JP7004972B6 - Method for producing polar group-containing olefin copolymer - Google Patents

Description

The present invention relates to an olefin copolymer containing a polar group-containing monomer having a specific structure as a constituent component, and more specifically, an olefin copolymer containing an ethylene and/or α-olefin monomer and a polar group-containing monomer having a specific structure (a polar group-containing monomer having a specific structure). This invention relates to a novel polar group-containing olefin copolymer having a unique structure, which is obtained by copolymerizing a vinylidene comonomer with

Among resin materials, olefin polymers have excellent properties such as physical properties and moldability, and are also highly economical and environmentally friendly, making them extremely versatile and important industrial materials.
However, since olefin polymers do not have polar groups, it has been difficult to apply them to applications that require physical properties such as adhesion with other materials, printability, or compatibility with fillers. As an improved material, a copolymer of ethylene and a polar group-containing vinyl monomer produced by a high-pressure radical polymerization process has been used alone or as a composition with other resins (Patent Document 1 and Patent Document 1) Reference 2). However, due to the polymer's multi-branched structure, it has low elastic modulus and poor mechanical properties, and its range of applications is limited, not only when used alone but also when used as a composition with other resins. It became.

On the other hand, in conventional methods for producing olefin polymers using metallocene catalysts, when copolymerizing ethylene and polar group-containing monomers, it has been said that the catalyst polymerization activity decreases and copolymerization is difficult. A method has been reported in which an organoaluminum compound or an organozinc compound is reacted with a polar comonomer (masking of a polar functional group) and then copolymerized with an olefin (Patent Documents 3 and 4). However, this method has the problem that a large amount of metal salt is precipitated at the same time as the copolymer is produced, and it has not become popular due to the cost of the organoaluminum compound.
Incidentally, in recent years, efforts have been made to copolymerize olefins and polar comonomers using late transition metal complex catalysts, so-called post-metallocenes, without using masking agents such as organoaluminum compounds. It is being So far, while having the characteristic that a linear copolymer with few branches can be obtained as a copolymer structure, as a polar comonomer, acrylic acid ester (Patent Documents 5 to 10), acrylonitrile (Non-patent Document 1), and vinyl ether (Non-patent Document 1) have been used. Patent Document 2) and the like have been reported.

Patent No. 2792982 Japanese Patent Application Publication No. 3-229713 Japanese Patent Application Publication No. 2003-327627 Japanese Patent Application Publication No. 03-207707 Special Publication No. 2002-521534 Japanese Patent Application Publication No. 6-184214 JP2008-223011A Japanese Patent Application Publication No. 2010-150246 Japanese Patent Application Publication No. 2010-150532 Japanese Patent Application Publication No. 2010-202647

K. Nozaki et al. , J. Am. Chem. Soc. , 2007, 129, 8948-8949. R. Jordan et al. , J. Am. Chem. Soc. , 2007, 129, 8946-8947.

However, among polar comonomers, vinylidene compounds, which are 1,1-disubstituted olefins, are less polymerizable with late transition metal complex catalysts than vinyl compounds, which are monosubstituted olefins. It was difficult to polymerize.
In view of these circumstances, an object of the present invention is to provide a polar group-containing olefin copolymer using a novel linear vinylidene comonomer and a method for producing the same.

The present inventors have conducted various searches in the production of polar group-containing olefin copolymers with the aim of solving the above-described problems of the present invention.
As a result, they discovered that the above problems could be solved by using a polymerization catalyst with a specific structure and a specific vinylidene comonomer, and completed the invention. Based on these results, we provide the following invention.

Above, the history of the creation of the present invention and the basic configuration and characteristics of the invention have been generally described, so to summarize the overall configuration of the present invention, the present invention has the following [1] ] to [16].
Here, the polar group-containing olefin copolymer having a specific structure in [1] is constituted as the basic invention [1], and each of the following inventions in [2] adds incidental requirements to the basic invention, or This figure shows the mode of its implementation. The inventions [4] to [16] define additional requirements regarding the method for producing the polar group-containing olefin copolymer having a specific structure of the present invention. All invention units are collectively referred to as an invention group.

[1]
A structural unit derived from ethylene and/or an α-olefin having 3 to 10 carbon atoms;
A polar group-containing olefin containing 20 to 0.001 mol% of structural units derived from at least one type selected from the group consisting of polar group-containing monomers represented by the following general formulas (1), (2), and (3). It is a copolymer,
and,
A polar group-containing olefin copolymer, which is a linear random copolymer with a methyl branching degree calculated by ¹³ C-NMR analysis of 20 or less per 1,000 carbons of the copolymer.

[In formulas (1), (2) and (3), FG is a halogen atom, a hydroxyl group, an aryl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or a hydroxyl group having 1 to 20 carbon atoms. Alkylthio group, substituted amino group having a hydrocarbon group having 1 to 20 carbon atoms, cyano group, carboxyl group, ester group having a hydrocarbon group having 1 to 20 carbon atoms, or hydrocarbon group having 1 to 20 carbon atoms It is an acyloxy group having a group.
R is an alkyl group having 1 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms substituted with a halogen atom, a halogen atom, or a cyano group, even if it forms a cyclic structure with FG. good. ]

[2]
The FG is a halogen atom, an aryl group having 6 to 20 carbon atoms, a substituted amino group having a hydrocarbon group having 1 to 20 carbon atoms, a cyano group, or an ester group having a hydrocarbon group having 1 to 20 carbon atoms. , or an acyloxy group having a hydrocarbon group having 1 to 20 carbon atoms, the polar group-containing olefin copolymer according to [1].

[3]
The FG is a halogen atom, an aryl group having 6 to 20 carbon atoms, an ester group having a hydrocarbon group having 1 to 20 carbon atoms, or an acyloxy group having a hydrocarbon group having 1 to 20 carbon atoms. The polar group-containing olefin copolymer according to [2], characterized by:

[4]
A method for producing a polar group-containing olefin copolymer according to any one of [1] to [3],
A method for producing a polar group-containing olefin copolymer, which comprises polymerizing using a compound containing a transition metal of Groups 8 to 10.

[5]
[4] The compound containing a transition metal of groups 8 to 10 is a metal complex obtained by reacting a carbene precursor compound and a complex precursor of a transition metal compound of groups 8 to 10. A method for producing a polar group-containing olefin copolymer as described in .

[6]
The method for producing a polar group-containing olefin copolymer according to [5], wherein the carbene precursor compound is represented by the following general formula (4) or general formula (5).

[In general formula (4) and general formula (5), Z is OR ³ , SR ³ , SO ₃ R ³ , N=CR ³ R ⁴ , CR ³ =NR ⁴ , N(R ³ ) ₂ , P( ^R3 _{) 2} , _CO2R3 , _CO2M ', C(O)N( ^R3 ) ₂ , C(O)R3, ^SO2R3 _, ^{SOR3 , OSO2R3 ,} P(O) (OR ³ ) _2-y (R ⁴ ) _y , SO ₃ M', PO ₃ M' ₂ , P(O)(OR ³ ) ₂ M', P(R ³ ) ₂ (O). (Here, R ³ and R ⁴ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and M' represents an alkali metal, an alkaline earth metal, ammonium, quaternary ammonium, or phosphonium. (y represents an integer from 0 to 2). R ¹ and R ² are each independently a hydrocarbon group having 1 to 40 carbon atoms that may contain a hydrogen atom or a hetero atom. X ¹ represents a saturated or unsaturated divalent hydrocarbon group having 3 to 9 carbon atoms, and may have a substituent on the ring formed by X ¹ . Ra is a hydrocarbon group having 1 to 10 carbon atoms that may contain a hydrogen atom or a heteroatom, and may be condensed with a part of the ring consisting of X ¹ . A ⁻ represents a counter anion and represents any anion. E ¹ and E ² each independently represent a carbon atom or a nitrogen atom. n represents an integer of 0 or 1. ]

[7]
The method for producing a polar group-containing olefin copolymer according to [6], wherein the carbene precursor compound is represented by the following general formula (6) or general formula (7).

[In general formula (6) or general formula (7), X ² represents a saturated or unsaturated divalent hydrocarbon group having 3 to 9 carbon atoms. The ring formed by X ² may have a substituent. A ⁻ , Z, R ¹ , R ² , X ¹ , E ¹ and E ² are as described in [6]. ]

[8]
The method for producing a polar group-containing olefin copolymer according to [7], wherein the carbene precursor compound is represented by the following general formula (8) or general formula (9).

[In general formula (8) or general formula (9), R ⁵ to R ⁹ represent a halogen atom, a hetero atom-containing group, or a hydrocarbon group having 1 to 40 carbon atoms which may contain a hetero atom. A ⁻ , Z, R ¹ , R ² , E ¹ and E ² are as described in [6]. ]

[9]
The method for producing a polar group-containing olefin copolymer according to [6], wherein the carbene precursor compound described above is represented by the following general formula (10) or general formula (11).

[In the general formula (10) or the general formula (11), R ¹⁰ represents a halogen atom, a heteroatom-containing group, or a hydrocarbon group having 1 to 40 carbon atoms which may contain a heteroatom. A ⁻ , Z, R ¹ , R ² , R ⁵ , R ⁶ , E ¹ and E ² are as described in [6] or [8]. ]

[10]
In general formulas (4) to (11), Z is OR ³ , SR ³ , SO ₃ R ³ , N=CR ³ R ⁴ , CR ³ =NR ⁴ , N(R ³ ) ₂ , P(R ³ ) ₂ , P(O)(OR ³ ) _2-y (R ⁴ ) _y , the production of the polar group-containing olefin copolymer according to any one of [6] to [9]. Method.

[11]
Production of a polar group-containing olefin copolymer according to [4], wherein the compound containing a transition metal of Groups 8 to 10 is represented by the following general formula (12) or general formula (13). Method.

[In general formula (12) or general formula (13), M ¹ represents a transition metal belonging to groups 8 to 10 of the periodic table. L ¹ and L ² represent a ligand attached to M ¹ , and each independently represents a hydrocarbon group having 1 to 20 carbon atoms containing a halogen atom, a hydrogen atom, or a hetero atom. L ¹ and L ² may be connected to each other to form a ring.
Z is ^OR3 , ^SR3 , _{SO3R3 , N=CR3R4, CR3=NR4, N(R3)2} ^{, P ( R3 ) 2} _{, CO2R3} ^, _CO2M ^' , C(O)N(R ³ ) ₂ , C(O)R ³ , SO ₂ R ³ , SOR ³ , OSO ₂ R ³ , P(O)(OR ³ ) _2-y (R ⁴ ) _y , SO ₃ M', PO ₃ M' ₂ , P(O)(OR ³ ) ₂ M', P(R ³ ) ₂ (O). (Here, R ³ and R ⁴ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and M' represents an alkali metal, an alkaline earth metal, ammonium, quaternary ammonium, or phosphonium. (y represents an integer from 0 to 2). R ¹ and R ² are each independently a hydrocarbon group having 1 to 40 carbon atoms that may contain a hydrogen atom or a hetero atom. X ¹ represents a saturated or unsaturated divalent hydrocarbon group having 3 to 9 carbon atoms, and may have a substituent on the ring formed by X ¹ . Ra is a hydrocarbon group having 1 to 10 carbon atoms that may contain a hydrogen atom or a heteroatom, and may be condensed with a part of the ring consisting of X ¹ . A ⁻ represents a counter anion and represents any anion. E ¹ and E ² each independently represent a carbon atom or a nitrogen atom. n represents an integer of 0 or 1. A ⁺ represents a countercation and represents any cation. ]

[12]
The method for producing a polar group-containing olefin copolymer according to [11], wherein M ¹ is a transition metal belonging to Group 10 of the periodic table.

