JP2023142959A - Method for producing olefin copolymer and transition metal compound - Google Patents

Abstract

To provide a method that can efficiently produce a cyclic olefin copolymer including an aromatic structure, preferably its high-molecular-weight body, and to provide a novel transition metal compound suitable as a component of a catalyst for olefinic polymerization in the production method.SOLUTION: According to a method herein, in the presence of a catalyst for olefinic polymerization, illustrated by a compound of the following structure with a hafnium atom, an ethylene, an aliphatic cyclic olefin and a cyclic olefin including an aromatic structure are copolymerized.SELECTED DRAWING: None

Description

The present invention relates to a method for producing an olefin copolymer. The present invention also relates to novel transition metal compounds.

BACKGROUND ART Catalysts comprising metallocene compounds and cocatalysts such as organoaluminumoxy compounds have been known as catalysts for producing olefin polymers such as ethylene/α-olefin copolymers. Specifically, transition metal compounds containing multiple cyclopentadienyl ligands, transition metal compounds containing multiple indenyl ligands, and transition metal compounds containing a cyclopentadienyl ligand and a fluorenyl ligand. This can be cited as a representative example.

Additionally, transition metal compounds containing cyclopentadienyl and indenyl ligands have also been reported. (Non-patent literature 1, 2)
Copolymers of ethylene and cyclic olefins (hereinafter sometimes referred to as COC) are known to be suitable for optical materials because they are amorphous, have excellent transparency, and have a high glass transition temperature. . Recently, it has also been used as a pickup lens for DVDs and as an imaging lens for mobile phones and smartphones.

It is known that the olefin polymerization catalyst containing the metallocene complex described above exhibits excellent copolymerization as one of its characteristics, but in the copolymerization reaction containing the cyclic olefin, the cyclic olefin does not react. It is known that there are cases where the molecular weight tends to be difficult to increase or the molecular weight tends to be difficult to increase.

Journal of the Chemical Society, Dalton Transactions: Inorganic Chemistry 1994, 5, 657. Macromolecules 2001, 34, 3830.

The catalyst for olefin polymerization using a transition metal compound described in Non-Patent Document 1 as a metallocene compound is considered to be suitable for a copolymer of ethylene, an alicyclic cyclic olefin, and a cyclic olefin containing an aromatic structure. However, studies conducted by the present inventors have shown that the polymerization activity and the molecular weight of the resulting polymer are not sufficient. This is because by using a cyclic olefin containing an aromatic structure, the active sites derived from the transition metal compound are affected by the electronics derived from the aromatic structure, decreasing the polymerization rate and relatively increasing the chain transfer rate. The possibility was considered.

Therefore, an object of the present invention is to provide a suitable method for producing a copolymer of ethylene, an alicyclic cyclic olefin, and a cyclic olefin containing an aromatic structure. Another object of the present invention is to provide a transition metal compound that is preferably suitable for the above-mentioned manufacturing method.

The present invention relates to, for example, the following [1] to [4].
[1]
(A) a transition metal compound represented by the following general formula [A] and (B) (B-1) an organometallic compound,
(B-2) Presence of an olefin polymerization catalyst comprising an organoaluminumoxy compound, and (B-3) at least one compound selected from the group consisting of a compound that reacts with the transition metal compound to form an ion pair. A method for producing an olefin copolymer, which comprises copolymerizing ethylene, an alicyclic olefin, and a cyclic olefin containing an aromatic structure.

[In formula [A],
M is a hafnium atom,
n is an integer from 1 to 4,
Y is carbon or silicon; Q is each independently a hydrogen atom, a halogen atom, a hydrocarbon group, a halogen-containing group, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a phosphorus-containing group, a boron-containing group , an aluminum-containing group, or a diene-based divalent derivative group,
R', R ^{1`</sup> to R <sup>10`} each independently represent a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogen atom, a halogen-containing group, a silicon-containing group, an oxygen-containing group, a nitrogen-containing group, a sulfur-containing group , or a phosphorus-containing group,
The plurality of R ^5' to R ^10' include structures in which two or more of them are connected to form a cyclic structure or a multiple bond structure, and R ^6' and R ^7' are structures in which they are bonded to each other. ]
[2]
The method for producing an olefin copolymer according to the above [1], wherein in the general formula [A], R ^{1`</sup> is a hydrocarbon group having 1 to 20 carbon atoms, and R <sup>2`} to R ^4` are hydrogen atoms.

[3]
A transition metal compound represented by the following general formula [A].

[In formula [A],
M is a hafnium atom,
n is an integer from 1 to 4,
Y is carbon or silicon; Q is each independently a hydrogen atom, a halogen atom, a hydrocarbon group, a halogen-containing group, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a phosphorus-containing group, a boron-containing group , an aluminum-containing group, or a diene-based divalent derivative group,
R', R ^{1`</sup> to R <sup>10`} each independently represent a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogen atom, a halogen-containing group, a silicon-containing group, an oxygen-containing group, a nitrogen-containing group, a sulfur-containing group , or a phosphorus-containing group,
The plurality of R ^5' to R ^10' include structures in which two or more of them are connected to form a cyclic structure or a multiple bond structure, and R ^6' and R ^7' are structures in which they are bonded to each other. ]

[4]
The transition metal compound according to the above [3], wherein in the general formula [A], R ^{1`</sup> is a hydrocarbon group having 1 to 20 carbon atoms, and R <sup>2`} to R ^4` are hydrogen atoms.

By using the method for producing an olefin copolymer of the present invention, a polymer with a high molecular weight can be produced with relatively high activity.
Furthermore, the transition metal compounds used in the method for producing an olefin copolymer of the present invention include novel compounds.

Hereinafter, the method for producing an olefin copolymer, the transition metal compound, etc. according to the present invention will be explained in more detail.
[Transition metal compounds]
The transition metal compound (A) used in the method for producing an olefin copolymer of the present invention is represented by the following general formula [A].

Moreover, the transition metal compound (A) having a specific structure among the transition metal compounds (A) is a novel compound.

[Transition metal compound (A)]
First, the transition metal compound (A) will be explained.
《M》
In formula [A], M represents a hafnium atom.

《R ^{`</sup> , R <sup>1`} ~ R ^{10`</sup> 》
In formula [A], R <sup>`} , R ^{1 `</sup> to R <sup>10 `} each independently represent a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogen atom, a halogen-containing group, a silicon-containing group, an oxygen-containing group, or a nitrogen atom. a sulfur-containing group, or a phosphorus-containing group.

R ^{1`</sup> to R <sup>10`} include a structure in which they are bonded to each other to form a cyclic structure. More specific examples of this cyclic structure include ring structures in which adjacent groups (substituents bonded to adjacent carbons) among R ^{1`</sup> to R <sup>10`} are bonded to each other, and multiple bonds (double bonds, triple bonds). combination). Further, a cyclic structure in which a plurality of groups bonded to the same carbon such as R ^5' to R ^8' are bonded to each other (for example, a cyclic structure in which two R ^5's are bonded) can be mentioned. Of course, improbable structures such as two R ^5's directly bonding to form a multiple bond are excluded from this definition.

Examples of the halogen atoms include fluorine, chlorine, bromine, and iodine.
Examples of the hydrocarbon group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, neopentyl, n-hexyl, etc. having 1 to 20 carbon atoms, preferably 1 to 10 linear or branched alkyl groups;
A linear or branched alkenyl group having 2 to 20 carbon atoms, preferably 2 to 10 carbon atoms, such as vinyl, allyl, isopropenyl;
A linear or branched alkynyl group having 2 to 20 carbon atoms, preferably 2 to 10 carbon atoms, such as ethynyl and propargyl;
A cyclic saturated hydrocarbon group having 3 to 20 carbon atoms, preferably 3 to 10 carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl;
Cyclic unsaturated hydrocarbon groups having 5 to 20 carbon atoms, such as cyclopentadienyl, indenyl, and fluorenyl; preferably 6 to 20 carbon atoms, such as phenyl, benzyl, naphthyl, biphenyl, terphenyl, phenanthryl, and anthracenyl. 6 to 10 aryl groups; and alkyl-substituted aryl groups such as tolyl, iso-propylphenyl, t-butylphenyl, dimethylphenyl, di-t-butylphenyl.

