and tritolylphosphine; phyto group (phosphide group); phosphonic acid group; phosphinic acid group; phosphide group; phosphoryl group;

Examples of silicon-containing groups include silyl groups, siloxy groups, hydrocarbon-substituted silyl groups, hydrocarbon-substituted siloxy groups, etc. Specific examples include methylsilyl, dimethylsilyl, trimethylsilyl, ethylsilyl, diethylsilyl, triethylsilyl, and tripropyl. Hydrocarbon substitution such as silyl, tricyclohexylsilyl, phenylsilyl, diphenylsilyl, diphenylmethylsilyl, triphenylsilyl, dimethylphenylsilyl, dimethyl-tert-butylsilyl, dimethyl(pentafluorophenyl)silyl, tritolylsilyl, trinaphthylsilyl, etc. silyl groups; hydrocarbon-substituted silyl ether groups such as trimethylsilyl ether; silicon-substituted alkyl groups such as trimethylsilylmethyl; silicon-substituted aryl groups such as trimethylsilylphenyl;

Germanium-containing groups and tin-containing groups include groups obtained by substituting germanium or tin for silicon in the above silicon-containing groups.

Examples of halogen-containing groups include fluorine-containing groups such as PF ₆ and BF ₄ , chlorine-containing groups such as ClO ₄ and SbCl ₆ , and iodine-containing groups such as IO ₄ .

Examples of aluminum-containing groups include groups such as alkyl group-substituted aluminum, aryl group-substituted aluminum, halogenated aluminum, and alkyl group-substituted aluminum halide.

Substituents for (ii) and (iii) in complex (1-2) include, for example, a hydrogen atom, a halogen atom, a hydrocarbon group, a hydrocarbon-substituted silyl group, a hydrocarbon-substituted siloxy group, an oxygen-containing group, a sulfur-containing groups, nitrogen-containing groups, phosphorus-containing groups, halogen-containing groups, heterocyclic compound residues, or hydrocarbon groups or hydrocarbon-substituted silyl groups containing these groups.

Examples of the bicyclic aliphatic hydrocarbon group in the complex (1-2) include spiro[2.2]pentane, spiro[2.3]hexane, spiro[2.4]heptane, spiro[2.5] octane, spiro[3.3]heptane, spiro[3.4]octane, spiro[3.5]nonane, spiro[4.4]nonane, spiro[4.5]decane, spiro[5.5]undecane, bicyclo[1.1.0]butane, bicyclo[2.1.0]pentane, bicyclo[2.2.0]hexane, bicyclo[3.1.0]hexane, bicyclo[3.2.0]heptane, bicyclo[3.3.0]octane, bicyclo[4.1.0]heptane, bicyclo[4.2.0]octane, bicyclo[4.3.0]nonane, bicyclo[4.4.0]decane, bicyclo[1.1.1]pentane, bicyclo[2.1.1]hexane, bicyclo[2.2.1]heptane, bicyclo[2.2.2.]octane, bicyclo[3.1.1]heptane , bicyclo[3.2.1]octane, bicyclo[3.2.2]nonane, bicyclo[3.3.1]nonane, bicyclo[3.3.2]decane, bicyclo[3.3.3]undecane is mentioned.

Examples of the aliphatic hydrocarbon group and alicyclic hydrocarbon group in the complex (1-3) include groups having 1 to 30 carbon atoms, specifically methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, tert-amyl, 1,2-dimethylpropyl, 1-ethylpropyl, isoamyl, 1-methylbutyl, 2-methylbutyl, neopentyl, n-hexyl, 1,3-dimethylbutyl, 3,3-dimethylbutyl, n-heptyl, 1-ethylpentyl, 1-methylhexyl, n-octyl, 1,5-dimethylhexyl, 2-ethylhexyl, 1-methylheptyl, 1- propylbutyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, 2-methylcyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2,2-dimethylcyclohexyl, 4-tert-butylcyclohexyl, 4-tert-butyl-2,-methylcyclohexyl, 2,3-dimethylcyclohexyl, 3,5-dimethylcyclohexyl, 3,5-di-tertbutylcyclohexyl, 2,6-dimethylcyclohexyl, 2,4,6-trimethylcyclohexyl, 2,2,6,6-tetramethylcyclohexyl, 3,3,5 ,5-tetramethylcyclohexyl, 2,3,4,5,6-pentamethylcyclohexyl, cycloheptyl, cyclooctyl, cyclododecyl, adamantyl, methylenecyclopropyl, methylenecyclobutyl, methylenecyclopentyl, methylenecyclohexyl, 1-cyclohexyl Examples include ethyl, benzyl, 1-naphthylenemethyl, 1-phenylethyl, 1-phenylpropyl and 1-1-diphenylmethyl.

Examples of the aromatic group in the complex (1-3) include aryl groups having 6 to 30 carbon atoms, preferably 6 to 20 carbon atoms such as phenyl, naphthyl, biphenyl, triphenyl, fluorenyl, anthranyl and phenanthryl; Examples thereof include groups further substituted with substituents such as alkyl groups having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, and aryl groups having 6 to 30 carbon atoms, preferably 6 to 20 carbon atoms.

The number of shortest bonds connecting Y and N in complex (2) can be counted as shown in (A) and (B) below. 5 in the case.
Moreover, when similarly counted, the number of shortest bonds connecting Y and N (adjacent to Z) in complex (4) is preferably 5 or 6.

（式（ＩＩ）中、Ｙは、酸素原子、窒素原子、リン原子または硫黄原子を示す。
Ｒ⁷～Ｒ¹⁰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、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、アルミニウム含有基、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、またはスズ含有基を示し、これらのうちＲ⁷～Ｒ¹⁰が炭化水素基の場合には、Ｒ⁷とＲ⁸は互いに連結して環を形成していてもよく、Ｒ⁹とＲ¹⁰は互いに連結して環を形成していてもよい。） Y, N and Z in complex (2) preferably have structures represented by the following formula (II).