[13]
The method for producing a polar group-containing olefin copolymer according to [4], wherein the compound containing a transition metal of Groups 8 to 10 is a metal complex represented by the following general formula (C1).

[In formula (C1),
M represents a metal atom of Group 10 of the periodic table,
X represents a phosphorus atom (P) or an arsenic atom (As),
Y ¹ is a carbon atom number optionally substituted with one or more groups selected from a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, an ester group having 2 to 10 carbon atoms, a silyl group, and a halogen atom. represents a divalent hydrocarbon group of 1 to 70,
Q is Y ¹ [-S(=O) ₂ -O-]M, Y ¹ [-C(=O)-O-]M, Y ¹ [-P(=O)(-OH)-O- ]M or Y ¹ [-S-] Represents a divalent group shown in "[ ]" of M (However, Y ¹ and M on both sides are written to indicate the bonding direction of the group. ),
R ¹⁵ is substituted with a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 30 carbon atoms, a hydrocarbon group having 1 to 30 carbon atoms substituted with a halogen atom, or an alkoxy group having 1 to 10 carbon atoms; a hydrocarbon group having 2 to 30 carbon atoms, a hydrocarbon group having 7 to 30 carbon atoms substituted with an aryloxy group having 6 to 20 carbon atoms, and an amide group having 2 to 10 carbon atoms. A substituent selected from the group consisting of a hydrocarbon group having 3 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, an aryloxy group having 6 to 30 carbon atoms, and an acyloxy group having 2 to 10 carbon atoms. represents,
R ¹⁶ and R ¹⁷ are each independently substituted with one or more groups selected from a hydrogen atom, an alkoxy group, an aryloxy group, a silyl group, an amino group, or a halogen atom, an alkoxy group, and an aryloxy group; represents a hydrocarbon group having 1 to 120 carbon atoms, and at least one of R ¹⁶ and R ¹⁷ is an alkyl group having 1 to 10 carbon atoms or a cycloalkyl group having 4 to 106 carbon atoms. Further, R ¹⁶ or R ¹⁷ may be combined with Y ¹ to form a ring structure.
L represents an electron donating ligand,
q is 0, 1/2, 1 or 2. ]

[14]
In general formula (C1), Q is -S(=O) ₂ -O- (however, S is bonded to Y ¹ and O is bonded to M), containing a polar group according to [13] A method for producing an olefin copolymer.

[15]
The compound represented by general formula (C1) is represented by general formula (C2)

[In formula (C2), R ¹¹² to R ¹¹⁵ are hydrogen atoms, halogen atoms, hydrocarbon groups having 1 to 20 carbon atoms, alkoxy groups having 1 to 8 carbon atoms, and aryloxy groups having 6 to 20 carbon atoms. , represents a hydrocarbon group having 1 to 20 carbon atoms substituted with a silyl group or a halogen atom. M, X, R ¹⁵ , R ¹⁶ , R ¹⁷ , L and q have the same meanings as described in general formula (C1). ]
The method for producing a polar group-containing olefin copolymer according to [13], which is a metal complex represented by:

[16]
The compound represented by general formula (C2) has general formula (C3) in which R ¹¹² is a silyl group

[In formula (C3), the three R ^116s each independently represent a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, and may be the same or different. M, X, R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹¹³ , R ¹¹⁴ , R ¹¹⁵ , L and q have the same meaning as described in general formula (C2). ]
The method for producing a polar group-containing olefin copolymer according to [15], which is a metal complex represented by:

The present invention provides a novel polar group-containing olefin copolymer using a specific vinylidene comonomer.
Moreover, in the present invention, it is possible to produce a polar group-containing olefin copolymer using a post-metallocene complex catalyst having a specific structure.
The polar group-containing olefin copolymer provided by the present invention has a wide range of applications and is very useful.

Hereinafter, the polar group-containing olefin copolymer of the present invention, as well as the method for producing and utilizing the copolymer, will be specifically and detailedly explained item by item.
[1] Polar group-containing monomer of the present invention (1) About the polar group-containing monomer The polar group-containing monomer used in the present invention is:
It is at least one selected from the group consisting of polar group-containing monomers represented by the following general formulas (1), (2), and (3).

[In formulas (1), (2) and (3), FG is a halogen atom, a hydroxyl group, an aryl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or a hydroxyl group having 1 to 20 carbon atoms. Alkylthio group, substituted amino group having a hydrocarbon group having 1 to 20 carbon atoms, cyano group, carboxyl group, ester group having a hydrocarbon group having 1 to 20 carbon atoms, or hydrocarbon group having 1 to 20 carbon atoms It is an acyloxy group having a group.
R is an alkyl group having 1 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms substituted with a halogen atom, a halogen atom, or a cyano group, even if it forms a cyclic structure with FG. good. ]

(2) Specific examples of polar group-containing monomers In formulas (1), (2) and (3), FG is preferably a halogen atom, an aryl group having 6 to 20 carbon atoms, or an aryl group having 1 to 20 carbon atoms. A substituted amino group having a hydrocarbon group, a cyano group, an ester group having a hydrocarbon group having 1 to 20 carbon atoms, or an acyloxy group having a hydrocarbon group having 1 to 20 carbon atoms, more preferably a halogen group. an aryl group having 1 to 20 carbon atoms, an ester group having a hydrocarbon group having 1 to 20 carbon atoms, or an acyloxy group having a hydrocarbon group having 1 to 20 carbon atoms.

Here, FG will be explained in detail.
The halogen atom is not particularly limited. Preferred examples of the halogen atom include chlorine, fluorine, bromine, and iodine.

The aryl group having 6 to 20 carbon atoms is specifically phenyl group, methylphenyl group, n-propylphenyl group, i-propylphenyl group, n-butylphenyl group, i-butylphenyl group, s-butyl group. Preferred examples include phenyl group, t-butylphenyl group, n-hexylphenyl group, trimethylphenyl group, pentamethylphenyl group, biphenyl group, and naphthyl group.

The alkoxy group having 1 to 20 carbon atoms is specifically methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy, s-butoxy, t-butoxy, n-pentoxy, n- Preferred examples include hexoxy, cyclopropoxy, cyclopentoxy, cyclohexoxy, n-octoxy, n-detoxy and the like.

Examples of the alkylthio group having 1 to 20 carbon atoms include methylthio group, ethylthio group, propylthio group, isopropylthio group, butylthio group, isobutylthio group, s-butylthio group, t-butylthio group, pentylthio group, and hexylthio group. Preferred examples include decylthio group, dodecylthio group, and the like.

Specifically, the substituted amino group having a hydrocarbon group having 1 to 20 carbon atoms includes a monomethylamino group, a dimethylamino group, a monoethylamino group, a diethylamino group, a monoisopropylamino group, a diisopropylamino group, and a monophenylamino group. Preferred examples include a diphenylamino group, a bis(trimethylsilyl)amino group, a morpholinyl group, and the like.

Specifically, the ester group having a hydrocarbon group having 1 to 20 carbon atoms includes a methoxycarbonyl group, an ethoxycarbonyl group, an n-propoxycarbonyl group, an isopropoxycarbonyl group, an n-butoxycarbonyl group, and a t-butoxycarbonyl group. Preferred examples include a (4-hydroxybutyl)carbonyl group, a (4-glycidylbutyl)carbonyl group, a phenoxycarbonyl group, a succinic anhydride group, and a succinimide group.

Preferred examples of the acyloxy group having a hydrocarbon group having 1 to 20 carbon atoms include an acetyloxy group, a propionyloxy group, a (meth)acryloyloxy group, and a benzoyloxy group.

Next, R will be explained in detail.
In formulas (1), (2) and (3), R is an alkyl group having 1 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms substituted with a halogen atom, a halogen atom, or a cyano group. Yes, and a cyclic structure may be formed with FG.
R, which is an alkyl group having 1 to 10 carbon atoms, specifically includes a methyl group, an ethyl group, a 1-propyl group, a 1-butyl group, a 1-pentyl group, a 1-hexyl group, a 1-heptyl group, 1-octyl group, 1-nonyl group, 1-decyl group, t-butyl group, tricyclohexylmethyl group, isopropyl group, 1-dimethylpropyl group, 1,1,2-trimethylpropyl group, 1,1-diethylpropyl group group, isobutyl group, 1,1-dimethylbutyl group, 2-pentyl group, 3-pentyl group, 2-hexyl group, 3-hexyl group, 2-ethylhexyl group, 2-heptyl group, 3-heptyl group, 4- Heptyl group, 2-propylheptyl group, 2-octyl group, 3-nonyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, methylcyclopentyl group, cyclohexyl group, methylcyclohexyl group, cycloheptyl group, cyclooctyl group, cyclododecyl group Preferred examples include 1-adamantyl group, 2-adamantyl group, and the like.
R, which is an alkyl group having 1 to 10 carbon atoms substituted with a halogen atom, preferably includes a structure in which the above-mentioned hydrocarbon group having 1 to 20 carbon atoms is substituted with a halogen atom. A specifically preferred example is a trifluoromethyl group.
Preferred specific examples of the halogen atom R are fluorine, chlorine, and bromine. Among these, a more preferred substituent is chlorine.

[2] α-olefin in the present invention The α-olefin used in the present invention is ethylene and/or α-olefin having 3 to 10 carbon atoms. Preferred specific examples include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 3-methyl-1-butene, and 4-methyl-1-pentene, and particularly preferred A specific example is ethylene. Furthermore, one type of α-olefin may be used, or a plurality of types may be used in combination.

[3] Copolymer composition (composition of polar group-containing olefin copolymer)
In the polar group-containing olefin copolymer of the present invention, the amount of structural units derived from the polar group-containing monomer in the polar group-containing olefin copolymer is preferably 0.001 to 10.000 mol%. Among these, it is particularly preferable to select it within the range of 0.010 to 5.000 mol%.
The amount of structural units can be controlled by selecting a catalyst, the amount of a polar group-containing monomer added during polymerization, and the pressure and temperature during polymerization. As specific means for increasing the amount of structural units derived from polar group-containing monomers in the copolymer, it is effective to increase the amount of polar group-containing monomers added during polymerization, reduce the olefin pressure during polymerization, and increase the polymerization temperature. be. For example, it is required to control these factors to achieve a desired copolymer region.

The polar group-containing olefin copolymer in the present invention has a ratio of weight average molecular weight (Mw) to number average molecular weight (Mn) determined by gel permeation chromatography (GPC) in the range of 1.5 to 3.5. It is preferable that there be. Among these, the range is more preferably from 1.6 to 3.3, and particularly preferably from 1.7 to 3.0.
When Mw/Mn satisfies this range, various processability including molding of a laminate will be sufficient, and adhesive strength will be excellent. Mw/Mn can be controlled by selecting the catalyst used.

The melting point of the polar group-containing olefin copolymer in the present invention is not particularly limited. The melting point is preferably 50°C to 138°C. Among these, the temperature range is particularly preferably 60°C to 135°C, and more preferably 70°C to 135°C. When this range is satisfied, heat resistance and adhesiveness will be excellent.
This melting point can be controlled by selecting the catalyst used and the amount of polar group-containing monomer added during polymerization. As specific means for increasing the melting point of the polar group-containing olefin copolymer, effective are reducing the amount of the polar group-containing monomer added during polymerization, increasing the olefin pressure during polymerization, and lowering the polymerization temperature. For example, it is required to control these factors to achieve a desired copolymer region.