Also included are those in which the hydrogen atom of the above-mentioned hydrocarbon group is substituted with a hydrocarbon group, such as an aryl-substituted alkyl group such as benzyl and cumyl.
Examples of structures having a ring formed by bonding adjacent groups among R ^{1`</sup> to R <sup>4`} and R ^{5`</sup> to R <sup>10`} include the following ring structures, and the ring structure is It may further have a substituent. Among the above, it is preferable that R ^1' to R ^4' have a structure in which they do not bond to each other.

Among the above structures, it may be preferable that R ^5' to R ^8' bonded to adjacent carbons directly bond to each other to form a multiple bond to form an aromatic ring structure. A specific example of such a structure can be expressed as follows.

In the present invention, when the structure is as described above, the polymerization activity is relatively high, and the molecular weight of the obtained polymer tends to increase easily.
Examples of the halogen-containing group include halogenated hydrocarbon groups having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, such as trifluoromethyl, pentafluorophenyl, and chlorophenyl.

Examples of the silicon-containing group include a silyl group, a siloxy group, a hydrocarbon-substituted silyl group, and a hydrocarbon-substituted siloxy group. Among these, specific hydrocarbon-substituted silyl groups include methylsilyl, dimethylsilyl, trimethylsilyl, ethylsilyl, diethylsilyl, triethylsilyl, diphenylmethylsilyl, triphenylsilyl, dimethylphenylsilyl, dimethyl-t-butylsilyl, dimethyl(pentafluoro phenyl)silyl, etc. Among these, methylsilyl, dimethylsilyl, trimethylsilyl, ethylsilyl, diethylsilyl, triethylsilyl, dimethylphenylsilyl, triphenylsilyl and the like are preferred. Particularly preferred are trimethylsilyl, triethylsilyl, triphenylsilyl, and dimethylphenylsilyl. Specific examples of the hydrocarbon-substituted siloxy group include trimethylsiloxy and the like.

Examples of the oxygen-containing group include an alkoxy 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, a carboxylic acid anhydride group, and a furyl group.

Among oxygen-containing groups, preferred examples of alkoxy groups include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, and tert-butoxy, and preferred examples of aryloxy groups include phenoxy, 2 ,6-dimethylphenoxy, and 2,4,6-trimethylphenoxy,
Preferred examples of ester groups include acetyloxy, benzoyloxy, methoxycarbonyl, phenoxycarbonyl, and p-chlorophenoxycarbonyl,
Preferred examples of the acyl group include formyl group, acetyl group, benzoyl group, p-chlorobenzoyl group, and p-methoxybenzoyl 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 thiocyanate group, an isothiocyanate group, a sulfone ester group, a sulfonamide group, Examples include thiocarboxyl group, dithiocarboxyl group, sulfo group, sulfonyl group, sulfinyl group, and sulfenyl group.

Among sulfur-containing groups, preferred examples of thioester groups include acetylthio, benzoylthio, methylthiocarbonyl, phenylthiocarbonyl,
Preferred examples of alkylthio groups include methylthio and ethylthio,
Preferred examples of the arylthio group include phenylthio, methylphenylthio, naphthylthio,
Preferred examples of the sulfone ester group include methyl sulfonate, ethyl sulfonate, phenyl sulfonate,
Preferred examples of the sulfonamide group include phenylsulfonamide, N-methylsulfonamide, and N-methyl-p-toluenesulfonamide.

Examples of the nitrogen-containing group include an amino group, an imino group, an amide group, an imido group, a pyrrolidino 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, Examples include ammonium salts of diazo groups and amino groups.

Among nitrogen-containing groups, preferred examples of amino groups include dimethylamino, ethylmethylamino, and diphenylamino,
Preferred examples of imino groups include methylimino, ethylimino, propylimino, butylimino, and phenylimino,
Preferred examples of amide groups include acetamide, N-methylacetamide, and N-methylbenzamide,
Preferred examples of imide groups include acetimide and benzimide.
Examples of the phosphorus-containing groups include phosphide, phosphoryl, thiophosphoryl, and phosphato groups.

(R ^{`</sup> , R <sup>1`} ~ R ^{4`</sup> )
One or more of R <sup>`} , R ^{1`</sup> to R <sup>4`} is particularly methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, neopentyl, n-hexyl, etc. a linear or branched alkyl group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms;
Aryl groups having 6 to 20 carbon atoms, preferably 6 to 10 carbon atoms, such as phenyl, naphthyl, biphenyl, terphenyl, phenanthryl, anthracenyl;
These aryl groups may be hydrocarbon groups having 1 to 20 carbon atoms, such as substituted aryl groups in which one or more hydrogen atoms are substituted with a halogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, etc. preferable.

It is also preferred that one or more of R ^1' to R ^4' be a hydrogen atom. In the present invention, the hydrogen atom refers to hydrogen as a substituent represented by H-.
Among the above embodiments, it is preferable that R ^1′ is a hydrocarbon group having 1 to 20 carbon atoms, and R ^2′ to R ^4′ are hydrogen atoms. The above R ^1' is preferably selected from a secondary hydrocarbon group and a tertiary hydrocarbon group, and a tertiary hydrocarbon group is particularly preferable.

(R ^{6`</sup> ~ R <sup>7`} )
In formula [A], R ^6' and R ^7' are characterized in that they are bonded to each other to form a cyclic structure. This cyclic structure is preferably a structure forming a so-called 3- to 10-membered ring containing R ^6' and R ^7' . The structure is more preferably a 4- to 8-membered ring, and even more preferably a 5- to 7-membered ring.
As such a structure, a structure such as the following formula [A ^'' ] can be exemplified.

In the formula [A ^'' ], the bonding form between the carbon atoms forming the skeleton of the cyclic structure formed by the bonding of R ^{6`</sup> and R <sup>7`} may be a single bond or a multiple bond. good. The number of R ¹¹ 's bonded to one carbon atom constituting the skeleton of the cyclic structure is 0, 1 or 2, depending on the type of bond. The above R ^{11`</sup> is the same defined substituent as the above R <sup>1`} to R ^10` , and m is preferably an integer of 1 to 8.

In addition to hydrogen atoms, the above cyclic structures include halogen atoms, hydrocarbon groups, halogen-containing groups, silicon-containing groups, oxygen-containing groups, sulfur-containing groups, nitrogen-containing groups, phosphorus-containing groups, boron-containing groups, and aluminum-containing groups. , or a structure containing a substituent such as a diene-based divalent derivative group. Specific structures of such substituents include structures similar to the above-mentioned examples of R ^{`</sup> , R <sup>1`} to R ^10` .

《n》
In formula [A], n is an integer of 1 to 4, and is selected depending on the valence of M and the type of X so that the transition metal compound (A) as a whole is electrically neutral.

《Q》
In formula [A], Q is each independently a hydrogen atom, a halogen atom, a hydrocarbon group, a halogen-containing group, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a phosphorus-containing group, a boron-containing group, aluminum containing group, or a diene-based divalent derivative group.

Among these, halogen atoms and hydrocarbon groups are preferred, and hydrocarbon groups are more preferred. Among the hydrocarbon groups, alkyl groups are preferred. Preferred examples of the alkyl group include a methyl group, an ethyl group, a propyl group, and a butyl group, more preferably a methyl group and an ethyl group, and particularly a methyl group.