(In Formula (II), Y represents an oxygen atom, a nitrogen atom, a phosphorus atom, or a sulfur atom.
R ⁷ to R ¹⁰ may be the same or different, and are hydrogen atom, halogen atom, hydrocarbon group, heterocyclic compound residue, oxygen-containing group, nitrogen-containing group, boron-containing group, aluminum-containing group, sulfur containing group, phosphorus-containing group, silicon-containing group, germanium-containing group, or tin-containing group, and when R ⁷ to R ¹⁰ among these are hydrocarbon groups, R ⁷ and R ⁸ are linked together to form a ring and R ⁹ and R ¹⁰ may be linked together to form a ring. )

〈MMAO〉
Aluminoxane, which is a partial hydrolyzate of alkylaluminum, can be simply expressed as [--Al(R)--O--] _n (R=alkyl group) using its unit structure. Said n is usually 1-100, preferably 1-50.
In this case, modified methylaluminoxane (MMAO) can be represented as [--Al(Me)--O--] _n --[--Al(R)--O--] _m .
MMAO used in step 1 may be one kind or two or more kinds.

An aluminoxane can usually be obtained by reacting an organoaluminum compound with water, and MMAO includes, as the organoaluminum compound, trimethylaluminum (TMAL) and one or more alkylaluminums other than TMAL ( AAL).
The ratio of TMAL and AAL used can be selected as appropriate. The order of addition of each component used in the reaction is not particularly limited. For example, after AAL and water are reacted, TMAL may be added and reacted.

The alkyl group in AAL is not particularly limited, and examples thereof include ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, hexyl, octyl, decyl and dodecyl groups. Among these, an isobutyl group is preferred.
Any of monoalkylaluminum, dialkylaluminum, and trialkylaluminum can be used for AAL, but trialkylaluminum is preferred.
That is, the MMAO is preferably modified methylaluminoxane obtained using trimethylaluminum and triisobutylaluminum. By using the MMAO, it is possible to easily obtain the present catalyst solution capable of producing an olefin polymer with higher catalytic activity even after long-term storage.

The water used in the reaction between the organoaluminum and water is not particularly limited, and water of crystallization contained in copper sulfate hydrate, aluminum sulfate hydrate, etc. and water generated in the reaction system are not limited to water. components can also be used.

The reaction between the organoaluminum and water is usually carried out in an inert hydrocarbon (solvent).
Examples of the inert hydrocarbon include aliphatic hydrocarbons, alicyclic hydrocarbons, and aromatic hydrocarbons, and specific examples include pentane, hexane, heptane, cyclohexane, methylcyclohexane, benzene, toluene, and xylene. etc. Among these, aliphatic hydrocarbons and aromatic hydrocarbons are preferred.
Two or more of these inert hydrocarbons may be used.

The amount of water used in the reaction between the organoaluminum and water is preferably 0.25 to 1.2 mol, more preferably 0.5 to 1 mol, per 1 mol of Al in the organoaluminum compound.
The reaction temperature is generally -70 to 100°C, preferably -20 to 20°C, and the reaction time is generally 5 minutes to 24 hours, preferably 10 minutes to 5 hours.

As MMAO, one synthesized by the method described above may be used, or a commercially available product may be used. As MMAO, a solution obtained after synthesis or a commercial product in the form of a solution may be used as it is or after being diluted.
Examples of the commercial product include MMAO-3A grade obtained by using trimethylaluminum and triisobutylaluminum manufactured by Tosoh Finechem Co., Ltd.

<solvent>
As the solvent, a solvent capable of dissolving the present complex and MMAO is preferable.
The solvent used in step 1 may be one kind, or two or more kinds.

Specific examples of solvents include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; alicyclic hydrocarbons such as cyclopentane, cyclohexane, methylcyclopentane, and methylcyclohexane; Aromatic hydrocarbons such as toluene and xylene are exemplified, preferably aromatic hydrocarbons such as hexane, heptane, octane, decane, cyclohexane and toluene, and more preferably aromatic hydrocarbons such as toluene.

The complex can be stably stored for a long period of time in a solution state, and the olefin polymer can be produced with higher catalytic activity. It is preferable to remove some or all of the impurities in the solvent by drying.

<Contact of each component>
In step 1, the operation of contacting each component can be performed by adding each component to a container in any order. It can be carried out by further adding a solvent depending on the situation. Each component may be added in multiple portions.
The inside of the container is preferably purged with an inert gas such as nitrogen before adding each component.
In addition, step 1 may be performed under heating or cooling, if necessary.

The concentration of the present complex in the catalyst solution obtained in step 1 is such that the concentration of transition metal atoms in the present complex is usually 1×10 ⁻¹⁰ to 1×10 ⁻¹ mol/L, preferably 1×10 ⁻⁸ The concentration is ∼1×10 ⁻² mol/L.

After preparing the catalyst solution in step 1, step 2 may be performed immediately, but the catalyst solution obtained in step 1 exhibits high catalytic activity even after long-term storage. After that, step 2 does not necessarily have to be performed immediately, and the present method preferably includes a step of storing the catalyst solution obtained in the contact, from the viewpoint that the effects of the present invention are more exhibited.
The storage period in the step of storing the catalyst solution is not particularly limited. It is preferably 12 hours or longer, more preferably 1 day or longer. Also, the upper limit is, for example, five years.

<Step 2>
Step 2 is not particularly limited as long as it is a step of polymerizing olefin using the catalyst solution obtained in Step 1.
In the present specification, the term "polymerization" may be used in the sense of including not only homopolymerization but also copolymerization, and the term "polymer" includes not only homopolymers but also copolymerization. It is sometimes used in a sense that also includes coalescence.
As the catalyst solution used in step 2, one kind may be used, or two or more kinds may be used.

The amount of the present complex in the catalyst solution obtained in Step 1 used in Step 2 is usually 10 ^-10 to 10 ^-2 mol, preferably 10 ^-9 to 10 ^-3 mol, per liter of reaction volume. It is used in such an amount that it becomes mol.

Step 2 is a step of polymerizing olefin in the polymerization vessel in the presence of a solution containing the catalyst solution obtained in Step 1 and a further organoaluminum (hereinafter also referred to as "additional organoaluminum"). is preferred. At this time, a solvent (hereinafter also referred to as "additional solvent") may be added.
Thus, in addition to the catalyst solution obtained in step 1, by adding an additional organoaluminum, in other words, by performing the addition of the organoaluminum in two stages of steps 1 and 2, the olefin polymerization An olefin polymer can be produced with higher catalytic activity while enjoying the advantage of not needing to prepare a solution containing the present complex immediately before.