The polar group-containing olefin copolymer in the present invention is a linear random copolymer with a degree of methyl branching calculated by ¹³ C-NMR analysis of 20 or less per 1,000 carbons of the copolymer. The degree of methyl branching is preferably 18 or less per 1,000 carbons of the copolymer.
If the methyl branches satisfy this value, the elastic modulus will be high and the mechanical strength of the molded product will also be high.
The degree of methyl branching can be controlled by selecting the catalyst used and the polymerization temperature. As a specific means for reducing the degree of methyl branching of a copolymer, lowering the polymerization temperature is effective. For example, it is required to control these factors to achieve a desired copolymer region.

[4] Compound Containing Transition Metal An example of the method for producing the polar group-containing olefin copolymer of the present invention is a method of polymerizing using a compound containing a transition metal of groups 8 to 10.
Specific examples of preferred transition metals include vanadium atoms, niobium atoms, tantalum atoms, chromium atoms, molybdenum atoms, tungsten atoms, manganese atoms, iron atoms, ruthenium atoms, cobalt atoms, rhodium atoms, nickel atoms, palladium atoms, etc. . Among these, vanadium atoms, iron atoms, cobalt atoms, nickel atoms, and palladium atoms are preferred, and nickel atoms and palladium atoms are particularly preferred. These metals may be used alone or in combination.

The compound containing a transition metal of groups 8 to 10 is preferably a metal complex obtained by reacting a carbene precursor compound and a complex precursor of a transition metal compound of groups 8 to 10.

It is preferable that the carbene precursor compound is a compound represented by the following general formula (4) or general formula (5). These compounds are N-heterocyclic carbene precursors.

In general formula (4) and general formula (5), Z is OR ³ , SR ³ , SO ₃ R ³ , N=CR ³ R ⁴ , CR ³ =NR ⁴ , N(R ³ ) ₂ , P(R ³ ) ₂ , _CO2R3 , _CO2M ', C(O)N( ^R3 ) ₂ , C(O) ^R3 , _SO2R3 , ^{SOR3 , OSO2R3} _, P ⁽ O)( OR ³ ) _2-y (R ⁴ ) _y , SO ₃ M', PO ₃ M' ₂ , P(O)(OR ³ ) ₂ M', P(R ³ ) ₂ (O). (Here, R ³ and R ⁴ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and M' represents an alkali metal, an alkaline earth metal, ammonium, quaternary ammonium, or phosphonium. (y represents an integer from 0 to 2). R ¹ and R ² are each independently a hydrocarbon group having 1 to 40 carbon atoms that may contain a hydrogen atom or a hetero atom. X ¹ represents a saturated or unsaturated divalent hydrocarbon group having 3 to 9 carbon atoms, and may have a substituent on the ring formed by X ¹ . Ra is a hydrocarbon group having 1 to 10 carbon atoms that may contain a hydrogen atom or a heteroatom, and may be condensed with a part of the ring consisting of X ¹ . A ⁻ represents a counter anion and represents any anion. E ¹ and E ² each independently represent a carbon atom or a nitrogen atom. n represents an integer of 0 or 1.

The N-heterocyclic carbene precursor represented by the general formula (4) or the general formula (5) of the present invention is typically a 1,3 diazole ring (5-membered imidazole) having two nitrogen atoms. The 5-membered ring is fused with another ring, and the fused ring contains one nitrogen atom to form a carbene at the carbon atom of the fused ring. That is, it is an N-heterocyclic carbene precursor in which a ring structure is connected to a 5-membered ring structure that generates a carbene, and the ring structure is connected to include a nitrogen atom in the 5-membered ring structure that generates a carbene. ing.

In the N-heterocyclic carbene precursor represented by general formula (4) or general formula (5), the ring fused to the 5-membered ring may be further fused, and these precursors are as follows. It is represented by general formula (6) or general formula (7).

In the general formula (6) or the general formula (7), X ² represents a saturated or unsaturated divalent hydrocarbon group having 3 to 9 carbon atoms. The ring formed by X ² may have a substituent. A ⁻ , Z, R ¹ , R ² , X ¹ , E ¹ and E ² are as described in general formula (4) or general formula (5).

The precursor compound represented by the general formula (6) or general formula (7) is more specifically a precursor compound represented by the following general formula (8) or general formula (9).

In the general formula (8) or the general formula (9), R ⁵ to R ⁹ represent a halogen atom or a hetero atom-containing group, or a hydrocarbon group having 1 to 40 carbon atoms which may contain a hetero atom. A ⁻ , Z, R ¹ , R ² , E ¹ and E ² are as described in general formula (4) or general formula (5).

The precursor compound represented by the general formula (8) or general formula (9) will be specifically exemplified below along with its synthesis method. The detailed contents are described in Japanese Patent Application Laid-Open No. 2016-135777.

Precursor compound (b) is 2-(2,6-diisopropylphenyl)imidazo[1,5-a]quinolinium-9-oleate.

Precursor compound (c) is 2-(2,6-dibenzhydryl-4-methylphenyl)imidazo[1,5-a]quinolinium-9-oleate.

Other examples of the N-heterocyclic carbene precursor represented by general formula (4) or general formula (5) are represented by general formula (10) or general formula (11) below.

In the general formula (10) or the general formula (11), R ¹⁰ represents a halogen atom, a heteroatom-containing group, or a C1-40 hydrocarbon group which may contain a heteroatom. A ⁻ , Z, R ¹ , R ² , R ⁵ , R ⁶ , E ¹ and E ² are as described in general formula (4) or general formula (8).

Here, representative examples of the carbene precursor compound of the present invention are as follows.

In general formulas (4) to (11), Z is OR ³ , SR ³ , SO ₃ R ³ , N=CR ³ R ⁴ , CR ³ =NR ⁴ , N(R ³ ) ₂ , P(R ³ ) ₂ , CO ₂ R ³ , CO ₂ M', C(O)N(R ³ ) ₂ , C(O)R ³ , SO ₂ R ³ , SOR ³ , OSO ₂ R ³ , P(O)(OR ³ ) _2-y (R ⁴ ) _y , SO ₃ M', PO ₃ M' ₂ , P(O)(OR ³ ) ₂ M', P(R ³ ) ₂ (O).

Specific examples of Z include OH, OCH ₃ , OCH ₂ CH ₃ , SH, SCH ₃ , SCH ₂ CH ₃ , SO ₃ H, SO ₃ CH ₃ , SO ₃ CH ₂ CH ₃ , N=CH ₂ , N= _CHCH3 , N= _CHCH2CH3 , N=CH(Dip), CH ₌ NH, CH= _NCH3 , CH=NCH2CH3, CH= _N (Dip), C( _CH3 )=N(Dip ₎ , NH ₂ , N(CH ₃ ) ₂ , N(CH ₂ CH ₃ ) ₂ , PH ₂ , P(CH ₃ ) ₂ , P(CH ₂ CH ₃ ) ₂ , P ⁱ Pr ₂ , PPh ₂ , CO ₂ H , _CO2CH3 , _CO2CH2CH3 , _{CO2K , C} (O)NH2 _, C(O)N( _CH3 ) _{2 ,} C(O)N( _{CH2CH3 ) 2} , C( O)H, _C (O) _{CH3 , C} (O)CH2CH3, SO2H _{, SO2CH3 , SO2CH2CH3} , SOH _{, SOCH3 , SOCH2CH3} , _OSO2H , _{OSO2CH3 , OSO2CH2CH3} , P(O)(OH)( _CH3 ), P(O)( _OCH3 ) _{( CH3 )} , SO3Na _{, SO3K} , _{PO3Na2 , PO3K2} , P(O)(OH) _2Na , P(O)( _OCH3 ) _2K , P( ^tBu ) _{2 (} O), P( ^iPr ) ₂ (O), PPh2 ₍ O ) etc. are exemplified. Here, Dip represents a 2,6-diisopropylphenyl group, Ph represents a phenyl group, ⁱ Pr represents an isopropyl group, ^{and t} Bu represents a tertiary butyl group.

R ¹ and R ² are each independently a hydrocarbon group having 1 to 40 carbon atoms that may contain a hydrogen atom or a hetero atom. Here, specific examples of the hydrocarbon group having 1 to 40 carbon atoms which may contain a heteroatom include C(O)CH ₃ , C(O)CH ₂ CH ₃ , CH ₂ OCH ₃ , CH ₂ OCH Examples include ₂ CH ₃ , CH ₂ NH ₂ , CH ₂ CH ₂ NH ₂ and the like.
The hydrocarbon group is preferably a hydrocarbon group having 1 to 33 carbon atoms, such as an alkyl group, a cycloalkyl group, or an aryl group. Preferred specific examples include 1-propyl group, 1-butyl group, 1-pentyl group, 1-hexyl group, 1-heptyl group, 1-octyl group, 1-nonyl group, 1-decyl group, t-butyl group, Tricyclohexylmethyl group, 1,1-dimethyl-2-phenylethyl group, isopropyl group, 1-dimethylpropyl group, 2,4,6-trimethylphenyl group, 2,6-diisopropylphenyl group, 2,6-dibenzhydryl group 4-methylphenyl group, etc.

Ra is a hydrocarbon group having 1 to 10 carbon atoms that may contain a hydrogen atom or a heteroatom, and includes CH ₃ , CH ₂ CH ₃ , C(O)CH ₃ , C(O)CH ₂ CH ₃ , Examples include CH ₂ OCH ₃ , CH ₂ OCH ₂ CH ₃ , CH ₂ NH ₂ , CH ₂ CH ₂ NH ₂ and the like.
A ^- represents a counter anion, and examples of the arbitrary anion include COO ^- , Cl ^- , and Br ^- . Among the Z mentioned above, there is a substituent that becomes negatively monovalently charged when the leaving group is removed, and in this case, the substituent becomes electrically neutral within the molecule and does not require A ^- .

In general formulas (8) to (11), examples of a halogen atom-containing group, a heteroatom-containing group, or a hydrocarbon group having 1 to 40 carbon atoms that may contain a heteroatom include a fluorine atom, a chlorine atom, a bromine atom, , _{CH3 , CH2CH3 ,} C(O) _CH3 , _{C (} O) _{CH2CH3 , CH2OCH3 , CH2OCH2CH3 , CH2NH2 , CH2CH2NH2} , NO ₂ etc. are exemplified.
More specifically, the hydrocarbon group is preferably a hydrocarbon group having 1 to 30 carbon atoms, such as an alkyl group, a cycloalkyl group, or an aryl group. Preferred specific examples include 1-propyl group, 1-butyl group, 1-pentyl group, 1-hexyl group, 1-heptyl group, 1-octyl group, 1-nonyl group, 1-decyl group, t-butyl group, These include tricyclohexylmethyl group, 1,1-dimethyl-2-phenylethyl group, isopropyl group, 1-dimethylpropyl group, phenyl group, biphenyl group, anthracenyl group, and 2,4,6-trimethylphenyl group.

[5] Metal complex [5.1] Metal complex (first example)
A first example of the metal complex used in the present invention is obtained by reacting a carbene precursor compound in any of the general formulas (4) to (11) with a complex precursor of a transition metal compound of Groups 8 to 10 of the periodic table. It is a metal complex characterized by being obtained by

Examples of such metal complexes include compounds represented by the following general formula (12) or general formula (13).