Specific embodiments of these halogen atoms, hydrocarbon groups, halogen-containing groups, silicon-containing groups, oxygen-containing groups, sulfur-containing groups, nitrogen-containing groups, and phosphorus-containing groups are as described above as R ^{1`</sup> to R <sup>10`} . This is the same as the specific embodiments of the halogen atom, hydrocarbon group, halogen-containing group, silicon-containing group, oxygen-containing group, sulfur-containing group, nitrogen-containing group, and phosphorus-containing group.

Examples of the boron-containing group include boranediyl group, boranetriyl group, diboranyl group, and groups such as alkyl group-substituted boron, aryl group-substituted boron, boron halide, and alkyl group-substituted boron halide.

Examples of alkyl-substituted boron are (Et) ₂ B-, (iPr) ₂ B-, (iBu) ₂ B-, (Et) ₃ B, (iPr) ₃ B, or (iBu) ₃ B. The groups that are
Examples of aryl-substituted boron include (C ₆ H ₅ ) ₂ B-, (C ₆ H ₅ ) ₃ B, (C ₆ F ₅ ) ₃ B, or (3,5-(CF ₃ ) ₂ C ₆ Examples include a group represented by H ₃ ) ₃ B,
Examples of boron halides include groups represented by BCl ₂ - or BCl ₃ ,
Examples of alkyl group-substituted boron halides include groups represented by (Et)BCl-, (iBu)BCl-, and (C ₆ H ₅ ) ₂ BCl. Among these, trisubstituted boron may be in a coordinate bonded state. Here, Et represents an ethyl group, iPr represents an isopropyl group, and iBu represents an isobutyl group.

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

Examples of alkyl-substituted aluminum include (Et) ₂ Al-, (iPr) ₂ Al-, (iBu) ₂ Al-, (Et) ₃ Al, (iPr) ₃ Al, or (iBu) ₃ Al. The groups that are
Examples of aryl group-substituted aluminum include a group represented by (C ₆ H ₅ ) ₂ Al-,
Examples of aluminum halides include groups represented by AlCl ₂ - or AlCl ₃ ,
Examples of alkyl group-substituted aluminum halides include groups represented by (Et)AlCl- and (iBu)AlCl-. Among these, trisubstituted aluminum may be in a coordinate bonded state. Here, Et represents an ethyl group, iPr represents an isopropyl group, and iBu represents an isobutyl group.

Examples of the diene-based divalent derivative group include a 1,3-butadienyl group, an isoprenyl (2-methyl-1,3-butadienyl) group, a piperylenyl (1,3-pentadienyl) group, a 2,4-hexadienyl group, Examples include metallocyclopentene groups such as 1,4-diphenyl-1,3-pentadienyl group and cyclopentadienyl group.

Further, Q has a structure in which the groups listed as specific examples of Q are bonded to each other, and may form a ring together with M. For example, Q is an alkylene group having a structure in which two alkyl groups are bonded, and this alkylene group may form a ring with M.

《Y》
In formula (A), Y is carbon or silicon, preferably carbon.
Specific examples of the transition metal compound (A) include compounds represented by the following formula.

Two or more types of these transition metal compounds can be used in combination.
In the presence of the transition metal compound (A), especially when copolymerizing ethylene, a cyclic olefin with an alicyclic structure, and a cyclic olefin containing an aromatic structure, a copolymer with a high molecular weight can be produced with relatively high activity. It can be manufactured with. This means that, as shown in Examples and Comparative Examples to be described later, effects similar to the present invention cannot be obtained with zirconium complexes having a complex structure similar to that of the present invention, and coordination outside the scope of the present invention This is an unexpected feature since hafnium complexes and zirconium complexes that have molecules give polymers with similar molecular weights. Although the reason for such an effect is not clear at present, the present inventors speculate as follows.

The transition metal complex of the present invention has a special structure in which R ^6' and R ^7' are bonded to each other to form a cyclic structure. This cyclic structure tends to increase electron donating properties, which probably increases the activity as a transition metal complex. In addition, the introduction of substituents such as R ^6' and R ^7' may impede the approach of the cyclic olefin to the metal M, but the rotation of the cyclic structure is less than that of a single substituent. It is presumed that the influence of the above-mentioned disturbance can be relatively small because of the suppression. Since M is hafnium, which is an atom larger than zirconium, the cyclic olefins in the controlled manner can easily approach hafnium, which is the active site of the polymerization reaction, and relatively reduce the effect of chain transfer agents such as hydrogen. It is also possible that they are.

The present inventors speculate that one or more of the above-mentioned effects may contribute to the transition metal complex of the present invention exhibiting unique performance in copolymerization reactions involving cyclic olefins. .
Such an effect is caused by a structure in which R ^5' to R ^8' bonded to adjacent carbons are directly bonded to each other to form a multiple bond, that is, an aromatic ring structure such as formula (A'). It can also be considered that the case of structure is more preferable. If it contains such an aromatic structure, in addition to the above-mentioned steric effect, it has the effect of increasing the interaction with the cyclic olefin containing the aromatic structure due to the electronic effect and activating hafnium, which is an active site. It is thought that it may be effective.

The transition metal compound (A) of the present invention is represented by the following general formula [A].

The above R', R ^{1`</sup> to R <sup>10`} , M, Q, Y and n all represent the transition metal compound (A) in the general formula [A], R', R ^{1`</sup> to R <sup>10`} , M, It is synonymous with Q, Y and n.
The above-mentioned compounds are novel compounds, and when these compounds are used as catalysts for olefin polymerization, there is a tendency to easily obtain polymers with high activity and high molecular weight as described above.

[Production method of transition metal compound]
The transition metal compound (A) of the present invention can be produced by combining known methods. Specifically, a well-known method may be mentioned in which an anion obtained by reacting a corresponding ligand compound precursor with an organic alkali metal compound such as alkyl lithium is reacted with a corresponding hafnium halide compound.

[Catalyst for olefin polymerization]
The olefin polymerization catalyst of the present invention is
(A) the above-mentioned transition metal compound according to the present invention;
(B) (B-1) organometallic compound,
(B-2) an organoaluminumoxy compound; and (B-3) at least one compound selected from the group consisting of a compound that reacts with the transition metal compound (A) to form an ion pair. There is.

The olefin polymerization catalyst of the present invention may further contain (C) a carrier and may further contain (D) an organic compound, if necessary.

<Compound (B)>
《Organometallic compound (B-1》)
Examples of the organometallic compound (B-1) (hereinafter also referred to as "component (B-1)") include organoaluminum compounds (B-1a) represented by the general formula (B-1a), A complex alkylated compound of Group 1 metal and aluminum represented by B-1b) (B-1b), a dialkyl compound of Group 2 or Group 12 metal represented by general formula (B-1c) (B-1b) Examples include organometallic compounds of Groups 1 and 2 and Groups 12 and 13, such as 1c).

(B-1a): R ^a _m Al (OR ^b ) _n H _p X _q
In formula (B-1a), R ^a and R ^b are each independently a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, X is a halogen atom, m is 0<m≦3, n is a number satisfying 0≦n<3, p is a number satisfying 0≦p<3, q is a number satisfying 0≦q<3, and m+n+p+q=3. Examples of the organic aluminum compound (B-1a) include trialkylaluminum such as trimethylaluminum, triethylaluminum, and triisobutylaluminum, dialkylaluminum hydride such as diisobutylaluminum hydride, and tricycloalkylaluminum.

(B-1b): M ² AlR ^a ₄
In formula (B-1b), M ² is Li, Na or K, and R ^a is a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms. Examples of the complex alkylated product (B-1b) include LiAl(C ₂ H ₅ ) ₄ and LiAl(C ₇ H ₁₅ ) ₄ .