Examples of the additional organoaluminum include the following organoaluminum compounds. The additional organoaluminum may be different than the MMAO used in Step 1, but is preferably the same MMAO.

<Organoaluminum compound>
Although the organoaluminum compound is not particularly limited, examples thereof include an organoaluminum compound represented by the following formula.
The organoaluminum compound may be used alone or in combination of two or more.

R ^a _m Al(OR ^b ) _n H _p X _q
(Wherein, R ^a and R ^b may be the same or different and represent a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms,
X represents a halogen atom,
m is 0<m≦3, n is 0≦n<3, p is 0≦p<3, q is a number of 0≦q<3, and m+n+p+q=3. )

Examples of such organoaluminum compounds include:
tri-n-alkylaluminum such as trimethylaluminum, triethylaluminum, tri-n-butylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum;
Tri-branched alkyls such as triisopropylaluminum, triisobutylaluminum, tri-sec-butylaluminum, tri-tert-butylaluminum, tri-2-methylbutylaluminum, tri-3-methylhexylaluminum, tri-2-ethylhexylaluminum aluminum;
tricycloalkylaluminum such as tricyclohexylaluminum, tricyclooctylaluminum;
triarylaluminum such as triphenylaluminum, tri(4-methylphenyl)aluminum;
dialkylaluminum hydride such as diethylaluminum hydride, diisopropylaluminum hydride, diisobutylaluminum hydride;
dialkylaluminum alkoxides such as dimethylaluminum methoxide, diethylaluminum ethoxide, dibutylaluminum butoxide;
partially alkoxylated aluminum alkyls having an average composition such as the formula R ^a _2.5 Al(OR ^b ) _0.5 ;
alkylaluminum aryloxides such as diethylaluminum phenoxide, diethylaluminum (2,6-di-tert-butyl-4-methylphenoxide);
dialkylaluminum halides such as dimethylaluminum chloride, diethylaluminum chloride, dibutylaluminum chloride, diethylaluminum bromide, diisobutylaluminum chloride;
partially halogenated aluminum alkyls such as alkylaluminum dihalides such as ethylaluminum dichloride;
alkylaluminum dihydrides such as ethylaluminum dihydride, propylaluminum dihydride and other partially hydrogenated alkylaluminums;
partially alkoxylated and halogenated aluminum alkyls such as ethylaluminum ethoxychloride, butylaluminum butoxychloride, ethylaluminum ethoxybromide;
is mentioned.

Compounds analogous to those represented by the formula R am Al _{(OR b ) n H p X q} ^{can also} _{be used .} Examples of such compounds include
Alkenyl such as isoprenylaluminum represented by the formula ( _iC4H9 ) _{xAly ( C5H10} ) _z , where _x , _y and z are positive numbers and z≤2x aluminum;
alkylaluminum alkoxides such as isobutylaluminum methoxide, isobutylaluminum ethoxide;
alkylaluminum sesquialkoxides such as ethylaluminum sesquiethoxide, butylaluminum sesquibutoxide;
alkylaluminum sesquihalides such as ethylaluminum sesquichloride, butylaluminum sesquichloride, ethylaluminum sesquibromide;
Organoaluminum compounds in which _two or more aluminum compounds are bonded via a nitrogen atom (e.g. ( _C2H5 ) _{2AlN ( C2H5} )Al _{( C2H5} ) ₂ );
is mentioned.

Among these organoaluminum compounds, tri-n-alkylaluminum, tri-branched alkylaluminum, tricycloalkylaluminum, triarylaluminum, dialkylaluminum hydride, dialkylaluminum halide, alkyl Aluminum dihydride and alkylaluminum dihalide are preferred, tri-n-alkylaluminum and tri-branched alkylaluminum are more preferred, and tri-branched alkylaluminum is even more preferred. Among the tri-branched alkylaluminums, triisobutylaluminum is particularly preferable from the viewpoint of the stability of the aluminum compound and the low property of degeneration to the metallocene compound.

In step 2, the concentration of organoaluminum (sum of MMAO in the catalyst solution obtained in step 1 and additional organoaluminum used as necessary) is preferably 0.005 mmol/L or more in terms of aluminum atoms, More preferably, it is 0.01 mmol/L or more, for example, 1,000 mmol/L or less.

Further, in step 2, if necessary, a transition metal complex other than the catalyst solution obtained in step 1 (hereinafter also referred to as "additional transition metal complex") is added to the extent that the effects of the present invention are not impaired. Complex alkylated product (B-1b), dialkyl compound (B-1c), organoaluminumoxy compound (B-2), compound (B- 3), other additives such as a carrier (C) and an organic compound component (D) may be used.
One of these other additives may be used, or two or more thereof may be used.
Specific examples of these other additives include each component described in JP-A-2018-165308.

When the additional organoaluminum, additional solvent, and/or other additives are used, the order in which they and the catalyst solution obtained in step 1 are used is not particularly limited. may be added to the polymerization vessel in any order.

Examples of olefins to be polymerized in step 2 include ethylene, propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3-methyl - 1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, vinylcyclohexane, etc. Linear or branched chain having 3 to 20 carbon atoms Examples include α-olefins.
One of these α-olefins may be used, or two or more thereof may be used. Thus, for example, ethylene alone may be used, or ethylene and propylene may be used.

In step 2, polymerization may be carried out in the presence of at least one other monomer selected from polar group-containing monomers, aromatic vinyl compounds, and cyclic olefins in the reaction system. Thus, for example, the polymerization may be carried out using the cyclic olefin 5-ethylidene-2-norbornene along with ethylene and propylene.
The amount of these other monomers to be used is, for example, 20 parts by mass or less, preferably 10 parts by mass or less per 100 parts by mass of the α-olefin.

Examples of the polar group-containing monomer include α,β-unsaturated carboxylic acids such as (meth)acrylic acid, fumaric acid and maleic anhydride, and metal salts such as sodium salts thereof; methyl (meth)acrylate; α,β-unsaturated carboxylic acid esters such as ethyl (meth)acrylate and n-propyl (meth)acrylate; vinyl esters such as vinyl acetate and vinyl propionate; unsaturated such as glycidyl (meth)acrylate Examples include glycidyls.