In general formula (12) or general formula (13), M ¹ represents a transition metal belonging to groups 8 to 10 of the periodic table. L ¹ and L ² represent a ligand attached to M ¹ , and each independently represents a hydrocarbon group having 1 to 20 carbon atoms containing a halogen atom, a hydrogen atom, or a hetero atom. L ¹ and L ² may be connected to each other to form a ring. Z, R ¹ , R ² , X ¹ , n, Ra, E ¹ and E ² are as described in general formula (4) or general formula (5). A ⁺ represents a counter cation, and examples of the arbitrary cation include K ⁺ and Na ⁺ . Depending on the valence of M ¹ and the types of Z, L ¹ and L ² , the complex as a whole may be negatively charged, in which case a countercation A ⁺ is required. Here, the valence of M ¹ means a formal oxidation number used in organometallic chemistry.
Examples of the transition metal M ¹ in general formula (12) or general formula (13) include Fe, Co, Ni, Pd, and Pt. Examples of the ligands L ¹ and L ² include a halogen atom, a methyl group, a phenyl group, a benzyl group, pyridine, and 2,6-lutidine.

The metal complexes represented by the general formula (12) or (13) are illustrated below along with their synthesis methods. The detailed contents are described in Japanese Patent Application Laid-Open No. 2016-135777.
The complex synthesis reaction may be carried out in the reactor used for polymerization or copolymerization of α-olefins, or may be carried out in a separate container from the reactor. After complex formation, the metal complex may be isolated and extracted and used as a catalyst, or may be used as a catalyst without being isolated.

This metal complex is formed from 2-(2,6-diisopropylphenyl)imidazo[1,5-a]quinolinium-9-oleate and chloro(methyl)(1,5-cyclooctadiene)palladium. .

This metal complex is made from 2-(2,6-diisopropylphenyl)imidazo[1,5-a]quinolinium-9-oleate and Ni(cod) ₂ (cod is 1,5-cyclooctadiene). It is formed.

[5.2] Metal complex (second example)
A second example of the metal complex used in the present invention will be described below.
The structure of the second example of the metal complex is represented by general formula (C1).

In the formula, M represents a metal atom of Group 10 of the periodic table, X represents a phosphorus atom (P) or an arsenic atom (As), and Y ¹ represents a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, a carbon represents a divalent hydrocarbon group having 1 to 70 carbon atoms which may be substituted with one or more groups selected from ester groups having 2 to 10 atoms, silyl groups, and halogen atoms, and Q represents Y ¹ [-S(=O) ₂ -O-]M, Y ¹ [-C(=O)-O-]M, Y ¹ [-P(=O)(-OH)-O-]M or Y ¹ [-S-] represents a divalent group shown in "[ ]" of M (however, Y ¹ and M on both sides are written to indicate the bonding direction of the group).

R ¹⁵ is substituted with a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 30 carbon atoms, a hydrocarbon group having 1 to 30 carbon atoms substituted with a halogen atom, or an alkoxy group having 1 to 10 carbon atoms; a hydrocarbon group having 2 to 30 carbon atoms, a hydrocarbon group having 7 to 30 carbon atoms substituted with an aryloxy group having 6 to 20 carbon atoms, and an amide group having 2 to 10 carbon atoms. A substituent selected from the group consisting of a hydrocarbon group having 3 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, an aryloxy group having 6 to 30 carbon atoms, and an acyloxy group having 2 to 10 carbon atoms. represents.

R ¹⁶ and R ¹⁷ are each independently substituted with one or more groups selected from a hydrogen atom, an alkoxy group, an aryloxy group, a silyl group, an amino group, or a halogen atom, an alkoxy group, and an aryloxy group; represents a hydrocarbon group having 1 to 120 carbon atoms, and at least one of R ¹⁶ and R ¹⁷ is an alkyl group having 1 to 10 carbon atoms or a cycloalkyl group having 4 to 106 carbon atoms. Further, R ¹⁶ or R ¹⁷ may be combined with Y ¹ to form a ring structure.
L represents an electron donating ligand, and q is 0, 1/2, 1 or 2.
Note that in this specification, "hydrocarbon" includes saturated and unsaturated aliphatic hydrocarbons, and aromatic hydrocarbons. It also includes chain structures and cyclic structures.

The structure of general formula (C1) will be explained below.
M represents a metal atom of Group 10 of the periodic table. Examples of metal atoms in Group 10 of the periodic table include Ni, Pd, and Pt, and from the viewpoint of catalytic activity and molecular weight of the resulting polymer, Ni and Pd are preferred, and Pd is more preferred.
X is a phosphorus atom (P) or an arsenic atom (As), and is coordinated with the central metal M with two electrons. As X, P is preferable from the viewpoint of easy availability and catalyst cost.

R ¹⁵ is substituted with a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 30 carbon atoms, a hydrocarbon group having 1 to 30 carbon atoms substituted with a halogen atom, or an alkoxy group having 1 to 10 carbon atoms; a hydrocarbon group having 2 to 30 carbon atoms, a hydrocarbon group having 7 to 30 carbon atoms substituted with an aryloxy group having 6 to 20 carbon atoms, and an amide group having 2 to 10 carbon atoms. A substituent selected from the group consisting of a hydrocarbon group having 3 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, an aryloxy group having 6 to 30 carbon atoms, or an acyloxy group having 2 to 10 carbon atoms. represents a group.

Preferred specific examples of the halogen atom represented by R ¹⁵ are a fluorine atom, a chlorine atom, and a bromine atom. Among these, a more preferred substituent is a chlorine atom.

The hydrocarbon group having 1 to 30 carbon atoms represented by R ¹⁵ is preferably a hydrocarbon group having 1 to 20 carbon atoms, more preferably a hydrocarbon group having 1 to 13 carbon atoms, and includes an alkyl group, a cycloalkyl group, and a hydrocarbon group having 1 to 30 carbon atoms. or aryl group.
Preferred specific examples include methyl group, ethyl group, 1-propyl group, 1-butyl group, 1-pentyl group, 1-hexyl group, 1-heptyl group, 1-octyl group, 1-nonyl group, and 1-decyl group. , t-butyl group, tricyclohexylmethyl group, 1,1-dimethyl-2-phenylethyl group, isopropyl group, 1-dimethylpropyl group, 1,1,2-trimethylpropyl group, 1,1-diethylpropyl group, 1-phenyl-2-propyl group, isobutyl group, 1,1-dimethylbutyl group, 2-pentyl group, 3-pentyl group, 2-hexyl group, 3-hexyl group, 2-ethylhexyl group, 2-heptyl group, 3-heptyl group, 4-heptyl group, 2-propylheptyl group, 2-octyl group, 3-nonyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, methylcyclopentyl group, cyclohexyl group, methylcyclohexyl group, cycloheptyl group , cyclooctyl group, cyclododecyl group, 1-adamantyl group, 2-adamantyl group, exo-norbornyl group, endo-norbornyl group, 2-bicyclo[2.2.2]octyl group, nopinyl group, decahydronaphthyl group, Menthyl group, neomenthyl group, neopentyl group, 5-decyl group, phenyl group, naphthyl group, anthracenyl group, fluorenyl group, tolyl group, xylyl group, benzyl group, and p-ethylphenyl group.
Among these, more preferred substituents are methyl group and benzyl group, and particularly preferred is methyl group.

The hydrocarbon group having 1 to 30 carbon atoms substituted with a halogen atom represented by R ¹⁵ is preferably a hydrocarbon group having 1 to 30 carbon atoms substituted with a fluorine atom, a chlorine atom, or a bromine atom. A specific preferred example of the group is a trifluoromethyl group or a pentafluorophenyl group.

The hydrocarbon group having 2 to 30 carbon atoms substituted with an alkoxy group having 1 to 10 carbon atoms represented by R ¹⁵ is preferably a methoxy group, an ethoxy group, A substituent substituted with an isopropoxy group, a 1-propoxy group, a 1-butoxy group, or a t-butoxy group. More preferably a hydrocarbon group having 2 to 6 carbon atoms substituted with a methoxy group or an ethoxy group, specifically a 1-(methoxymethyl)ethyl group, a 1-(ethoxymethyl)ethyl group, a 1- Examples include (phenoxymethyl)ethyl group, 1-(methoxyethyl)ethyl group, 1-(ethoxyethyl)ethyl group, di(methoxymethyl)methyl group, di(ethoxymethyl)methyl group, and di(phenoxymethyl)methyl group. It will be done. Particularly preferred are 1-(methoxymethyl)ethyl group and 1-(ethoxymethyl)ethyl group.

The hydrocarbon group having 7 to 30 carbon atoms substituted with the aryloxy group having 6 to 20 carbon atoms represented by R ¹⁵ is preferably a hydrocarbon group having 1 to 30 carbon atoms substituted with a phenoxy group, 4 - A substituent substituted with a methylphenoxy group, a 4-methoxyphenoxy group, a 2,6-dimethylphenoxy group, or a 2,6-di-t-butylphenoxy group. More preferred is a hydrocarbon group having 1 to 6 carbon atoms substituted with a phenoxy group or a 2,6-dimethylphenoxy group, and particularly preferred is a 1-(phenoxymethyl)ethyl group or a 1-(2,6-dimethylphenoxy group). -dimethylphenoxy group (methyl)ethyl group.

The hydrocarbon group having 3 to 30 carbon atoms substituted with the amide group having 2 to 10 carbon atoms represented by R ¹⁵ is preferably acetamido group, propionylamino group, etc. A substituent substituted with a group, a butyrylamino group, an isobutyrylamino group, a valerylamino group, an isovalerylamino group, a pivaloylamino group, or a benzoylamino group. More preferred are 2-acetamidophenyl group, 2-propionylaminophenyl group, 2-valerylaminophenyl group, and 2-benzoylphenyl group, and particularly preferred is 2-acetamidophenyl group.

The alkoxy group having 1 to 30 carbon atoms represented by R ¹⁵ is preferably an alkoxy group having 1 to 20 carbon atoms, more preferably an alkoxy group having 1 to 6 carbon atoms, and specific examples include a methoxy group, Examples include ethoxy group, isopropoxy group, 1-propoxy group, 1-butoxy group, and t-butoxy group. Among these, more preferred substituents are methoxy group, ethoxy group, and isopropoxy group, and particularly preferred is methoxy group.

The aryloxy group having 6 to 30 carbon atoms represented by R ¹⁵ is preferably an aryloxy group having 6 to 12 carbon atoms, and specific examples thereof include phenoxy group, 4-methylphenoxy group, and 4-methoxyphenoxy group. , 2,6-dimethylphenoxy group, and 2,6-di-t-butylphenoxy group. Among these, a more preferred substituent is a phenoxy group or a 2,6-dimethylphenoxy group, and a phenoxy group is particularly preferred.

The acyloxy group having 2 to 10 carbon atoms represented by R ¹⁵ is preferably an acyloxy group having 2 to 8 carbon atoms, and specific examples thereof include an acetyloxy group, a propionyloxy group, a butyryloxy group, and an isobutyryloxy group. , valeryloxy group, isovaleryloxy group, pivaloyloxy group, and benzoyloxy group.
Among these, more preferred substituents are an acetyloxy group, a propionyloxy group, and a benzoyloxy group, and particularly preferred are an acetyloxy group and a propionyloxy group.