(B-1c): R ^a R ^b M ³
In formula (B-1c), R ^a and R ^b are each independently a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, and M ³ is Mg, Zn or Cd. Examples of the compound (B-1c) include dimethylmagnesium, diethylmagnesium, di-n-butylmagnesium, ethyl-n-butylmagnesium, diphenylmagnesium, dimethylzinc, diethylzinc, di-n-butylzinc, and diphenylzinc.

Among the organometallic compounds (B-1), organoaluminum compounds (B-1a) are preferred.
The organometallic compound (B-1) may be used alone or in combination of two or more.

《Organoaluminumoxy compound (B-2)》
As the organoaluminumoxy compound (B-2) (hereinafter also referred to as "component (B-2)"), conventionally known aluminoxane can be used as is. Specifically, the following general formula [B2-1]:

and/or the following general formula [B2-2]:

(In the formula, R is a hydrocarbon group having 1 to 10 carbon atoms, and n is an integer of 2 or more.)
Compounds represented by: benzene-insoluble organic aluminum oxy compounds described in JP-A-2-78687 and JP-A-2-167305; two or more types of alkyl groups described in JP-A-3-103407 Examples include aluminoxane having the following.

Further, examples of the organoaluminumoxy compound (B-2) include modified methylaluminoxane as represented by the following general formula [B2-3].

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

This modified methylaluminoxane is prepared using trimethylaluminum and an alkyl aluminum other than trimethylaluminum. Such compounds are commonly called MMAO. Such MMAO can be prepared by the methods listed in US Pat. No. 4,960,878 and US Pat. No. 5,041,584.

Furthermore, examples of the organoaluminumoxy compound (B-2) include boron-containing organoaluminumoxy compounds represented by the following general formula [B2-4].

(In the formula, R ^c represents a hydrocarbon group having 1 to 10 carbon atoms. R ^d may be the same 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 organoaluminumoxy compound (B-2), methylaluminoxane, which is easily available as a commercial product, and MMAO prepared using trimethylaluminum and triisobutylaluminum are preferred. Among these, MMAO, which has improved solubility in various solvents and storage stability, is particularly preferred.

<<Compound (B-3) that reacts with transition metal complex (A) to form an ion pair>>
The compound (B-3) that reacts with the transition metal complex (A) to form an ion pair (hereinafter also referred to as "ionic compound (B-3)" or "component (B-3)") is a compound that reacts with the transition metal complex (A) to form an ion pair. Table 1-501950, Special Table 1-502036, JP 3-179005, JP 3-179006, JP 3-207703, JP 3-207704, U.S. Examples include Lewis acids, ionic compounds, borane compounds, and carborane compounds described in Patent No. 5321106 and the like. Furthermore, mention may also be made of heteropoly compounds and isopoly compounds. However, the above-mentioned (B-2) organoaluminumoxy compound is not included.

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

In the formula, R ^{e +} includes H ⁺ , a carbenium cation, an oxonium cation, an ammonium cation, a phosphonium cation, a cycloheptyltrienyl cation, a ferrocenium cation having a transition metal, and the like. R ^f to R ⁱ may be the same or different and are substituents selected from a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, a nitrogen-containing group, an oxygen-containing group, a halogen atom, and a halogen-containing group. It is preferably a substituted aryl group.

Examples of the boron compound represented by the general formula [B3-1] include those described in [0133] to [0144] of International Publication No. 2015/122414.
The ionic compound (B-3) may be used alone or in combination of two or more.

(Carrier (C))
The carrier (C) is an inorganic or organic compound in the form of granules or particulate solids, and is conventionally used in olefin polymerization using a transition metal complex and a carrier as a catalyst component, such as those used in JP-A Those described in [0110] to [0122] of Publication No. 2011-122146 can be used.

(Organic compound component (D))
As a component of the olefin polymerization catalyst, an organic compound component (D) may be used as necessary. The organic compound component (D) is used for the purpose of improving polymerization performance and physical properties of the produced polymer. Examples of the organic compound component (D) include alcohols, phenolic compounds, carboxylic acids, phosphorus compounds, amides, polyethers, and sulfonate salts.

[Method for producing olefin copolymer]
The method for producing an olefin copolymer of the present invention involves using ethylene, an alicyclic cyclic olefin, and a cyclic olefin containing an aromatic structure (these are collectively referred to as " It is characterized by copolymerizing olefins (also referred to as olefins).

In the polymerization, the method of using each component constituting the olefin polymerization catalyst of the present invention and the order of addition to the polymerization vessel can be arbitrarily selected, but the following methods are exemplified. Hereinafter, the transition metal complex (A), the compound (B), the carrier (C), and the organic compound component (D) are also referred to as "components (A) to (D)", respectively.
(1) A method in which component (A) is added alone to a polymerization vessel.
(2) A method in which component (A) and component (B) are added to a polymerization vessel in any order.
(3) A method in which a catalyst component in which component (A) is supported on component (C) and component (B) are added to a polymerization vessel in any order.
(4) A method in which a catalyst component in which component (B) is supported on component (C) and component (A) are added to a polymerization vessel in any order.
(5) A method in which a catalyst component in which component (A) and component (B) are supported on component (C) is added to a polymerization vessel.

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

Olefin polymerization can be carried out by any of liquid phase polymerization methods such as solution polymerization and suspension polymerization, or gas phase polymerization methods. Examples of the inert hydrocarbon medium used in the liquid phase polymerization method include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; cyclopentane, cyclohexane, methylcyclopentane, etc. alicyclic hydrocarbons; aromatic hydrocarbons such as benzene, toluene, and xylene; and halogenated hydrocarbons such as ethylene chloride, chlorobenzene, and dichloromethane. The inert hydrocarbon medium may be used alone or in combination of two or more. When producing a cyclic olefin copolymer, it is preferable that the inert hydrocarbon medium contains an alicyclic hydrocarbon. Specific preferred examples include cyclohexane and methylcyclopentane.

When polymerizing olefins using the above catalyst for olefin polymerization, the transition metal compound (A) is usually 1×10 ⁻¹² to 1×10 −2 mol, preferably 1×10 ⁻² mol per 1 liter of reaction volume. It is used in an amount of ×10 ⁻¹⁰ to 1×10 ⁻³ mol.

The organometallic compound (B-1) usually has a molar ratio [(B-1)/M] of the organometallic compound (B-1) and all the transition metal atoms (M) in the transition metal compound (A). It is used in an amount of 0.01 to 50,000, preferably 0.05 to 10,000.

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

The ionized ionic compound (B-3) has a molar ratio [(B-3)/M] of the ionized ionic compound (B-3) and the transition metal atom (M) in the transition metal compound (A). , usually in an amount of 1 to 10,000, preferably 1 to 5,000.

When using the carrier (C), the weight ratio [(A)/(C)] of the transition metal compound (A) and the carrier (C) is preferably 0.0001 to 1, more preferably 0.0005 to 0. .5, more preferably 0.001 to 0.1.

In the production method of the present invention, the polymerization temperature 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. It's pressure. The polymerization reaction can be carried out in any of the batch, semi-continuous and continuous methods. Furthermore, the polymerization can be carried out in two or more stages with different reaction conditions.

The molecular weight of the resulting olefin polymer can be adjusted by allowing hydrogen to be present in the polymerization system, by changing the polymerization temperature, or by changing the amount of compound (B) used. When hydrogen is added, the appropriate amount is about 0.001 to 5,000 NL per 1 kg of olefin polymer to be produced.

The olefin subjected to the polymerization reaction in the method for producing an olefin polymer of the present invention is ethylene, and a linear or branched α-olefin having 3 or more carbon atoms can also be used in combination. In addition, the following cyclic olefins are also essential components. That is, they are an alicyclic cyclic olefin (Z-2) and a cyclic olefin containing an aromatic structure (Z-3).