Examples of the aromatic vinyl compound include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, o,p-dimethylstyrene, methoxystyrene, vinyl benzoic acid, methyl vinyl benzoate, vinyl benzyl acetate, Hydroxystyrene, p-chlorostyrene, divinylbenzene, α-methylstyrene and allylbenzene.

Examples of the cyclic olefins 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. types are mentioned.

The polymerization is not particularly limited, and liquid phase polymerization methods such as solution polymerization and suspension polymerization, gas phase polymerization methods, and the like can be mentioned.
The liquid phase polymerization can be carried out using an inert hydrocarbon medium. Examples of the inert hydrocarbon medium include the same compounds as the solvents listed in the column of Step 1. This inert hydrocarbon medium may be the catalyst solution obtained in step 1 as it is, or may be obtained by adding a new inert hydrocarbon medium (additional solvent) to the catalyst solution obtained in step 1. . The newly added inert hydrocarbon medium may be the same as or different from the solvent used in Step 1.

The polymerization temperature in step 2 is usually −50 to +200° C., preferably 0 to 180° C., and the polymerization pressure is usually atmospheric pressure to 10 MPa gauge pressure, preferably atmospheric pressure to 5 MPa gauge pressure.
The polymerization reaction can be carried out in any of a batch system, a semi-continuous system and a continuous system. Furthermore, the polymerization can be carried out in two or more stages with different reaction conditions.
Moreover, the molecular weight of the olefin polymer to be obtained may be adjusted by a conventionally known method, for example, by allowing hydrogen or the like to exist in the polymerization system or by changing the polymerization temperature.

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples, but the present invention is not limited to these examples as long as the gist thereof is not exceeded.

The reagents used in the following test examples are as follows.
- Toluene was used after being purified using an organic solvent refining device manufactured by Glass Contour.
- Xylene was used after removing impurities with activated alumina.
・As MMAO, MMAO-3A (manufactured by Tosoh Finechem Co., Ltd.), which is a 10 wt% modified methylaluminoxane / hexane solution, is added to 0.010 mol / L for catalyst contact and 1.0 mol / L for polymerization. Used after dilution.
The transition metal complex (1) used the compound (B-1) synthesized according to [Synthesis Example 1] of WO 2012/098865. Note that the transition metal complex (1) is represented by the following formula.
- Transition metal complex (2) was synthesized according to [Synthesis Example 2] of WO 2012/098865. Note that the transition metal complex (2) is represented by the following formula.

[Example 1]
[Contact operation 1] (Preparation of toluene solution of transition metal complex (1) containing 2 equivalents of MMAO)
2.5 mg of the transition metal complex (1) and 36.0 mL of toluene were charged at 25° C. into a 2-necked glass flask having an internal volume of 500 mL which was sufficiently purged with nitrogen, and then MMAO was added to 1 mol of the transition metal complex (1 ) at a ratio of 2 mol (this corresponds to (M _Al /M _M )=2), and toluene is added to make the total amount 360 mL, so that the concentration of the transition metal complex (1) is A solution was prepared that was 0.01 mmol/L.
Next, the prepared solution was immediately subdivided into three glass two-necked flasks having an internal volume of 100 mL that were sufficiently nitrogen-substituted to obtain solutions (A-1), (A-1′) and (A-1″). ).

[Storage of solution]
The resulting solutions (A-1), (A-1′) and (A-1″) were stored in a cool dark place at a temperature of 5° C. under a nitrogen atmosphere for 1 hour, 7 days or 14 days, respectively.

[Polymerization step (production of polyethylene)]
After charging 250 mL of xylene into a glass reactor having an inner volume of 0.5 L which was sufficiently purged with nitrogen, the temperature was raised to 100°C. 100 L/hr of ethylene was continuously supplied thereto to saturate the liquid phase and gas phase. Subsequently, while ethylene was continuously supplied, 0.25 mL (0.25 mmol) of a hexane solution (1.0 mol/L) of MMAO-3A was added, and 5.0 mL of solution (A-1) after storage for 1 hour (this 0.00005 mmol of transition metal complex (1) was added to the solution, and polymerization was carried out at 100° C. for 5 minutes under normal pressure. Polymerization was terminated by adding a small amount of isobutanol. The resulting polymerization reaction solution was added to 1 L of methanol containing 1 mL of hydrochloric acid to precipitate a polymer.
After washing the obtained polymer with methanol, it was dried under reduced pressure at 100° C. for 10 hours to obtain 1.61 g of polyethylene. The mileage per 1 mmol of zirconium atoms in the transition metal complex (1) was 32.3 kg. Table 1 shows the results.

[Comparative Example 1]
[Comparative Contact Operation 1] (Preparation of Toluene Solution of Transition Metal Complex (1) Not Containing MMAO)
The same operation as in contact operation 1 was performed except that MMAO was not used, a solution having a concentration of transition metal complex (1) of 0.01 mmol / L was prepared, and a glass with an internal volume of 100 mL was sufficiently replaced with nitrogen. The solutions (A-0), (A-0′) and (A-0″) were obtained by immediately subdividing the prepared solutions into three two-necked flasks.

[Storage of solution]
The resulting solutions (A-0), (A-0') and (A-0'') were stored in a cool dark place at a temperature of 5° C. under a nitrogen atmosphere for 1 hour, 7 days or 14 days, respectively.

[Polymerization step (production of polyethylene)]
Polymerization was carried out in the same manner as in Example 1, except that the solution (A-1) was changed to the solution (A-0).
The polyethylene obtained was 1.65 g. The mileage per 1 mmol of zirconium atoms in the transition metal complex (1) was 33.1 kg. Table 1 shows the results.

[Example 2]
[Contact operation 2] (Preparation of toluene solution of transition metal complex (1) containing 3 equivalents of MMAO)
A solution having a transition metal complex (1) concentration of 0.01 mmol/L was prepared by performing the same operation as in the contact operation 1 except that the amount of MMAO added to the transition metal complex (1) was changed to 3 equivalents, The solutions (A-2), (A-2′) and (A-2″) were obtained by immediately subdividing the prepared solution into three two-necked glass flasks having an internal volume of 100 mL which were sufficiently replaced with nitrogen. Obtained.