Among these groups preferred as R ¹⁵ , more preferred are hydrocarbon groups having 1 to 20 carbon atoms, hydrocarbon groups having 2 to 30 carbon atoms substituted with alkoxy groups, and alkoxy groups having 1 to 20 carbon atoms. Particularly preferred examples include a methyl group, a benzyl group, a methoxy group, a 2-acetamidophenyl group, and an acetyloxy group.

R ¹⁶ and R ¹⁷ are each independently substituted with one or more groups selected from a hydrogen atom, an alkoxy group, an aryloxy group, a silyl group, an amino group, or a halogen atom, an alkoxy group, and an aryloxy group; Represents a hydrocarbon group having 1 to 120 carbon atoms. However, at least one of R ¹⁶ and R ¹⁷ is an alkyl group having 1 to 10 carbon atoms or a cycloalkyl group having 4 to 106 carbon atoms. Further, R ¹⁶ or R ¹⁷ may be combined with Y ¹ to form a ring structure.

The alkoxy group represented by R ¹⁶ and R ¹⁷ preferably has 1 to 20 carbon atoms, and examples thereof include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, and the like. The aryloxy group represented by R ¹⁶ and R ¹⁷ preferably has 6 to 24 carbon atoms, such as a phenoxy group. Examples of the silyl group represented by R ¹⁶ and R ¹⁷ include trimethylsilyl group. Examples of the amino group represented by R ¹⁶ and R ¹⁷ include an amino group, a methylamino group, and a dimethylamino group. Specific examples of the hydrocarbon group having 1 to 120 carbon atoms which may be substituted with one or more groups selected from a halogen atom, an alkoxy group, and an aryloxy group represented by R ¹⁶ and R ¹⁷ include a methyl group, Ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, n-pentyl group, 2-pentyl group, 3-pentyl group, neopentyl group, n-hexyl group, 2-hexyl group, 3-hexyl group, 2-heptyl group, 3-heptyl group, 4-heptyl group, 2-methyl-4-heptyl group, 2,6-dimethyl-4-heptyl group, 3-methyl -4-heptyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, 1-adamantyl group, trifluoromethyl group, benzyl group, 2'-methoxybenzyl group, 3'- Methoxybenzyl group, 4'-methoxybenzyl group, 4'-trifluoromethylbenzyl group, phenyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 2,6-dimethylphenyl group, 3 , 5-dimethylphenyl group, 2,4,6-trimethylphenyl group, 2-isopropylphenyl group, 3-isopropylphenyl group, 4-isopropylphenyl group, 2,6-diisopropylphenyl group, 3,5-diisopropylphenyl group , 2,4,6-triisopropylphenyl group, 2-t-butylphenyl group, 2-cyclohexylphenyl group, 2-methoxyphenyl group, 3-methoxyphenyl group, 4-methoxyphenyl group, 2,6-dimethoxyphenyl group group, 3,5-dimethoxyphenyl group, 2,4,6-trimethoxyphenyl group, 4-fluorophenyl group, pentafluorophenyl group, 4-trifluoromethylphenyl group, 3,5-bis(trifluoromethyl) Phenyl group, 1-naphthyl group, 2-naphthyl group, 2-furyl group, 2-biphenyl group, 2',6'-dimethoxy-2-biphenyl group, 2'-methyl-2-biphenyl group, 2',4 Examples include ',6'-triisopropyl-2-biphenyl group.

Further, R ¹⁶ and R ¹⁷ may be the same or different. Furthermore, R ¹⁶ and R ¹⁷ may be combined to form a ring structure. R ¹⁶ and/or R ¹⁷ may be combined with Y ¹ to form a ring structure.

Note that at least one of R ¹⁶ and R ¹⁷ represents an alkyl group having 1 to 10 carbon atoms or a cycloalkyl group having 4 to 106 carbon atoms. As the alkyl group having 1 to 10 carbon atoms, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, and t-butyl group are preferable. Examples of the cycloalkyl group having 4 to 106 carbon atoms include a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and the cycloalkyl group represented by the following general formula (5) Particularly preferred.

In the formula, R represents an alkylene group having 1 to 14 carbon atoms which may have a substituent, and R ¹⁹ , R ¹¹⁰ and R ¹¹¹ each independently represent a hydrogen atom, an alkoxy group, an aryloxy group, Represents a hydrocarbon group having 1 to 30 carbon atoms that may be substituted with a silyl group, an amino group, or one or more groups selected from a halogen atom, an alkoxy group, and an ^{aryloxy group} ; At least one of them may not be a hydrogen atom, and R ¹⁹ , R ¹¹⁰ , R ¹¹¹ and the alkylene group R may be bonded to each other to form a ring structure. In addition, in the formula, the bond between the carbon atom and X in general formula (C1) is also described.

Further, R ¹⁶ and R ¹⁷ are preferably both cycloalkyl groups represented by the general formula (5) above for ease of synthesis.

As described above, in general formula (5), at least one of R ¹⁹ and R ¹¹⁰ is not a hydrogen atom. It is thought that this substituent R ¹⁹ or R ¹¹⁰ , which is not a hydrogen atom, suppresses chain transfer of the polymer due to β-hydrogen elimination during the polymerization reaction, thereby improving the molecular weight of the obtained polymer. ^A carbon atom which may be substituted with an alkoxy group, an aryloxy group, a silyl group, an amino group, or one or more groups selected from a halogen atom, an alkoxy group, and an aryloxy group represented by R ¹⁹ , R ¹¹⁰ and R 111 Specific examples of the hydrocarbon group having numbers 1 to 30 include those similar to the above-mentioned specific examples of R ¹⁶ and R ¹⁷ .
The alkylene group R preferably has 2 to 6 carbon atoms, more preferably 4 carbon atoms.

At least one of R ¹⁹ and R ¹¹⁰ is preferably an alkyl group having 1 to 6 carbon atoms or a cycloalkyl group having 3 to 8 carbon atoms. Furthermore, it is preferable that at least one of R ¹⁹ and R ¹¹⁰ is an isopropyl group.

Specific examples of the X--R ¹⁶ or X--R ¹⁷ moiety when R ¹⁶ or R ¹⁷ represents a group represented by general formula (5) are listed below. Note that Me represents a methyl group, and the bonds between X and M and between X and ^Y1 are omitted.

Among these, R ¹⁶ and R ¹⁷ are preferably a 2-isopropyl-5-methylcyclohexyl group (menthyl group) represented by the following formula. Furthermore, it is more preferable that both R ¹⁶ and R ¹⁷ are menthyl groups.

In general formula (C1), Q is represented by -S(=O) ₂ -O-, -C(=O)-O-, -P(=O)(-OH)-O-, or -S-. It represents a divalent group that coordinates with M with one electron. The left side of each of the above formulas is bonded to ^Y1 , and the right side is bonded to M. Among these, -S(=O) ₂ -O- is particularly preferred from the viewpoint of catalytic activity.

In the Y ¹ -Q site, an oxygen atom or a sulfur atom with high electronegativity is coordinated with one electron to the metal atom M. The bonding electron between Y ¹ -QM can also be formally expressed as Y ¹ -Q in an anion state and M in a cation state.

In the general formula (C1), Y ¹ is substituted with one or more groups selected from a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, an ester group having 2 to 10 carbon atoms, a silyl group, and a halogen atom. Represents a divalent hydrocarbon group having 1 to 70 carbon atoms, which may have 1 to 70 carbon atoms.
Examples of the silyl group as a substituent on Y ¹ include trimethylsilyl group, triethylsilyl group, tripropylsilyl group, tributylsilyl group, triisopropylsilyl group, t-butyldimethylsilyl group, t-butyldiphenylsilyl group, etc. Among them, trimethylsilyl group and triethylsilyl group are particularly preferred.
The alkoxy group having 1 to 10 carbon atoms which is a substituent on Y ¹ is preferably an alkoxy group having 1 to 6 carbon atoms. Preferred specific examples include methoxy group, ethoxy group, isopropoxy group, and phenoxy group, with methoxy group and phenoxy group being particularly preferred.
The ester group having 2 to 10 carbon atoms, which is a substituent on Y ¹ , is preferably an ester group having 2 to 8 carbon atoms, and preferred specific examples include methoxycarbonyl group, ethoxycarbonyl group, n-propoxycarbonyl group. group, isopropoxycarbonyl group, n-butoxycarbonyl group, t-butoxycarbonyl group, (4-hydroxybutoxy)carbonyl group, (4-glycidylbutoxy)carbonyl group, phenoxycarbonyl group, succinic anhydride group, succinimide Examples include groups. Preferred examples include methoxycarbonyl group, ethoxycarbonyl group, (4-hydroxybutoxy)carbonyl group, and succinic anhydride group, and particularly preferred are methoxycarbonyl group and succinic anhydride group.
Examples of the halogen atom as a substituent on Y ¹ include fluorine, chlorine, bromine, etc., with fluorine and chlorine being particularly preferred.
The hydrocarbon group having 1 to 70 carbon atoms is preferably a hydrocarbon group having 1 to 12 carbon atoms, preferably an alkylene group, an arylene group, etc., and an arylene group is particularly preferred.

Y ¹ is a crosslinking site that connects X and Q sites. Specific examples of Y ¹ in which X is a P atom are shown below. Here, the plurality of R ^104s may be the same or different, and include a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, and an alkoxy group having 6 to 20 carbon atoms. represents a hydrocarbon group having 1 to 20 carbon atoms substituted with an aryloxy group, a silyl group, or a halogen atom. However, the upper limit of the number of carbon atoms as Y ¹ is 70.

Specific examples of the halogen atom, alkoxy group, aryloxy group, and silyl group represented by R ¹⁰⁴ are the same as those explained for Y ¹ . The hydrocarbon group having 1 to 20 carbon atoms and the hydrocarbon group having 1 to 20 carbon atoms substituted with a halogen atom represented by R ¹⁰⁴ include methyl group, ethyl group, n-propyl group, isopropyl group, n- Butyl group, isobutyl group, sec-butyl group, t-butyl group, n-pentyl group, 2-pentyl group, 3-pentyl group, neopentyl group, n-hexyl group, 2-hexyl group, 3-hexyl group, cyclo Propyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclododecyl group, 1-adamantyl group, 2-adamantyl group, exo-norbonyl group, endo-norbonyl group, menthyl group, neomenthyl group, Trifluoromethyl group, benzyl group, 4'-trifluoromethylbenzyl group, phenyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 2,6-dimethylphenyl group, 3,5- Dimethylphenyl group, 2,4,6-trimethylphenyl group, 2-isopropylphenyl group, 3-isopropylphenyl group, 4-isopropylphenyl group, 2,6-diisopropylphenyl group, 3,5-diisopropylphenyl group, 2, 4,6-triisopropylphenyl group, 2-t-butylphenyl group, 2-cyclohexylphenyl group, 4-fluorophenyl group, pentafluorophenyl group, 4-trifluoromethylphenyl group, 3,5-bis(trifluoro methyl) phenyl group, 1-naphthyl group, 2-naphthyl group, 2-furyl group, 2-biphenyl group, 2'-methyl-2-biphenyl group, 2',4',6'-triisopropyl-2-biphenyl group, vinyl group, allyl group, butenyl group, cyclohexenyl group, cinnamyl group, styryl group, anthracenyl group, fluorenyl group, and the like.