(Z-1) Ethylene and any linear or branched α-olefin having 3 or more carbon atoms In the method for producing an olefin polymer of the present invention, ethylene is subjected to a polymerization reaction.
Further, a linear or branched α-olefin having 3 or more carbon atoms may optionally be subjected to the polymerization reaction. The α-olefin preferably has 3 to 30 carbon atoms, more preferably 2 to 30 carbon atoms.

Specific examples of α-olefins include propylene, 1-butene, 2-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, Included are 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene.

Hereinafter, ethylene and any linear or branched α-olefin having 3 or more carbon atoms will also be collectively referred to as “α-olefin (Z-1)”.

(Z-2) Alicyclic cyclic olefin The alicyclic cyclic olefin (Z-2) (hereinafter also simply referred to as "cyclic olefin (Z-2)") is represented by the following general formula [Z-2]. The compounds represented are preferred. By using such a compound, a polymer with a high refractive index tends to be easily obtained.

(In the above formula [Z-2], n is 0 or 1, m is 0 or a positive integer, q is 0 or 1, and R ¹ to R ¹⁸ and R ^a and R ^b are each independently a hydrogen atom, a halogen atom, or a hydrocarbon group optionally substituted with a halogen atom; R ¹⁵ to R ¹⁸ may be bonded to each other to form a monocyclic or polycyclic ring; The monocyclic or polycyclic ring may have a double bond, and R ¹⁵ and R ¹⁶ or R ¹⁷ and R ¹⁸ may form an alkylidene group.However, the monocyclic ring and Polycycles do not include aromatic rings.)

Among these, the olefin copolymer produced by the production method of the present invention has structural units derived from bicyclo[2.2.1]-2-heptene, tetracyclo[6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene-derived structural units and hexacyclo[6,6,1,1 ^3,6 , 1 ^10,13 , 0 ^2,7 , 0 ^9,14 ] heptadeca-4-ene-derived structural units. It preferably contains at least one kind of structural unit selected from the group consisting of bicyclo[2.2.1]-2-heptene-derived structural units and tetracyclo[6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene-derived structural unit, and more preferably contains at least one structural unit selected from structural units derived from tetracyclo[6.2.1.1 ^3,6 . 0 ^2,7 ] It is particularly preferable to include a structural unit derived from dodec-4-ene.

(Z-3) Cyclic olefin containing an aromatic structure The cyclic olefin containing an aromatic structure (Z-3) (hereinafter also simply referred to as "cyclic olefin (Z-3)") is, for example, the following formula (Z- Examples include a compound represented by the following formula (Z-31), a compound represented by the following formula (Z-32), and a compound represented by the following formula (Z-33). These cyclic olefins having an aromatic structure may be used alone or in combination of two or more.

In the above formula (Z-31), n and q are each independently 0, 1 or 2. Preferably, n is 0 or 1, and more preferably 0. q is preferably 0 or 1, more preferably 0.

R ¹ to R ¹⁷ are each independently a hydrogen atom, a halogen atom excluding a fluorine atom, or a hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a halogen atom excluding a fluorine atom, and R ¹⁰ to One of R ¹⁷ is a bond, and preferably R ¹⁵ is a bond.

R ¹ to R ¹⁷ are preferably each independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and more preferably a hydrogen atom.
Furthermore, when q=0, R ¹⁰ and R ¹¹ , R ¹¹ and R ¹² , R ¹² and R ¹³ , R ¹³ and R ¹⁴ , R ¹⁴ and R ¹⁵ , and R ¹⁵ and R ¹⁰ each independently bond to each other. may form a monocyclic or polycyclic ring, and when q=1 or 2, R ¹⁰ and R ¹¹ , R ¹¹ and R ¹⁷ , R ¹⁷ and R ¹⁷ , R ¹⁷ and R ^{12 , R 12 and} R ¹³ , R ¹³ and R ¹⁴ , R ¹⁴ and R ¹⁵ , R ¹⁵ and R ¹⁶ , R ¹⁶ and R ¹⁶ , R ¹⁶ and R ¹⁰ each independently combine with each other to form a monocyclic or polycyclic ring. Alternatively, the monocyclic ring or the polycyclic ring may have a double bond, and the monocyclic ring or the polycyclic ring may be an aromatic ring.

Among the above formulas (Z-31), compounds represented by formula (Z-31') described below are preferred.

In the above formula (Z-32), n and m are each independently 0, 1 or 2, and q is 1, 2 or 3. m is preferably 0 or 1, more preferably 1. Preferably, n is 0 or 1, and more preferably 0. q is preferably 1 or 2, more preferably 1.

R ¹⁸ to R ³¹ are each independently a hydrogen atom, a halogen atom excluding a fluorine atom, or a hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a halogen atom excluding a fluorine atom.

R ¹⁸ to R ³¹ are preferably each independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and more preferably a hydrogen atom.
Furthermore, when q=1, R ²⁸ and R ²⁹ , R ²⁹ and R ³⁰ , and R ³⁰ and R ³¹ may each independently bond to each other to form a monocyclic or polycyclic ring, and when q=2 or 3, R ²⁸ and R ²⁸ , R ²⁸ and R ²⁹ , R ²⁹ and R ³⁰ , R ³⁰ and R ³¹ , R ³¹ and R ³¹ each independently combine with each other to form a monocyclic or polycyclic ring. The monocyclic ring or the polycyclic ring may have a double bond, or the monocyclic ring or the polycyclic ring may be an aromatic ring.

In the above formula (Z-33), q is 1, 2 or 3, preferably 1 or 2, and more preferably 1.
R ³² to R ³⁹ are each independently a hydrogen atom, a halogen atom excluding a fluorine atom, or a hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a halogen atom excluding a fluorine atom.

R ³² to R ³⁹ are each preferably independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and more preferably a hydrogen atom.
Furthermore, when q=1, R ^{36 and} R 37 , R ³⁷ and R ³⁸ , and R ³⁸ and R ³⁹ may each independently bond to each other to form a monocyclic or polycyclic ring, and when q=2 or 3, R ³⁶ and R ³⁶ , R ³⁶ and R ³⁷ , R ³⁷ and R ³⁸ , R ³⁸ and R ³⁹ , R ³⁹ and R ³⁹ each independently combine with each other to form a monocyclic or polycyclic ring. The monocyclic ring or the polycyclic ring may have a double bond, or the monocyclic ring or the polycyclic ring may be an aromatic ring.

Examples of the hydrocarbon group having 1 to 20 carbon atoms include, for example, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, and an aromatic hydrocarbon group. It will be done. More specifically, examples of the alkyl group include methyl group, ethyl group, propyl group, isopropyl group, amyl group, hexyl group, octyl group, decyl group, dodecyl group, and octadecyl group, and examples of the cycloalkyl group include cyclohexyl group. Examples of the aromatic hydrocarbon group include aryl or aralkyl groups such as phenyl, tolyl, naphthyl, benzyl, and phenylethyl groups. These hydrocarbon groups may be substituted with halogen atoms other than fluorine atoms.

Among these, the cyclic olefin (Z-3) having an aromatic structure is preferably one having one aromatic ring, for example, at least one selected from benzonorbornadiene, indenorbornene, and methylphenylnorbornene. preferable.

Further, as the cyclic olefin (Z-3) having an aromatic structure, for example, a compound represented by the following formula (Z-31'), a compound represented by the following formula (Z-32'), a compound represented by the following formula (Z- Also included are compounds represented by 33'). These cyclic olefins (Z-3) having an aromatic structure may be used alone or in combination of two or more.