[Storage of solution]
The resulting solutions (A-2), (A-2') and (A-2'') were stored in a cool dark place at a temperature of 5° C. under a nitrogen atmosphere for 1 hour, 7 days or 14 days, respectively.

[Polymerization step (production of polyethylene)]
Polymerization was carried out in the same manner as in Example 1, except that the solution (A-1) was changed to the solution (A-2).
The polyethylene obtained was 1.66 g. The mileage per 1 mmol of zirconium atoms in the transition metal complex (1) was 33.2 kg. Table 1 shows the results.

[Example 3]
[Contact operation 3] (Preparation of toluene solution of transition metal complex (1) containing 5 equivalents of MMAO)
A solution having a transition metal complex (1) concentration of 0.01 mmol/L was prepared by performing the same operation as in the contact operation 1 except that the amount of MMAO added to the transition metal complex (1) was changed to 5 equivalents, By immediately subdividing the solution after preparation into three 2-necked glass flasks with an internal volume of 100 mL that were sufficiently nitrogen-substituted, solutions (A-3), (A-3′) and (A-3″) were obtained. Obtained.

[Storage of solution]
The resulting solutions (A-3), (A-3') and (A-3'') were stored in a cool dark place at a temperature of 5°C under a nitrogen atmosphere for 1 hour, 7 days or 14 days, respectively.

[Polymerization step (production of polyethylene)]
Polymerization was carried out in the same manner as in Example 1, except that the solution (A-1) was changed to the solution (A-3).
The polyethylene obtained was 1.60 g. The mileage per 1 mmol of zirconium atoms in the transition metal complex (1) was 31.9 kg. Table 1 shows the results.

[Comparative Example 2]
[Comparative contact operation 2] (Preparation of toluene solution of transition metal complex (1) containing 10 equivalents of MMAO)
A solution having a transition metal complex (1) concentration of 0.01 mmol/L was prepared by performing the same operation as in the contact operation 1 except that the amount of MMAO added to the transition metal complex (1) was changed to 10 equivalents, By immediately subdividing the solution after preparation into three 2-necked glass flasks with an internal volume of 100 mL that were sufficiently nitrogen-substituted, solutions (A-4), (A-4′) and (A-4″) were obtained. Obtained.

[Storage of solution]
The resulting solutions (A-4), (A-4') and (A-4'') were stored in a cool dark place at a temperature of 5°C under a nitrogen atmosphere for 1 hour, 7 days or 14 days, respectively.

[Polymerization step (production of polyethylene)]
Polymerization was carried out in the same manner as in Example 1, except that the solution (A-1) was changed to the solution (A-4).
The polyethylene obtained was 1.44 g. The mileage per 1 mmol of zirconium atoms in the transition metal complex (1) was 28.7 kg. Table 1 shows the results.

[Comparative Example 3]
[Comparative contacting operation 3] (Preparation of toluene solution of transition metal complex (1) containing 20 equivalents of MMAO)
A solution having a transition metal complex (1) concentration of 0.01 mmol/L was prepared by performing the same operation as the contact operation 1 except that the amount of MMAO added to the transition metal complex (1) was changed to 20 equivalents, By immediately subdividing the solution after preparation into three 2-necked glass flasks with an internal volume of 100 mL that were sufficiently nitrogen-substituted, solutions (A-5), (A-5′) and (A-5″) were obtained. Obtained.

[Storage of solution]
The resulting solutions (A-5), (A-5') and (A-5'') were stored in a cool dark place at a temperature of 5° C. under a nitrogen atmosphere for 1 hour, 7 days or 14 days, respectively.

[Polymerization step (production of polyethylene)]
Polymerization was carried out in the same manner as in Example 1, except that the solution (A-1) was changed to the solution (A-5).
The polyethylene obtained was 1.40 g. The mileage per 1 mmol of zirconium atoms in the transition metal complex (1) was 28.1 kg. Table 1 shows the results.

[Example 4] (Production of polyethylene using a toluene solution of transition metal complex (1) containing 2 equivalents of MMAO, stored for 7 days)
Polymerization was carried out in the same manner as in Example 1, except that the solution (A-1) was changed to the solution (A-1').
The polyethylene obtained was 1.65 g. The mileage per 1 mmol of zirconium atoms in the transition metal complex (1) was 33.1 kg. Table 2 shows the results.

[Comparative Example 4] (Production of polyethylene using a toluene solution of transition metal complex (1) containing no MMAO, stored for 7 days)
Polymerization was carried out in the same manner as in Example 1, except that the solution (A-1) was changed to the solution (A-0').
The polyethylene obtained was 1.47 g. The mileage per 1 mmol of zirconium atoms in the transition metal complex (1) was 29.4 kg. Table 2 shows the results.

[Example 5] (Production of polyethylene using a toluene solution of transition metal complex (1) containing 3 equivalents of MMAO, stored for 7 days)
Polymerization was carried out in the same manner as in Example 1, except that the solution (A-1) was changed to the solution (A-2').
The polyethylene obtained was 1.66 g. The mileage per 1 mmol of zirconium atoms in the transition metal complex (1) was 33.3 kg. Table 2 shows the results.

[Example 6] (Production of polyethylene using a toluene solution of transition metal complex (1) containing 5 equivalents of MMAO, stored for 7 days)
Polymerization was carried out in the same manner as in Example 1, except that the solution (A-1) was changed to the solution (A-3').
The polyethylene obtained was 1.58 g. The mileage per 1 mmol of zirconium atoms in the transition metal complex (1) was 31.6 kg. Table 2 shows the results.

[Comparative Example 5] (Production of polyethylene using a toluene solution of transition metal complex (1) containing 10 equivalents of MMAO, stored for 7 days)
Polymerization was carried out in the same manner as in Example 1, except that the solution (A-1) was changed to the solution (A-4').
The polyethylene obtained was 1.39 g. The mileage per 1 mmol of zirconium atoms in the transition metal complex (1) was 27.8 kg. Table 2 shows the results.

[Comparative Example 6] (Production of polyethylene using a toluene solution of transition metal complex (1) containing 20 equivalents of MMAO, stored for 7 days)
Polymerization was carried out in the same manner as in Example 1, except that the solution (A-1) was changed to the solution (A-5').
The polyethylene obtained was 0.70 g. The mileage per 1 mmol of zirconium atoms in the transition metal complex (1) was 14.1 kg. Table 2 shows the results.