The substituent R ¹⁶ or R ¹⁷ may be bonded to the Y ¹ moiety to form a ring structure. Specifically, the structures shown below can be mentioned. Note that the following example shows a case where the substituent R ¹⁶ and the Y ¹ site are bonded to form a ring structure.

Among the metal complexes represented by the general formula (C1), those represented by the following general formula (C2) are particularly preferred.

In general formula (C2), R ¹¹² to R ¹¹⁵ are a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, and an aryloxy group having 6 to 20 carbon atoms. , represents a hydrocarbon group having 1 to 20 carbon atoms substituted with a silyl group or a halogen atom. These specific examples are similar to those described for R ¹⁰⁴ . M, X, R ¹⁵ , R ¹⁶ , R ¹⁷ , L and q have the same meanings as described in general formula (C1).

In general formula (C2), those represented by the following general formula (C3) in which R ^{1 1 2} is a silyl group are preferred.

In the formula, three independent R ^116s may be the same or different and represent a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms. M, X, R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹¹³ , R ¹¹⁴ , R ¹¹⁵ , L and q have the same meaning as described in general formula (C2).

In general formula (C3), R ¹¹⁶ is preferably a hydrocarbon group having 1 to 4 carbon atoms, and it is particularly preferable that all three R ¹¹⁶ are methyl groups. R ¹¹³ is preferably a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, and particularly preferably a hydrogen atom, an isopropyl group, or a phenyl group. R ¹¹⁴ and R ¹¹⁵ are preferably a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms, and particularly preferably a hydrogen atom.

The catalytic metal complex represented by general formula (C1) can be synthesized by a method similar to that described in known literature (for example, J. Am. Chem. Soc. 2007, 129, 8948). That is, a metal complex is synthesized by reacting a zero-valent or divalent M source with a ligand in general formula (C1).

In the compounds represented by general formula (C2) and general formula (C3), Y ¹ and Q in general formula (C1) are replaced with specific groups corresponding to general formula (C2) and general formula (C3). It can be synthesized by

Examples of zero-valent M sources include tris(dibenzylideneacetone)dipalladium as a palladium source, and tetracarbonylnickel(0):Ni(CO) ₄ , bis(1,5-cyclooctadiene) as a nickel source. Nickel is an example.

The divalent M source includes (1,5-cyclooctadiene)(methyl)palladium chloride, palladium chloride, palladium acetate, bis(acetonitrile)dichloropalladium: PdCl ₂ (CH ₃ CN) ₂ , bis( benzonitrile) dichloropalladium: PdCl ₂ (PhCN) ₂ , (N,N,N',N'-tetramethylethylenediamine) dichloropalladium(II): PdCl ₂ (TMEDA), (N,N,N',N' -tetramethylethylenediamine)dimethylpalladium(II): _PdMe2 (TMEDA),bis(acetylacetonato)palladium(II):Pd(acac) ₂ (acac=acetylacetonato),(palladium(II) trifluoromethanesulfonate :Pd(OSO ₂ CF ₃ ) ₂ as a nickel source, (allyl) nickel chloride, (allyl) nickel bromide, nickel chloride, nickel acetate, bis(acetylacetonato)nickel(II):Ni(acac) ₂ , (1,2-dimethoxyethane)dichloronickel(II):NiCl ₂ (DME), and nickel(II) trifluoromethanesulfonate:Ni(OSO ₂ CF ₃ ) ₂ .

The metal complex represented by general formula (C1) can be used in isolation, but it can be used by bringing the metal source containing M into contact with the ligand precursor in a reaction system without isolating the complex. can also be subjected to polymerization in situ. In particular, when R ¹⁵ in general formula (C1) is a hydrogen atom, it is possible to react the metal source containing zero valent M with the ligand precursor and then directly subject it to polymerization without isolating the complex. preferable.

In this case, the ligand precursor is of the general formula (C1),

(The symbols in the formula have the same meanings as above.)
It is indicated by.

The ratio ((C1 ligand)/M) of the M source (M) and the ligand precursor (C1-1) (C1 ligand) in general formula (C1) is 0.5 to 2.0. More preferably, it is selected within the range of 1.0 to 1.5.

When isolating the metal complex of general formula (C1), it is also possible to use one that has been stabilized by coordination with an electron-donating ligand (L) in advance. In this case, q is 1/2, 1 or 2. When q is 1/2, it means that one divalent electron-donating ligand is coordinated to two metal complexes. q is preferably 1/2 or 1 in order to stabilize the metal complex catalyst. Note that when q is 0, it means that there is no ligand.

The electron-donating ligand (L) is a compound that has an electron-donating group and can coordinate to the metal atom M to stabilize the metal complex.
Examples of the electron-donating ligand (L) having a sulfur atom include dimethyl sulfoxide (DMSO). Those having a nitrogen atom include trialkylamines having an alkyl group having 1 to 10 carbon atoms, dialkylamines having an alkyl group having 1 to 10 carbon atoms, pyridine, 2,6-dimethylpyridine (also known as 2,6-lutidine) ), aniline, 2,6-dimethylaniline, 2,6-diisopropylaniline, N,N,N',N'-tetramethylethylenediamine (TMEDA), 4-(N,N-dimethylamino)pyridine (DMAP), Examples include acetonitrile, benzonitrile, quinoline, 2-methylquinoline and the like. Examples of those having an oxygen atom include diethyl ether, tetrahydrofuran, and 1,2-dimethoxyethane. From the viewpoint of the stability and catalytic activity of the metal complex, dimethyl sulfoxide (DMSO), pyridine, 2,6-dimethylpyridine (also known as 2,6-lutidine), N,N,N',N'-tetramethylethylenediamine ( TMEDA) is preferred, and dimethyl sulfoxide (DMSO) and 2,6-dimethylpyridine (also known as 2,6-lutidine) are more preferred.

[6] Polymerization catalyst The polymerization catalyst of the present invention is a copolymer of α-olefin such as ethylene and (meth)acrylic acid ester or allyl monomer, which has good catalytic activity, high molecular weight, and high comonomer content. It is a catalyst that makes production possible.
This catalyst has the above-described metal complex as the main catalyst component (A), and as component (B), a compound or ion-exchangeable layered silicate that reacts with component (A) to form an ion pair. Component (C), an organoaluminum compound, is used as necessary.

Specific examples of component (B) include the following (B-1) to (B-3).
(B-1) Aluminum oxy compound (B-2) Ionic compound or Lewis acid capable of reacting with component (A) to convert component (A) into a cation (B-3) Solid acid

(B-1) Regarding aluminum oxy compounds, it is well known that aluminum oxy compounds can activate post-metallocene complexes, and specific examples of such compounds include the following general formulas (II) to (IV). Examples include compounds represented by:

In each of the above general formulas, R ^a represents a hydrogen atom or a hydrocarbon group, preferably a hydrocarbon group having 1 to 10 carbon atoms, particularly preferably 1 to 6 carbon atoms. Further, the plurality of R ^a 's may be the same or different. Further, p represents an integer of 0 to 40, preferably 2 to 30. Among the general formulas, the compounds represented by the first and second formulas are also called aluminoxane, and among these, methylaluminoxane or methylisobutylaluminoxane is preferable. It is also possible to use a plurality of the above aluminoxanes in combination within each group and between each group. The above aluminoxane can be prepared under various known conditions.
The compound represented by the third formula in the general formula is a mixture of one type of trialkylaluminum or two or more types of trialkylaluminum and an alkylboronic acid represented by the general formula R ^b B (OH) ₂ in a ratio of 10:1 to It can be obtained by a reaction of 1:1 (molar ratio). In the general formula, R ^b represents a hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms.

The compound (B-2) is an ionic compound or Lewis acid that can react with component (A) to convert component (A) into a cation, and such ionic compounds include carbonium Examples include complexes of cations such as cations and ammonium cations and organic boron compounds such as triphenylboron, tris(3,5-difluorophenyl)boron, and tris(pentafluorophenyl)boron.
Furthermore, examples of the above-mentioned Lewis acids include various organic boron compounds, such as tris(pentafluorophenyl)boron. Alternatively, metal halogen compounds such as aluminum chloride and magnesium chloride are exemplified.
In addition, some of the above Lewis acids can also be understood as ionic compounds capable of reacting with component (A) to convert component (A) into a cation.

Examples of the solid acid (B-3) include alumina, silica-alumina, and silica-magnesia.

The polymerization catalyst of the present invention comprises a carbene precursor compound or a phosphorus sulfonic acid compound represented by general formulas (4) to (11), and a compound of groups 8 to 10 (late period type; Fe, Co, Ni, Pd, etc.). It is an α-olefin polymerization catalyst obtained by reacting with a transition metal compound.
Synthesis of the catalyst composition can generally be carried out by contacting the Group 8-10 transition metal compound and the novel carbene precursor compound or phosphorus sulfonic acid compound in a solution or slurry.
Preferably, the transition metal compound is a Group 10 transition metal compound, such as bis(dibenzylideneacetone)palladium, tetrakis(triphenylphosphine)palladium, palladium sulfate, palladium acetate, bis(allylpalladium chloride), palladium chloride, or bromide. Palladium, (cyclooctadiene) palladium (methyl) chloride, dimethyl (tetramethylethylenediamine) palladium, bis (cyclooctadiene) nickel, nickel chloride, nickel bromide, (tetramethylethylenediamine) nickel (methyl) chloride, dimethyl (tetra It is synthesized using nickel (methylethylenediamine), (cyclooctadiene)nickel (methyl)chloride, etc.

The complex formation reaction may be carried out in the reactor used for copolymerization with the α-olefin, or may be carried out in a separate vessel from the reactor. After the complex formation, the metal complex may be isolated and extracted and used as a catalyst, or may be used as a catalyst without being isolated. Furthermore, it is also possible to carry out in the presence of a porous carrier, which will be described later.
Further, the catalyst composition of the present invention may be used alone or in combination of multiple types. In particular, for the purpose of widening the molecular weight distribution and comonomer content distribution, it is useful to use a plurality of catalyst compositions in combination.

The polymerization catalyst of the present invention may be used alone or supported on a carrier. Any carrier can be used as long as it does not detract from the gist of the present invention.
In general, inorganic oxides and polymer carriers can be suitably used. Specifically, SiO ₂ , Al ₂ O ₃ , MgO, ZrO ₂ , TiO ₂ , B ₂ O ₃ , CaO, ZnO, BaO, ThO ₂ and mixtures thereof are mentioned, and SiO ₂ -Al ₂ O ₃ , SiO ₂ -V ₂ O ₅ , SiO ₂ -TiO ₂ , SiO ₂ -MgO, SiO ₂ -Cr ₂ O ₃ and other mixed oxides can also be used, inorganic silicates, polyethylene carriers, polypropylene carriers, Polystyrene carriers, polyacrylic acid carriers, polymethacrylic acid carriers, polyacrylic ester carriers, polyester carriers, polyamide carriers, polyimide carriers, etc. can be used.
These carriers are not particularly limited in particle size, particle size distribution, pore volume, specific surface area, etc., and any carrier can be used.