In the above formula (Z-31'), formula (Z-32') and formula (Z-33'), m and n are 0, 1 or 2, and R ¹ to R ³⁶ are each independently a hydrogen atom. , a hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a halogen atom excluding a fluorine atom, or a halogen atom excluding a fluorine atom, and R ¹⁰ and R ¹¹ , R ¹¹ and R ¹² , R ¹² and R ¹³ , R ¹³ and R ¹⁴ , R ²⁵ and R ²⁶ , R ²⁶ and R ²⁷ , R ²⁷ and R ²⁸ , R ³³ and R ³⁴ , R ³⁴ and R ³⁵ , R ³⁵ and R ³⁶ are each independently, They may be bonded to each other to form a single ring, and the single ring may have a double bond.

Furthermore, in the above formula (Z-31'), formula (Z-32') and formula (Z-33'), m is preferably 0 or 1, more preferably 1. Preferably, n is 0 or 1, and more preferably 0. R ¹ to R ³⁶ are preferably a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and more preferably a hydrogen atom.

Examples of the hydrocarbon group having 1 to 20 carbon atoms include, for example, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, and an aromatic hydrocarbon group. It will be done. More specifically, examples of the alkyl group include methyl group, ethyl group, propyl group, isopropyl group, amyl group, hexyl group, octyl group, decyl group, dodecyl group, and octadecyl group, and examples of the cycloalkyl group include cyclohexyl group. Examples of the aromatic hydrocarbon group include aryl or aralkyl groups such as phenyl, tolyl, naphthyl, benzyl, and phenylethyl groups. These hydrocarbon groups may be substituted with halogen atoms other than fluorine atoms.

Among these, the cyclic olefin (Z-3) having an aromatic structure is preferably one having one aromatic ring, for example, at least one selected from benzonorbornadiene, indenorbornene, and methylphenylnorbornene. preferable.

The cyclic olefin (Z-3) having an aromatic structure as described above can be used as a material for lenses by the method of the present invention, for example, since the Abbe number of the olefin copolymer obtained by the method of the present invention can be adjusted. This is suitable for controlling physical properties when obtaining an olefin copolymer with good physical properties.

Examples of the olefin to be subjected to the polymerization reaction in the method for producing an olefin polymer of the present invention further include conjugated/non-conjugated polyenes and vinylcyclohexane.

Examples of the conjugated/non-conjugated polyene include cyclic or chain hydrocarbons having 4 to 30 carbon atoms, preferably 4 to 20 carbon atoms, and having two or more double bonds. Specific examples include butadiene, isoprene, 4-methyl-1,3-pentadiene, 1,3-pentadiene, 1,4-pentadiene, 1,5-hexadiene, 1,4-hexadiene, 1,3-hexadiene, 1,3-octadiene, 1,4-octadiene, 1,5-octadiene, 1,6-octadiene, 1,7-octadiene, ethylidenenorbornene, vinylnorbornene, dicyclopentadiene, 7-methyl-1,6-octadiene, 4-ethylidene-8-methyl-1,7-nonadiene, 5,9-dimethyl-1,4,8-decatriene-butadiene, isoprene, ethylidenenorbornene, vinylnorbornene, dicyclopentadiene, etc. in JP-A-2011-122146 Examples include the compounds exemplified in [0211] of [0211].

In the method for producing an olefin polymer of the present invention, polymerizable compounds other than olefins may be polymerized together with the above-mentioned olefins. Examples of such polymerizable compounds include polar groups and polymerizable unsaturated bonds. Examples include compounds having the same compound, aromatic vinyl compounds, and functional group-containing styrene derivatives.

Specific examples of compounds having a polar group and a polymerizable unsaturated bond include compounds exemplified as unsaturated hydrocarbons having a polar group in [0208] to [0211] of JP-A No. 2011-122146.

Specific examples of aromatic vinyl compounds and functional group-containing styrene derivatives include compounds exemplified in [0211] of JP-A No. 2011-122146.
A preferred embodiment of the production method of the present invention includes ethylene and tetracyclo[6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene and benzonorbornadiene, indenorbornene, or methylphenylnorbornene (preferably benzonorbornadiene) as the cyclic olefin (Z-3) are copolymerized.

In the production method of the present invention, the pressure of α-olefin (Z-1) and the concentration of cyclic olefins (Z-2) and (Z-3) can be set arbitrarily, and are not particularly limited. . The pressure of the α-olefin (Z-1) is preferably the above polymerization pressure.

For example, in the case of liquid phase polymerization using the inert solvent, the cyclic olefin (Z-2) is preferably 0.0001 to 100 mol/liter, more preferably 0.001 to 10 mol/liter, and It is preferably used at a concentration of 0.01 to 1 mol/liter. Further, the concentration of the cyclic olefin (Z-3) is preferably 0.0001 to 1000 mol/liter, more preferably 0.001 to 100 mol/liter, and still more preferably 0.01 to 10 mol/liter. Used in conditions.

The molar ratio of (Z-2)/(Z-3) used can also be set arbitrarily, but is preferably 0.01 to 10. A more preferable lower limit is 0.02, further preferably 0.05, particularly preferably 0.1. On the other hand, a more preferable upper limit is 5, still more preferably 2, and particularly preferably 1.

As mentioned above, the olefin polymer obtained by the method for producing an olefin polymer of the present invention can be made into a resin with adjusted refractive index, Abbe number, etc., and therefore can be used, for example, as a material for lenses. .

EXAMPLES Hereinafter, the present invention will be explained in more detail based on Examples, but the present invention is not limited thereto.
[Measuring method]
[Structure of transition metal compounds]
The structure of the transition metal compound was determined by ¹ H-NMR spectrum (270 MHz, JEOL GSH-270).

[Weight average molecular weight (Mw), molecular weight distribution (Mw/Mn) of polymer]
The weight average molecular weight (Mw) and number average molecular weight (Mn) of the olefin polymer were determined by gel permeation chromatography (GPC). It was calculated from the molecular weight distribution curve obtained by Waters'"Alliance GPC 2000" gel permeation chromatograph (high temperature size exclusion chromatograph), and the operating conditions were as follows:

<Equipment used and conditions>
Measuring device: Gel permeation chromatograph alliance GPC2000 type (Waters)
Analysis software; chromatography data system Empower (trademark, Waters Inc.)
Column; TSKgel GMH6-HT×2 + TSKgel GMH6-HT×2
(Inner diameter 7.5mm x length 30cm, Tosoh Corporation)
Mobile phase: o-dichlorobenzene [=ODCB] (Fujifilm Wako Pure Chemical Industries, Ltd. special grade reagent)
Detector: Differential refractometer (built-in device)
Column temperature: 140℃
Flow rate: 1.0mL/min
Injection volume: 400μL
Sampling time interval: 1 second Sample concentration: 0.15% (w/v)
Molecular weight calibration Monodisperse polystyrene (Tosoh Corporation) / molecular weight from 495 to 20.6 million

[Polymer comonomer (cyclic olefin) content]
According to the descriptions in [0216] to [0219] of JP-A-2011-122146, the comonomer (cyclic olefin) content of the polymer was determined by ¹³ C-NMR spectrum.

[Tg of polymer]
DSC measurement was performed under the following conditions to determine the glass transition temperature (Tg) of the polymer.
Equipment: SII Nanotechnology DSC6220
Measurement conditions: Tg was determined in the process of rapidly cooling a sample held at 300° C. for 5 minutes to 0° C. and then increasing the temperature to 250° C. at a heating rate of 20° C./min.