[Example 7] (Production of polyethylene using a toluene solution of transition metal complex (1) containing 2 equivalents of MMAO, stored for 14 days)
Polymerization was carried out in the same manner as in Example 1, except that the solution (A-1) was changed to the solution (A-1'').
The polyethylene obtained was 1.59 g. The mileage per 1 mmol of zirconium atoms in the transition metal complex (1) was 31.9 kg. Table 3 shows the results.

[Comparative Example 7] (Production of polyethylene using a toluene solution of transition metal complex (1) containing no MMAO, stored for 14 days)
Polymerization was carried out in the same manner as in Example 1, except that the solution (A-1) was changed to the solution (A-0'').
The polyethylene obtained was 0.94 g. The mileage per 1 mmol of zirconium atoms in the transition metal complex (1) was 18.9 kg. Table 3 shows the results.

[Example 8] (Production of polyethylene using a toluene solution of transition metal complex (1) containing 3 equivalents of MMAO, stored for 14 days)
Polymerization was carried out in the same manner as in Example 1, except that the solution (A-1) was changed to the solution (A-2″).
The polyethylene obtained was 1.69 g. The mileage per 1 mmol of zirconium atoms in the transition metal complex (1) was 33.9 kg. Table 3 shows the results.

[Example 9] (Production of polyethylene using a toluene solution of transition metal complex (1) containing 5 equivalents of MMAO, stored for 14 days)
Polymerization was carried out in the same manner as in Example 1, except that the solution (A-1) was changed to the solution (A-3″).
The polyethylene obtained was 1.60 g. The mileage per 1 mmol of zirconium atoms in the transition metal complex (1) was 31.9 kg. Table 3 shows the results.

[Comparative Example 8] (Production of polyethylene using a toluene solution of transition metal complex (1) containing 10 equivalents of MMAO, stored for 14 days)
Polymerization was carried out in the same manner as in Example 1, except that the solution (A-1) was changed to the solution (A-4'').
The polyethylene obtained was 1.09 g. The mileage per 1 mmol of zirconium atoms in the transition metal complex (1) was 21.8 kg. Table 3 shows the results.

[Comparative Example 9] (Production of polyethylene using a toluene solution of transition metal complex (1) containing 20 equivalents of MMAO, stored for 14 days)
Polymerization was carried out in the same manner as in Example 1, except that the solution (A-1) was changed to the solution (A-5'').
The polyethylene obtained was 0.15 g. The mileage per 1 mmol of zirconium atoms in the transition metal complex (1) was 3.0 kg. Table 3 shows the results.

<Comparison between Comparative Examples 1, 4, and 7 and Examples 1 to 9>
Comparing Comparative Examples 1, 4 and 7, the longer the storage period of the catalyst solution, the lower the activity. On the other hand, in Examples 1 to 9 using catalyst solutions in which 2 to 5 equivalents of MMAO were added to the transition metal complex, the activity was maintained even when the storage period of the catalyst solution was long. , it can be seen that the storage stability is excellent.

<Comparison between Examples 3, 6 and 9 and Comparative Examples 2, 3, 5, 6, 8 and 9>
In Examples 3, 6, and 9, in which the catalyst solution containing 5 equivalents of MMAO was added to the transition metal complex, the activity was maintained even when the catalyst solution was stored for a long period of time. In Comparative Examples 2, 5, and 8 using catalyst solutions to which 10 equivalents of MMAO were added, the activity was slightly reduced when the storage period was 7 days, but it cannot be said that the activity was sufficient when the storage period was 14 days. . Furthermore, in Comparative Examples 3, 6 and 9 using the catalyst solution to which 20 equivalents of MMAO was added, the activity decreased significantly as the storage period became longer. It turns out that it is inferior in stability.

[Example 10]
[Contact operation 4] (Preparation of toluene solution of transition metal complex (2) containing 2 equivalents of MMAO)
2.9 mg of the transition metal complex (2) and 40.1 mL of toluene were charged at 25° C. into a glass two-necked flask having an internal volume of 500 mL which was sufficiently purged with nitrogen, and then MMAO was added to 1 mol of the transition metal complex (2 ), and then toluene was added to bring the total amount to 401 mL, thereby preparing a solution having a transition metal complex (2) concentration of 0.01 mmol/L.
Next, the solution after preparation was immediately subdivided into three 2-necked glass flasks with an internal volume of 100 mL that were sufficiently nitrogen-substituted to obtain solutions (B-1), (B-1′) and (B-1″). ).

[Storage of solution]
The resulting solutions (B-1), (B-1′) and (B-1″) were stored in a cool dark place at a temperature of 5° C. under a nitrogen atmosphere for 1 hour, 7 days or 14 days, respectively.

[Polymerization step (production of polyethylene)]
After charging 250 mL of xylene into a glass reactor having an inner volume of 0.5 L which was sufficiently purged with nitrogen, the temperature was raised to 100°C. 100 L/hr of ethylene was continuously supplied thereto to saturate the liquid phase and gas phase. Subsequently, while ethylene was continuously supplied, 0.25 mL (0.25 mmol) of a hexane solution (1.0 mol/L) of MMAO-3A was added, and 5.0 mL of the solution (B-1) after storage for 1 hour (this 0.00005 mmol of transition metal complex (2) was added to the solution, and polymerization was carried out at 100° C. for 5 minutes under normal pressure. Polymerization was terminated by adding a small amount of isobutanol. The resulting polymerization reaction solution was added to 1 L of methanol containing 1 mL of hydrochloric acid to precipitate a polymer.
After washing the obtained polymer with methanol, it was dried under reduced pressure at 100° C. for 10 hours to obtain 1.29 g of polyethylene. The mileage per 1 mmol of zirconium atoms in the transition metal complex (2) was 25.9 kg. Table 4 shows the results.

[Comparative Example 10]
[Comparative Contact Operation 4] (Preparation of Toluene Solution of Transition Metal Complex (2) Not Containing MMAO)
The same operation as in contact operation 4 was performed except that MMAO was not used, to prepare a solution having a concentration of transition metal complex (2) of 0.01 mmol / L, and a glass with an internal volume of 100 mL that was sufficiently nitrogen-substituted The solutions (B-0), (B-0′) and (B-0″) were obtained by immediately subdividing the prepared solutions into three two-necked flasks.