The catalyst for olefin polymerization of the present invention can be prepared by bringing the above-mentioned components (A) and (B) into contact with each other in the presence or absence of the monomer to be polymerized inside or outside a polymerization tank.
That is, components (A) and (B) and, if necessary, component (C) may be introduced into the polymerization tank separately, or components (A) and (B) may be brought into contact with each other beforehand and then introduced into the polymerization tank. You may. Alternatively, a mixture of components (A) and (B) may be impregnated with component (C) and then introduced into the polymerization tank.
The above-mentioned components may be contacted in an inert gas such as nitrogen and an inert hydrocarbon solvent such as pentane, hexane, heptane, toluene, and xylene. The contact temperature is preferably in the range of -20° C. to the boiling point of the solvent, particularly in the range of room temperature to the boiling point of the solvent. The catalyst prepared in this manner may be used without being washed after preparation, or may be used after washing. Furthermore, after preparation, a new combination of components may be used as necessary.

The catalyst component may be prepolymerized in the presence of the olefin within the polymerization tank or outside the polymerization tank. Olefin refers to a hydrocarbon containing at least one carbon-carbon double bond, and examples thereof include ethylene, propylene, 1-butene, 1-hexene, 3-methylbutene-1, styrene, and divinylbenzene. There are no limitations, and mixtures of these and other olefins may also be used. Preferably it is an olefin having 2 or 3 carbon atoms. Any method of supplying the olefin can be used, such as a method of supplying the olefin to the reaction tank at a constant rate or a constant pressure state, a combination thereof, or a stepwise change.

[7] Copolymerization reaction The copolymerization reaction in the present invention is performed using a hydrocarbon solvent such as propane, n-butane, isobutane, n-hexane, n-heptane, toluene, xylene, cyclohexane, methylcyclohexane, or a liquefied α-olefin. Liquids such as diethyl ether, ethylene glycol dimethyl ether, tetrahydrofuran, dioxane, ethyl acetate, methyl benzoate, acetone, methyl ethyl ketone, formylamide, acetonitrile, methanol, isopropyl alcohol, ethylene glycol, etc. It is carried out in the presence or absence of a polar solvent such as. Also, mixtures of the liquid compounds described herein may be used as solvents. Note that in order to obtain high polymerization activity and high molecular weight, the above-mentioned hydrocarbon solvents are more preferable.

During the copolymerization in the present invention, the copolymerization can be carried out in the presence or absence of known additives. As the additive, a radical polymerization inhibitor or an additive having an effect of stabilizing the produced copolymer is preferable. Examples of preferable additives include quinone derivatives and hindered phenol derivatives.
Specifically, monomethyl ether hydroquinone, 2,6-di-t-butyl 4-methylphenol (BHT), the reaction product of trimethylaluminum and BHT, and the reaction product of tetravalent titanium alkoxide and BHT. objects etc. can be used.
Furthermore, inorganic and/or organic fillers may be used as additives, and polymerization may be carried out in the presence of these fillers.

In the present invention, there is no particular restriction on the polymerization type. Slurry polymerization in which at least part of the produced polymer becomes a slurry in a medium, bulk polymerization in which the liquefied monomer itself is used as a medium, gas phase polymerization carried out in a vaporized monomer, or polymer produced in a monomer liquefied at high temperature and high pressure. High-pressure ionic polymerization in which at least a portion of the polymer is dissolved is preferably used.
Further, the polymerization mode may be any of batch polymerization, semi-batch polymerization, and continuous polymerization.

Unreacted monomers and media may be separated from the produced copolymer and recycled for use. During recycling, these monomers and media may be purified and reused, or may be reused without being purified. Conventional known methods can be used to separate the produced copolymer from unreacted monomers and the medium. For example, methods such as filtration, centrifugation, solvent extraction, and reprecipitation using a poor solvent can be used.

Although there are no particular restrictions on the copolymerization temperature, copolymerization pressure, and copolymerization time, optimal settings can usually be made from the following ranges in consideration of productivity and process capacity.
That is, the copolymerization temperature is usually -20°C to 290°C, preferably 0°C to 250°C, the copolymerization pressure is 0.1 MPa to 100 MPa, preferably 0.3 MPa to 90 MPa, and the copolymerization time is 0. The time can be selected from the range of 1 minute to 50 hours, preferably 0.5 minutes to 40 hours, and more preferably 1 minute to 30 hours.
In the present invention, copolymerization is generally carried out under an inert gas atmosphere. For example, a nitrogen or argon atmosphere can be used, and a nitrogen atmosphere is preferably used. Note that a small amount of oxygen or air may be mixed in.

There are no particular restrictions on the supply of the catalyst and monomer to the copolymerization reactor, and various supply methods can be used depending on the purpose. For example, in the case of batch polymerization, it is possible to supply a predetermined amount of monomer to a copolymerization reactor in advance, and then supply a catalyst thereto. In this case, additional monomers and additional catalysts may be supplied to the copolymerization reactor. Further, in the case of continuous polymerization, a method can be adopted in which a predetermined amount of monomer and catalyst are continuously or intermittently supplied to a copolymerization reactor to carry out the copolymerization reaction continuously.

Regarding the control of the composition of the copolymer, a method can generally be used in which a plurality of monomers are supplied to a reactor and controlled by changing the supply ratio. Other methods include controlling the copolymerization composition by utilizing differences in the monomer reactivity ratio due to differences in catalyst structure, and controlling the copolymerization composition by utilizing the polymerization temperature dependence of the monomer reactivity ratio. .
Conventionally known methods can be used to control the molecular weight of the copolymer. Namely, methods to control molecular weight by controlling polymerization temperature, methods to control molecular weight by controlling monomer concentration, methods to control molecular weight by using chain transfer agents, and methods to control ligand structure in transition metal complexes. For example, controlling the molecular weight by
When using a chain transfer agent, a conventionally known chain transfer agent can be used. For example, hydrogen, metal alkyl, etc. can be used.

In the following, the present invention will be specifically explained with reference to Examples, and the rationality, significance, usefulness, and superiority of the configuration of the present invention over the prior art will be demonstrated.

[1] Method for analyzing structure of polymer [1-1] Comonomer content of copolymer The comonomer content of the copolymer obtained in the example was determined by NMR analysis using Ascend 500 manufactured by Bruker. The molar ratio of ethylene:comonomer was determined by ¹ H-NMR measurement at 120° C. using 1,1,2,2-tetrachloroethane- _d2 as a solvent and incorp. It is listed in Table 1 as (%). incorp. (%) means comonomer content (mol%).
[1-2] Amount of methyl branching 200 mg of sample was mixed with 2.4 ml of o-dichlorobenzene/deuterated bromide benzene (C6D5Br) = 4/1 (volume ratio) and hexamethyldisiloxane, which is a reference material for chemical shift, to the inner diameter. The mixture was placed in a 10 mmφ NMR sample tube, purged with nitrogen, sealed, and heated to dissolve as a homogeneous solution, which was then subjected to NMR measurement. For NMR measurement, an NMR device AVANCE III400 manufactured by Bruker Biospin Co., Ltd. equipped with a 10 mmφ cryoprobe was used.
The amount of methyl branching is 20.0 ppm when the sum of the integrated intensities of the signals in the range of 10 to 180 ppm in the ¹³ C-NMR spectrum is normalized to 1,000, and the average of the integrated intensities of the characteristic signals of 33.2 ppm is 1. It was calculated as the number of methyl branches per 000C.

[2] Number average molecular weight (Mn) and weight average molecular weight (Mw)
Using Tosoh Corporation's high-temperature GPC device HLC-8121GPC/HT equipped with Tosoh Corporation's TSKgel GMHHR-H (S) HT column (two 7.8 mm ID x 30 cm in series), Calculated by size exclusion chromatography (solvent: 1,2-dichlorobenzene, temperature: 145°C) using monodisperse polystyrene as a molecular weight standard.
Note that in Table 1, which will be described later, Mw/Mn is expressed as PDI.

In the following synthesis examples, unless otherwise specified, operations were performed in a purified argon atmosphere, and the solvent used was one that had been dehydrated and deoxygenated. Metal complex 1 and metal complex 2 used as catalysts were described in Non-Patent Document 3; Nozaki et al. , J. Am. Chem. Soc. , 2015, 137, 10934-10937, Non-Patent Document 11; Synthesized according to JP 2014-219220A. In addition, as a comonomer, methyl methacrylate (MMA; Kanto Kagaku), α-methylstyrene (α-MS); TCI, β-methallyl chloride (MACl); TCI ), methyl butenyl acetate (MBAc); Aldrich), and methallyl phenyl ether (MAPE); Alfa Aesar) were used. All of these comonomers were used after distillation. Among these comonomers, the structural formulas of methyl methacrylate (MMA), methyl butenyl acetate (MBAc), α-methylstyrene (α-MS), and methallylphenyl ether (MAPE) are shown below.

[3] Synthesis of polar group-containing olefin copolymers of Examples 1, 2, 4, 5, 6, 8, 9, 10, 11, and 12 Under an argon atmosphere, the following catalyst (metal complex 1) was added in a predetermined amount ( A predetermined amount (amount shown in Table 1) of toluene and a predetermined amount (amount shown in Table 1) of each comonomer (amount shown in Table 1) were placed in a 50 mL autoclave manufactured by Pressure Glass Industry Co., Ltd. ) was added. After filling a predetermined amount (amount listed in Table 1) of ethylene, the autoclave was stirred at a predetermined temperature (temperature listed in Table 1) for a predetermined time (time listed in Table 1). After cooling to room temperature, methanol (approximately 20 mL) was added into the autoclave. The resulting copolymer was collected by filtration. The copolymer was dissolved in ODCB (ortho-dichlorobenzene) and then reprecipitated in methanol. Thereafter, it was dried under reduced pressure to obtain a copolymer.

[4] Synthesis of polar group-containing olefin copolymers of Examples 3 and 7. A fixed amount (amounts listed in Table 1) of toluene and a predetermined amount (amounts listed in Table 1) of each comonomer (listed in Table 1) were added. After filling a predetermined amount (amount listed in Table 1) of ethylene, the autoclave was stirred at a predetermined temperature (temperature listed in Table 1) for a predetermined time (time listed in Table 1). After cooling to room temperature, methanol (approximately 20 mL) was added into the autoclave. The resulting copolymer was collected by filtration. The copolymer was placed in a Soxhlet extractor and washed with methyl ethyl ketone for 5 days. Thereafter, it was dried under reduced pressure to obtain a copolymer.

[5] Synthesis of polar group-containing olefin copolymer of Example 13 In an argon atmosphere in a 50 mL autoclave manufactured by Pressure Glass Industry Co., Ltd. containing a predetermined amount (amount shown in Table 1) of the following catalyst (metal complex 2) To this were added a predetermined amount (amounts listed in Table 1) of toluene and a predetermined amount (amounts listed in Table 1) of each comonomer (listed in Table 1). After filling a predetermined amount (amount listed in Table 1) of ethylene, the autoclave was stirred at a predetermined temperature (temperature listed in Table 1) for a predetermined time (time listed in Table 1). After cooling to room temperature, methanol (approximately 20 mL) was added into the autoclave. The resulting copolymer was collected by filtration. The copolymer was dissolved in ODCB (ortho-dichlorobenzene) and then reprecipitated in methanol. Thereafter, it was dried under reduced pressure to obtain a copolymer.

[6] Results and Discussion Table 1 shows the experimental results. It was confirmed that polar group-containing olefin copolymers were obtained in all Examples. According to this example, a novel polar group-containing olefin copolymer that exhibits physical properties such as adhesiveness, printability, or compatibility with fillers is provided. Moreover, according to this example, a polar group-containing olefin copolymer is efficiently produced.
It was confirmed that the olefin copolymer was a linear random copolymer with a degree of methyl branching calculated by ¹³ C-NMR analysis of 20 or less per 1,000 carbons of the copolymer.