[Manufacture of ligands, hafnium, and zirconium compounds]
[Synthesis example 1]
1.99 g (12.7 mmol) of 1,2,3,5-tetrahydro-s-indacene and 100 mL of tert-butyl methyl ether were added to a 200 mL reactor that had been sufficiently dried and purged with nitrogen, and n-butyl lithium was added at 0°C. 9.0 mL of solution (n-hexane solution, 1.58 M, 14.3 mmol) was added, the temperature was returned to room temperature, and the mixture was stirred for 20 hours. Separately, 3.23 g (14.0 mmol) of 6,6-diphenylfulvene and 100 mL of tert-butyl methyl ether were added to a 500 mL reactor that had been thoroughly dried and purged with nitrogen, and then the reaction solution prepared above was added. The mixture was refluxed at 55°C for an hour. The temperature was returned to room temperature, an aqueous ammonium chloride solution was added, water was added, and the mixture was extracted with diethyl ether. The resulting solution was washed with an aqueous sodium hydrogen carbonate solution and saturated brine, dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure. The obtained powder was washed with hexane and dried to obtain 3.16 g of 5-(1,3-cyclopentadienyldiphenylmethyl)-1,2,3,5-tetrahydro-s-indacene as a pale yellow powder. (64%).
¹ H-NMR (270 MHz, CDCl ₃ ) δ 7.40-7.15 (9H, m, ArH), 6.96 (1H, s, ArH), 6.62-6.17 (5H, m, CpH+IndH ), 4.84/4.79 (1H, s, IndH), 3.06/2.90 (2H, s, CpH), 2.84-2.79 (2H, m, CH2), 2.74 -2.68 (2H, m, CH2), 2.05-1.97 (2H, m, CH2) ppm

[Example A1]
Thoroughly heat and dry, place 5-(1,3-cyclopentadienyldiphenylmethyl)-1,2,3,5-tetrahydro-s- synthesized in Synthesis Example 1 in a 100 mL flask under nitrogen atmosphere. 2.1 mL (1.58 M, 3.26 mmol) of n-butyllithium was added to 600.2 mg (1.55 mmol) of indacene, 229.5 mg (3.18 mmol) of tetrahydrofuran, and 50 mL of toluene at 0°C, and the mixture was kept at 45°C for 5 hours. It refluxed. After the temperature was returned to room temperature and the solvent was distilled off under reduced pressure, 614.1 mg ((1.13 mmol)) of the dilithio compound was washed with hexane as a yellow powder. Create a nitrogen atmosphere, add 525.7 mg (1.13 mmol) of tetrachlorobis(tetrahydrofuran) hafnium and 50 mL of dehydrated diethyl ether to a 100 mL flask, and add 2.1 mL of methyllithium solution (diethyl ether solution, 1.08 M, 2.26 mmol). ) was added at 0°C and stirred for 30 minutes. The isolated dilithio compound was added to this reaction solution at -78°C, and the mixture was stirred for 17 hours. After the temperature was returned to room temperature and the solvent was distilled off under reduced pressure, the mixture was extracted with toluene, and the solvent was distilled off and washed with hexane to obtain 605.4 mg (yield: 65%) of hafnium compound (1) as a reddish-orange powder.
¹ H-NMR (270 MHz, C ₆ D ₆ ) δ 7.82 (2H, d, J = 7.3 Hz, ArH), 7.75 (1H, d, J = 7.8 Hz, ArH), 7.59 (1H, d, J=7.8Hz, ArH), 7.31 (1H, s, IndH), 7.12-6.92 (6H, m, ArH), 6.60 (1H, d, J= 3.2Hz, IndH), 6.28-6.24 (1H, m, CpH), 6.20 (2H, br s, ArH + CpH), 5.76 (1H, d, J = 3.2Hz, IndH) , 5.51-5.48 (1H, m, CpH), 5.25-5.22 (1H, m, CpH), 2.88-2.67 (2H, m, CH2), 2.45- 2.36 (2H, m, CH2), 1.77-1.66 (2H, m, CH2), -0.13 (3H, s, CH3), -1.12 (3H, s, CH3) ppm
FD-MS: m/Z=594 (M+)

[Experiment example A2]
In a thoroughly heated and dried 100 mL flask under a nitrogen atmosphere, 350.0 mg (1.01 mmol) of 1-(cyclopentadienyldiphenylmethyl)-1H-indene synthesized in Synthesis Example 1 and 0.17 mL (2.0 mmol) of dehydrated tetrahydrofuran were added. 09 mmol) was dissolved in 50 mL of dehydrated toluene. 1.3 mL (1.59 M, 2.07 mmol) of n-butyllithium was added in an ice bath, and the mixture was heated in a 45° C. oil bath for 5 hours. After cooling, the concentrated residue of the reaction solution was washed with hexane to obtain 439.0 mg (0.83 mmol) of a yellow powder dilithio compound. Subsequently, 381 mg (1.01 mmol) of tetrachlorobis(tetrahydrofuran) hafnium was dissolved in 50 mL of dehydrated diethyl ether under a nitrogen atmosphere in a 100 mL flask. 1.53 mL (1.09 M, 2.02 mmol) of methyllithium was charged in an ice bath and stirred for 15 minutes. This reaction solution was cooled to −78° C. in an acetone-dry ice bath, and then the dehydrated tetrahydrofuran solution of the dilithio compound described above was added dropwise. The mixture was stirred for 17 hours while gradually raising the temperature to room temperature. The concentrated residue was extracted with toluene and filtered through Celite. The residue after concentrating the filtrate was washed with hexane to obtain 210 mg (yield 38%) of hafnium compound (2) as a pale orange powder.
^1H -NMR (270MHz, CDCl ₃ ) δ 7.76 (2H, d, J = 7.6Hz, ArH), 7.70 (1H, d, J = 7.8Hz, ArH), 7.46-7 .43 (3H, m, ArH), 7.09-6.86 (6H, m, ArH), 6.59 (1H, d, J = 3.6Hz, ArH), 6.45 (1H, dd, J=8.5, 6.8Hz, ArH), 6.29 (1H, d, J=8.5Hz, ArH) 6.22-6.19 (1H, m, CpH), 6.15-6. 12 (1H, m, CpH), 5.76 (1H, d, J = 3.6Hz, ArH), 5.38-5.35 (1H, m, CpH), 5.22-5.19 (1H , m, CpH), -0.18 (3H, s, HfMe), -1.22 (3H, s, HfMe) ppm
FD-MS: m/Z=554 (M+)

[Synthesis example A3]
Thoroughly heat and dry, place 5-(1,3-cyclopentadienyldiphenylmethyl)-1,2,3,5-tetrahydro-s- synthesized in Synthesis Example 1 in a 100 mL flask under nitrogen atmosphere. 1.0 mL (1.59 M, 1.63 mmol) of n-butyllithium was added to 300.1 mg (0.78 mmol) of indacene, 229.5 mg (1.63 mmol) of tetrahydrofuran, and 25 mL of toluene at 0°C, and the mixture was kept at 45°C for 5 hours. It refluxed. After the temperature was returned to room temperature and the solvent was distilled off under reduced pressure, 291.6 mg (0.54 mmol) of the dilithio compound was obtained as a yellow powder by washing with hexane. Create a nitrogen atmosphere, add 120.0 mg (0.54 mmol) of zirconium tetrachloride and 50 mL of dehydrated diethyl ether to a 100 mL flask, and add 1.0 mL of methyllithium solution (diethyl ether solution, 1.09 M, 1.07 mmol) at 0 °C. and stirred for 30 minutes. The isolated dilithio compound was added to this reaction solution at -78°C, and the mixture was stirred for 15 hours. After the temperature was returned to room temperature and the solvent was distilled off under reduced pressure, the mixture was extracted with toluene, and after distillation of the solvent, the mixture was washed with hexane to obtain 257.9 mg (yield: 65%) of zirconium compound (3) as a reddish-orange powder.
^1H -NMR (270MHz, CDCl ₃ ) δ 7.82 (2H, d, J = 7.2Hz, ArH), 7.75 (1H, d, J = 7.2Hz, ArH), 7.59 (1H , J=7.2Hz, ArH), 7.30 (1H, s, ArH), 7.11-6.92 (6H, m, ArH) 6.60 (1H, d, J=2.2Hz, IndH ), 6.27-6.24 (1H, m, CpH), 6.21-6.19 (1H, m, CpH), 6.20 (1H, s, ArH), 5.76 (1H, d , J=2.2Hz, IndH), 5.51-5.48 (1H, m, CpH), 5.25-5.22 (1H, m, CpH), 2.88-2.67 (2H, m, CH ₂ ), 2.50-2.30 (2H, m, CH ₂ ), 1.80-1.63 (2H, m, CH ₂ ), -0.13 (3H, s, CH ₃ ) ,-1.12(3H,s,CH ₃ )ppm

[Synthesis example A4]
Zirconium compound (4) was produced with reference to the literature (J. Chem. Soc., Dalton Trans.: Inorg. Chem. 1994, 5, 657.).

[Manufacture of olefin polymer]
[Example B1]
A dry pressure-resistant autoclave with an internal volume of 1.5 L was sufficiently purged with nitrogen, and 703 mL of a dehydrated and purified cyclohexane/hexane (3/1) mixed solution, 120 mmol of tetracyclododecene (TD), 209 mmol of benzonorbornadiene (BNBD), and triisobutyl were added. 10.0 mmol of aluminum was sequentially introduced under a nitrogen stream. Next, the temperature was raised to 50° C., and ethylene was supplied so that the ethylene partial pressure became 0.1 MPaG, and this state was maintained. Thereafter, 0.005 mmol of the hafnium compound (1) obtained in Example A1 was added, and then 0.02 mmol of triphenylcarbenium tetrakis(pentafluorophenyl)borate was added to initiate polymerization. While maintaining the internal temperature of 50° C., ethylene was supplied so that the ethylene partial pressure was maintained at 0.1 MPaG, and polymerization was carried out for 5 minutes. After a predetermined period of time had passed, the supply of ethylene was stopped and a small amount of methanol was added to stop the polymerization. The reactant was added to 3 liters of acetone/methanol (3/1) mixed solvent containing a small amount of hydrochloric acid to precipitate a polymer. After washing with the same solvent, it was dried under reduced pressure at 130° C. for 10 hours to obtain 0.45 g of ethylene/tetracyclododecene/benzonorbornadiene copolymer. The polymerization activity and physical property values of the ethylene/tetracyclododecene/benzonorbornadiene copolymer are as follows.
Polymerization activity: 90g-polymer/mmol-Hf
Glass transition temperature: 146℃
Intrinsic viscosity [η]: 0.69 dl/g
Weight average molecular weight (Mw): 150,000g/mol
Mw/Mn: 1.70
Structural unit molar ratio (ethylene:TD:BNBD) = 61.2:21.7:17.2

[Comparative example B1]
The same operation as in Example B1 was performed except that the hafnium compound (1) was changed to the hafnium compound (2) obtained in Synthesis Example A2, and 0.28 g of an ethylene/tetracyclododecene copolymer was obtained. The polymerization activity and physical property values of the ethylene/tetracyclododecene/benzonorbornadiene copolymer are as follows.
Polymerization activity: 60g-polymer/mmol-Hf
Glass transition temperature: 145℃
Intrinsic viscosity [η]: 0.48 dl/g
Weight average molecular weight (Mw): 86,700g/mol
Mw/Mn: 1.51
Structural unit molar ratio (ethylene:TD:BNBD) = 59.3:24.0:16.6

[Comparative example B2]
The same operation as in Example B1 was performed except that the hafnium compound (1) was changed to the zirconium compound (3) obtained in Synthesis Example A3, to obtain 3.19 g of an ethylene/tetracyclododecene copolymer. The polymerization activity and physical property values of the ethylene/tetracyclododecene/benzonorbornadiene copolymer are as follows.
Polymerization activity: 640g-polymer/mmol-Zr
Glass transition temperature: 156℃
Intrinsic viscosity [η]: 0.39 dl/g
Weight average molecular weight (Mw): 76,800g/mol
Mw/Mn: 1.80
Structural unit molar ratio (ethylene:TD:BNBD) = 58.7:21.0:20.4

[Comparative example B3]
The same procedure as in Example B1 was carried out except that the hafnium compound (1) was changed to the zirconium compound (4) obtained in Synthesis Example A4 and the polymerization time was changed to 10 minutes. 4.24 g of polymer was obtained. The polymerization activity and physical property values of the ethylene/tetracyclododecene/benzonorbornadiene copolymer are as follows.
Polymerization activity: 850g-polymer/mmol-Zr
Glass transition temperature: 156℃
Intrinsic viscosity [η]: 0.43 dl/g
Weight average molecular weight (Mw): 83,800g/mol
Mw/Mn: 1.80
Structural unit molar ratio (ethylene:TD:BNBD) = 56.6:23.5:19.9

From the above Examples and Comparative Examples, it can be seen that the olefin polymerization method of the present invention can more easily produce a cyclic olefin copolymer containing an aromatic structure with a high molecular weight than when using the corresponding zirconium compound. .

In compounds having a ligand structure outside the scope of the transition metal compounds of the present invention, there is no significant difference in the molecular weight of the resulting copolymers between hafnium compounds and zirconium compounds. Therefore, it can be said that the performance of the transition metal compound as described in the present application is an unexpectedly favorable effect.

Claims (4)

(A) a transition metal compound represented by the following general formula [A] and (B) (B-1) an organometallic compound,
(B-2) Presence of an olefin polymerization catalyst comprising an organoaluminumoxy compound, and (B-3) at least one compound selected from the group consisting of a compound that reacts with the transition metal compound to form an ion pair. A method for producing an olefin copolymer, which comprises copolymerizing ethylene, an alicyclic olefin, and a cyclic olefin containing an aromatic structure.
[In formula [A],
M is a hafnium atom,
n is an integer from 1 to 4,
Y is carbon or silicon; Q is each independently a hydrogen atom, a halogen atom, a hydrocarbon group, a halogen-containing group, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a phosphorus-containing group, a boron-containing group , an aluminum-containing group, or a diene-based divalent derivative group,
R', R ^{1`</sup> to R <sup>10`} each independently represent a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogen atom, a halogen-containing group, a silicon-containing group, an oxygen-containing group, a nitrogen-containing group, a sulfur-containing group , or a phosphorus-containing group,
The plurality of R ^5' to R ^10' include structures in which two or more of them are connected to form a cyclic structure or a multiple bond structure, and R ^6' and R ^7' are structures in which they are bonded to each other. ] The method for producing an olefin copolymer according to claim 1, wherein in the general formula [A], R ^1' is a hydrocarbon group having 1 to 20 carbon atoms, and R ^2' to R ^4' are hydrogen atoms. . A transition metal compound represented by the following general formula [A].
[In formula [A],
M is a hafnium atom,
n is an integer from 1 to 4,
Y is carbon or silicon; Q is each independently a hydrogen atom, a halogen atom, a hydrocarbon group, a halogen-containing group, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a phosphorus-containing group, a boron-containing group , an aluminum-containing group, or a diene-based divalent derivative group,
R', R ^{1`</sup> to R <sup>10`} each independently represent a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogen atom, a halogen-containing group, a silicon-containing group, an oxygen-containing group, a nitrogen-containing group, a sulfur-containing group , or a phosphorus-containing group,
The plurality of R ^5' to R ^10' include structures in which two or more of them are connected to form a cyclic structure or a multiple bond structure, and R ^6' and R ^7' are structures in which they are bonded to each other. ] 4. The transition metal compound according to claim 3, wherein in the general formula [A], R ^1' is a hydrocarbon group having 1 to 20 carbon atoms, and R ^2' to R ^4' are hydrogen atoms.