[Storage of solution]
The resulting solutions (B-0), (B-0′) and (B-0″) were stored in a cool dark place at 5° C. under a nitrogen atmosphere for 1 hour, 7 days or 14 days, respectively.

[Polymerization step (production of polyethylene)]
Polymerization was carried out in the same manner as in Example 10, except that the solution (B-1) was changed to the solution (B-0).
The polyethylene obtained was 1.29 g. The mileage per 1 mmol of zirconium atoms in transition metal complex (2) was 25.8 kg. Table 4 shows the results.

[Example 11]
[Contact operation 5] (Preparation of toluene solution of transition metal complex (2) containing 3 equivalents of MMAO)
A solution having a transition metal complex (2) concentration of 0.01 mmol/L was prepared by performing the same operation as the contact operation 4 except that the amount of MMAO added to the transition metal complex (2) was changed to 3 equivalents. , By immediately subdividing the solution after preparation into three 2-necked glass flasks with an internal volume of 100 mL that were sufficiently nitrogen-substituted, solutions (B-2), (B-2') and (B-2") got

[Storage of solution]
The resulting solutions (B-2), (B-2') and (B-2'') were stored in a cool dark place at a temperature of 5°C under a nitrogen atmosphere for 1 hour, 7 days or 14 days, respectively.

[Polymerization step (production of polyethylene)]
Polymerization was carried out in the same manner as in Example 10, except that the solution (B-1) was changed to the solution (B-2).
The polyethylene obtained was 1.27 g. The mileage per 1 mmol of zirconium atoms in transition metal complex (2) was 25.2 kg. Table 4 shows the results.

[Example 12]
[Contact operation 6] (Preparation of toluene solution of transition metal complex (2) containing 5 equivalents of MMAO)
A solution having a transition metal complex (2) concentration of 0.01 mmol/L was prepared by performing the same operation as in the contact operation 4, except that the amount of MMAO added to the transition metal complex (2) was changed to 5 equivalents. , By immediately subdividing the prepared solution into three 2-necked glass flasks with an internal volume of 100 mL that were sufficiently nitrogen-substituted, solutions (B-3), (B-3') and (B-3") got

[Storage of solution]
The resulting solutions (B-3), (B-3′) and (B-3″) were stored in a cool dark place at 5° C. under a nitrogen atmosphere for 1 hour, 7 days or 14 days, respectively.

[Polymerization step (production of polyethylene)]
Polymerization was carried out in the same manner as in Example 10, except that the solution (B-1) was changed to the solution (B-3).
The polyethylene obtained was 1.20 g. The mileage per 1 mmol of zirconium atoms in transition metal complex (2) was 24.0 kg. Table 4 shows the results.

[Comparative Example 11]
[Comparative contacting operation 5] (Preparation of toluene solution of transition metal complex (2) containing 10 equivalents of MMAO)
A solution having a transition metal complex (2) concentration of 0.01 mmol/L was prepared by performing the same operation as in the contact operation 4 except that the amount of MMAO added to the transition metal complex (2) was changed to 10 equivalents. , By immediately subdividing the prepared solution into three 2-necked glass flasks with an internal volume of 100 mL that were sufficiently nitrogen-substituted, solutions (B-4), (B-4') and (B-4") got

[Storage of solution]
The resulting solutions (B-4), (B-4') and (B-4'') were stored in a cool dark place at a temperature of 5°C under a nitrogen atmosphere for 1 hour, 7 days or 14 days, respectively.

[Polymerization step (production of polyethylene)]
Polymerization was carried out in the same manner as in Example 10, except that the solution (B-1) was changed to the solution (B-4).
The polyethylene obtained was 1.14 g. The mileage per 1 mmol of zirconium atoms in transition metal complex (2) was 22.7 kg. Table 4 shows the results.

[Comparative Example 12]
[Comparative contacting operation 6] (Preparation of toluene solution of transition metal complex (2) containing 20 equivalents of MMAO)
A solution having a transition metal complex (2) concentration of 0.01 mmol/L was prepared by performing the same operation as the contact operation 4 except that the amount of MMAO added to the transition metal complex (2) was changed to 20 equivalents. , By immediately subdividing the solution after preparation into three 2-neck glass flasks with an internal volume of 100 mL that were sufficiently nitrogen-substituted, solutions (B-5), (B-5') and (B-5") got

[Storage of solution]
The resulting solutions (B-5), (B-5') and (B-5'') were stored in a cool dark place at a temperature of 5° C. under a nitrogen atmosphere for 1 hour, 7 days or 14 days, respectively.

[Polymerization step (production of polyethylene)]
Polymerization was carried out in the same manner as in Example 10, except that the solution (B-1) was changed to the solution (B-5).
The polyethylene obtained was 1.14 g. The mileage per 1 mmol of zirconium atoms in transition metal complex (2) was 22.6 kg. Table 4 shows the results.

[Example 13] (Production of polyethylene using a toluene solution of transition metal complex (2) containing 2 equivalents of MMAO, stored for 7 days)
Polymerization was carried out in the same manner as in Example 10, except that the solution (B-1) was changed to the solution (B-1').
The polyethylene obtained was 1.31 g. The mileage per 1 mmol of zirconium atoms in transition metal complex (2) was 26.2 kg. Table 5 shows the results.

[Comparative Example 13] (Production of polyethylene using a toluene solution of transition metal complex (2) containing no MMAO, stored for 7 days)
Polymerization was carried out in the same manner as in Example 10, except that the solution (B-1) was changed to the solution (B-0').
The polyethylene obtained was 1.17 g. The mileage per 1 mmol of zirconium atoms in the transition metal complex (2) was 23.4 kg. Table 5 shows the results.

[Example 14] (Production of polyethylene using a toluene solution of transition metal complex (2) containing 3 equivalents of MMAO, stored for 7 days)
Polymerization was carried out in the same manner as in Example 10, except that the solution (B-1) was changed to the solution (B-2').
The polyethylene obtained was 1.28 g. The mileage per 1 mmol of zirconium atoms in transition metal complex (2) was 25.6 kg. Table 5 shows the results.

[Example 15] (Production of polyethylene using a toluene solution of transition metal complex (2) containing 5 equivalents of MMAO, stored for 7 days)
Polymerization was carried out in the same manner as in Example 10, except that the solution (B-1) was changed to the solution (B-3').
The polyethylene obtained was 1.19 g. The mileage per 1 mmol of zirconium atoms in the transition metal complex (2) was 23.7 kg. Table 5 shows the results.

[Comparative Example 14] (Production of polyethylene using a toluene solution of transition metal complex (2) containing 10 equivalents of MMAO, stored for 7 days)
Polymerization was carried out in the same manner as in Example 10, except that the solution (B-1) was changed to the solution (B-4').
The polyethylene obtained was 1.05 g. The mileage per 1 mmol of zirconium atoms in the transition metal complex (2) was 21.0 kg. Table 5 shows the results.

[Comparative Example 15] (Production of polyethylene using a toluene solution of transition metal complex (2) containing 20 equivalents of MMAO, stored for 7 days)
Polymerization was carried out in the same manner as in Example 10, except that the solution (B-1) was changed to the solution (B-5').
The polyethylene obtained was 0.95 g. The mileage per 1 mmol of zirconium atoms in the transition metal complex (2) was 18.9 kg. Table 5 shows the results.

[Example 16] (Production of polyethylene using a toluene solution of transition metal complex (2) containing 2 equivalents of MMAO, stored for 14 days)
Polymerization was carried out in the same manner as in Example 10, except that the solution (B-1) was changed to the solution (B-1'').
The polyethylene obtained was 1.18 g. The mileage per 1 mmol of zirconium atoms in the transition metal complex (2) was 23.6 kg. Table 6 shows the results.

[Comparative Example 16] (Production of polyethylene using a toluene solution of transition metal complex (2) containing no MMAO, stored for 14 days)
Polymerization was carried out in the same manner as in Example 10, except that the solution (B-1) was changed to the solution (B-0'').
The polyethylene obtained was 0.89 g. The mileage per 1 mmol of zirconium atoms in the transition metal complex (2) was 17.8 kg. Table 6 shows the results.

[Example 17] (Production of polyethylene using a toluene solution of transition metal complex (2) containing 3 equivalents of MMAO, stored for 14 days)
Polymerization was carried out in the same manner as in Example 10, except that the solution (B-1) was changed to the solution (B-2″).
The polyethylene obtained was 1.32 g. The mileage per 1 mmol of zirconium atoms in the transition metal complex (2) was 26.4 kg. Table 6 shows the results.

[Example 18] (Production of polyethylene using a toluene solution of transition metal complex (2) containing 5 equivalents of MMAO, stored for 14 days)
Polymerization was carried out in the same manner as in Example 10, except that the solution (B-1) was changed to the solution (B-3″).
The polyethylene obtained was 1.25 g. The mileage per 1 mmol of zirconium atoms in transition metal complex (2) was 24.9 kg. Table 6 shows the results.

[Comparative Example 17] (Production of polyethylene using a toluene solution of transition metal complex (2) containing 10 equivalents of MMAO, stored for 14 days)
Polymerization was carried out in the same manner as in Example 10, except that the solution (B-1) was changed to the solution (B-4'').
The polyethylene obtained was 0.85 g. The mileage per 1 mmol of zirconium atoms in the transition metal complex (2) was 17.0 kg. Table 6 shows the results.

[Comparative Example 18] (Production of polyethylene using a toluene solution of transition metal complex (2) containing 20 equivalents of MMAO, stored for 14 days)
Polymerization was carried out in the same manner as in Example 10, except that the solution (B-1) was changed to the solution (B-5'').
The polyethylene obtained was 0.56 g. The mileage per 1 mmol of zirconium atoms in the transition metal complex (2) was 11.1 kg. Table 6 shows the results.

<Comparison between Comparative Examples 10, 13, and 16 and Examples 10 to 18>
Comparing Comparative Examples 10, 13 and 16, the activity decreases as the storage period of the catalyst solution increases. On the other hand, in Examples 10 to 18 using catalyst solutions in which 2 to 5 equivalents of MMAO were added to the transition metal complex, the activity was maintained even when the catalyst solution was stored for a long period of time. , it can be seen that the storage stability is excellent.

<Comparison between Examples 12, 15 and 18 and Comparative Examples 11, 12, 14, 15, 17 and 18>
In Examples 12, 15 and 18, in which the catalyst solution containing 5 equivalents of MMAO was added to the transition metal complex, the activity was maintained even when the catalyst solution was stored for a long period of time. In Comparative Examples 11, 14, and 17 using catalyst solutions to which 10 equivalents of MMAO were added, the activity was slightly reduced when the storage period was 7 days, but it cannot be said that the activity was sufficient when the storage period was 14 days. . Furthermore, in Comparative Examples 12, 15 and 18 using catalyst solutions to which 20 equivalents of MMAO were added, the activity decreased significantly as the storage period became longer. It turns out that it is inferior in stability.

Claims (4)

Step 1 of contacting a transition metal complex having an imine group, a modified methylaluminoxane (MMAO), and a solvent to prepare a catalyst solution;
Step 2 of polymerizing an olefin using the catalyst solution;
including
In the step 1, the MMAO and the transition metal complex are combined into a ratio (M _Al /M _M ) of the moles (M _Al ) of the aluminum atoms in the MMAO and the moles (M _M ) of the central metal of the transition metal complex. is used in an amount of 0.1 to 9.5,
A method for producing an olefin polymer. 2. The method for producing an olefin polymer according to claim 1, wherein said MMAO is modified methylaluminoxane obtained using trimethylaluminum and triisobutylaluminum. 3. The method for producing an olefin polymer according to claim 1 or 2, wherein said step 1 is a step of contacting said transition metal complex, said MMAO and said solvent, and then storing the obtained solution for 1 hour or more. . comprising a transition metal complex having an imine group, a modified methylaluminoxane (MMAO), and a solvent;
The ratio (M _Al /M _M ) between the moles (M _Al ) of aluminum atoms in the MMAO and the moles (M _M ) of the central metal of the transition metal complex is 0.1 to 9.5.
Catalyst solution for olefin polymerization.