The present invention is not limited to the embodiments detailed above, and various modifications and changes can be made within the scope of the claims of the present invention.

According to the present invention, there is provided a novel polar group-containing olefin copolymer that has good adhesiveness and printability or exhibits good compatibility with fillers, etc. Since it is an olefin copolymer, it can be used in a wide range of applications. This olefin copolymer can be produced by the production method of the present invention and has high industrial applicability.
In particular, the olefin copolymer of the present invention can be suitably used in applications that require physical properties such as adhesion with other materials, printability, or compatibility with fillers.

Claims (14)

A structural unit derived from ethylene and/or an α-olefin having 3 to 10 carbon atoms;
A polar group-containing olefin containing 20 to 0.001 mol% of structural units derived from at least one type selected from the group consisting of polar group-containing monomers represented by the following general formulas (1), (2), and (3). It is a copolymer,
and,
A method for producing a polar group-containing olefin copolymer, characterized in that the copolymer is a linear random copolymer with a degree of methyl branching calculated by ¹³ C-NMR analysis of 20 or less per 1,000 carbons of the copolymer, , a method for producing a polar group-containing olefin copolymer, which is characterized by polymerization using a metal complex obtained by reacting a carbene precursor compound and a complex precursor of a transition metal compound of Groups 8 to 10.

[In formulas (1), (2) and (3), FG is a halogen atom, a hydroxyl group, an aryl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or a hydroxyl group having 1 to 20 carbon atoms. Alkylthio group, substituted amino group having a hydrocarbon group having 1 to 20 carbon atoms, cyano group, carboxyl group, ester group having a hydrocarbon group having 1 to 20 carbon atoms, or hydrocarbon group having 1 to 20 carbon atoms It is an acyloxy group having a group.
R is an alkyl group having 1 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms substituted with a halogen atom, a halogen atom, or a cyano group, even if it forms a cyclic structure with FG. good. ] The FG is a halogen atom, an aryl group having 6 to 20 carbon atoms, a substituted amino group having a hydrocarbon group having 1 to 20 carbon atoms, a cyano group, or an ester group having a hydrocarbon group having 1 to 20 carbon atoms. , or an acyloxy group having a hydrocarbon group having 1 to 20 carbon atoms , the method for producing a polar group-containing olefin copolymer according to claim 1. The FG is a halogen atom, an aryl group having 6 to 20 carbon atoms, an ester group having a hydrocarbon group having 1 to 20 carbon atoms, or an acyloxy group having a hydrocarbon group having 1 to 20 carbon atoms. 3. The method for producing a polar group-containing olefin copolymer according to claim 2. The method for producing a polar group-containing olefin copolymer according to claim 1 , wherein the carbene precursor compound is represented by the following general formula (4) or general formula (5).

[In general formula (4) and general formula (5), Z is OR ³ , SR ³ , SO ₃ R ³ , N=CR ³ R ⁴ , CR ³ =NR ⁴ , N(R ³ ) ₂ , P( ^R3 _{) 2} , _CO2R3 , _CO2M ', C(O)N( ^R3 ) ₂ , C(O)R3, ^SO2R3 _, ^{SOR3 , OSO2R3 ,} P(O) (OR ³ ) _2-y (R ⁴ ) _y , SO ₃ M', PO ₃ M' ₂ , P(O)(OR ³ ) ₂ M', P(R ³ ) ₂ (O). (Here, R ³ and R ⁴ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and M' represents an alkali metal, an alkaline earth metal, ammonium, quaternary ammonium, or phosphonium. (y represents an integer from 0 to 2). R ¹ and R ² are each independently a hydrocarbon group having 1 to 40 carbon atoms that may contain a hydrogen atom or a hetero atom. X ¹ represents a saturated or unsaturated divalent hydrocarbon group having 3 to 9 carbon atoms, and may have a substituent on the ring formed by X ¹ . Ra is a hydrocarbon group having 1 to 10 carbon atoms that may contain a hydrogen atom or a heteroatom, and may be condensed with a part of the ring consisting of X ¹ . A ⁻ represents a counter anion and represents any anion. E ¹ and E ² each independently represent a carbon atom or a nitrogen atom. n represents an integer of 0 or 1. ] The method for producing a polar group-containing olefin copolymer according to claim 4 , wherein the carbene precursor compound is represented by the following general formula (6) or general formula (7).

[In general formula (6) or general formula (7), X ² represents a saturated or unsaturated divalent hydrocarbon group having 3 to 9 carbon atoms. The ring formed by X ² may have a substituent. A ⁻ , Z, R ¹ , R ² , X ¹ , E ¹ and E ² are as described in claim 4 . ] The method for producing a polar group-containing olefin copolymer according to claim 5 , wherein the carbene precursor compound is represented by the following general formula (8) or general formula (9).

[In general formula (8) or general formula (9), R ⁵ to R ⁹ represent a halogen atom, a hetero atom-containing group, or a hydrocarbon group having 1 to 40 carbon atoms which may contain a hetero atom. A ⁻ , Z, R ¹ , R ² , E ¹ and E ² are as described in claim 4 . ] 5. The method for producing a polar group-containing olefin copolymer according to claim 4 , wherein the carbene precursor compound is represented by the following general formula (10) or general formula (11).

[In the general formula (10) or the general formula (11), R ¹⁰ represents a halogen atom, a heteroatom-containing group, or a hydrocarbon group having 1 to 40 carbon atoms which may contain a heteroatom. A ⁻ , Z, R ¹ , R ² , R ⁵ , R ⁶ , E ¹ and E ² are as described in claim 4 or 6 . ] In general formulas (4) to (11), Z is OR ³ , SR ³ , SO ₃ R ³ , N=CR ³ R ⁴ , CR ³ =NR ⁴ , N(R ³ ) ₂ , P(R ³ ) ₂ , P(O)(OR ³ ) _2-y (R ⁴ ) _y , the method for producing a polar group-containing olefin copolymer according to any one of claims 4 to 7 . Production of a polar group-containing olefin copolymer according to claim 1 , wherein the compound containing a transition metal of Groups 8 to 10 is represented by the following general formula (12) or general formula (13). Method.

[In general formula (12) or general formula (13), M ¹ represents a transition metal belonging to groups 8 to 10 of the periodic table. L ¹ and L ² represent a ligand attached to M ¹ , and each independently represents a hydrocarbon group having 1 to 20 carbon atoms containing a halogen atom, a hydrogen atom, or a hetero atom. L ¹ and L ² may be connected to each other to form a ring.
Z is ^OR3 , ^SR3 _{, SO3R3} , N= ^CR3R4 , ^CR3 = ^NR4 , N( ^R3 ) ² , P( ^R3 ) ₂ , _CO2R3 ^, _CO2M ^' , C(O)N(R ³ ) ₂ , C(O)R ³ , SO ₂ R ³ , SOR ³ , OSO ₂ R ³ , P(O)(OR ³ ) _2-y (R ⁴ ) _y , SO ₃ M', PO ₃ M' ₂ , P(O)(OR ³ ) ₂ M', P(R ³ ) ₂ (O). (Here, R ³ and R ⁴ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and M' represents an alkali metal, an alkaline earth metal, ammonium, quaternary ammonium, or phosphonium. (y represents an integer from 0 to 2). R ¹ and R ² are each independently a hydrocarbon group having 1 to 40 carbon atoms that may contain a hydrogen atom or a hetero atom. X ¹ represents a saturated or unsaturated divalent hydrocarbon group having 3 to 9 carbon atoms, and may have a substituent on the ring formed by X ¹ . Ra is a hydrocarbon group having 1 to 10 carbon atoms that may contain a hydrogen atom or a heteroatom, and may be condensed with a part of the ring consisting of X ¹ . E ¹ and E ² each independently represent a carbon atom or a nitrogen atom. n represents an integer of 0 or 1. A ⁺ represents a countercation and represents any cation. ] 10. The method for producing a polar group-containing olefin copolymer according to claim 9 , wherein ^M1 is a transition metal belonging to Group 10 of the periodic table. The method for producing a polar group-containing olefin copolymer according to claim 1 , wherein the compound containing a transition metal of Groups 8 to 10 is a metal complex represented by the following general formula (C1).

[In formula (C1),
M represents a metal atom of Group 10 of the periodic table,
X represents a phosphorus atom (P) or an arsenic atom (As),
Y ¹ is a carbon atom number optionally substituted with one or more groups selected from a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, an ester group having 2 to 10 carbon atoms, a silyl group, and a halogen atom. represents a divalent hydrocarbon group of 1 to 70,
Q is Y ¹ [-S(=O) ₂ -O-]M, Y ¹ [-C(=O)-O-]M, Y ¹ [-P(=O)(-OH)-O- ]M or Y ¹ [-S-] Represents a divalent group shown in "[ ]" of M (However, Y ¹ and M on both sides are written to indicate the bonding direction of the group. ),
R ¹⁵ is substituted with a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 30 carbon atoms, a hydrocarbon group having 1 to 30 carbon atoms substituted with a halogen atom, or an alkoxy group having 1 to 10 carbon atoms; a hydrocarbon group having 2 to 30 carbon atoms, a hydrocarbon group having 7 to 30 carbon atoms substituted with an aryloxy group having 6 to 20 carbon atoms, and an amide group having 2 to 10 carbon atoms. A substituent selected from the group consisting of a hydrocarbon group having 3 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, an aryloxy group having 6 to 30 carbon atoms, and an acyloxy group having 2 to 10 carbon atoms. represents,
R ¹⁶ and R ¹⁷ are each independently substituted with one or more groups selected from a hydrogen atom, an alkoxy group, an aryloxy group, a silyl group, an amino group, or a halogen atom, an alkoxy group, and an aryloxy group; represents a hydrocarbon group having 1 to 120 carbon atoms, and at least one of R ¹⁶ and R ¹⁷ is an alkyl group having 1 to 10 carbon atoms or a cycloalkyl group having 4 to 106 carbon atoms. Further, R ¹⁶ or R ¹⁷ may be combined with Y ¹ to form a ring structure.
L represents an electron donating ligand,
q is 0, 1/2, 1 or 2. ] 12. The polar group-containing compound according to claim 11 , wherein in general formula (C1), Q is -S(=O) ₂ -O- (S is bonded to Y ¹ and O is bonded to M). A method for producing an olefin copolymer. The compound represented by general formula (C1) is represented by general formula (C2)

[In formula (C2), R ¹¹² to R ¹¹⁵ are hydrogen atoms, halogen atoms, hydrocarbon groups having 1 to 20 carbon atoms, alkoxy groups having 1 to 8 carbon atoms, and aryloxy groups having 6 to 20 carbon atoms. , represents a hydrocarbon group having 1 to 20 carbon atoms substituted with a silyl group or a halogen atom. M, X, R ¹⁵ , R ¹⁶ , R ¹⁷ , L and q have the same meanings as described in general formula (C1). ]
The method for producing a polar group-containing olefin copolymer according to claim 11 , which is a metal complex represented by: The compound represented by general formula (C2) has general formula (C3) in which R ¹¹² is a silyl group

[In formula (C3), the three R ^116s each independently represent a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, and may be the same or different. M, X, R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹¹³ , R ¹¹⁴ , R ¹¹⁵ , L and q have the same meaning as described in general formula (C2). ]
The method for producing a polar group-containing olefin copolymer according to claim 13 , which is a metal complex represented by: