JP2018141138A - Polar group-containing olefin copolymer, and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a novel polar group-containing olefin copolymer using a vinylidenecomonomer which can be widely used in practical use, and a method for producing the same. SOLUTION: At least one selected from a structural unit derived from ethylene and / or an α-olefin having 3 to 10 carbon atoms and a polar group-containing monomer represented by the formulas (1), (2) and (3). A polar group-containing olefin copolymer containing 20 to 0.001 mol% of structural units derived from. [FG is a halogen atom, a hydroxyl group, an aryl group of C6 to 20, an alkoxy group of C1 to 20, an alkylthio group of C1 to 20, a substituted amino group having a hydrocarbon group of C1 to 20, a cyano group, a carboxyl group, and C1 to C1. An ester group having 20 hydrocarbon groups or an acyloxy group having C1 to 20 hydrocarbon groups] [Selection diagram] None

Description

  The present invention relates to an olefin copolymer comprising a polar group-containing monomer having a specific structure as a constituent component, and more specifically, an ethylene and / or α-olefin monomer and a polar group-containing monomer having a specific structure (polar group). Is a novel polar group-containing olefin copolymer having a unique structure.

Olefin polymers are excellent industrial properties such as physical properties and moldability, high economic efficiency and compatibility with environmental problems, and are very versatile and important industrial materials.
However, since the olefin polymer does not have a polar group, it has been difficult to apply to applications that require adhesive properties with other materials, printability, or compatible physical properties 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 as a simple substance or a composition with another resin (Patent Document 1 and Patent). Reference 2). However, due to the polymer multi-branched structure, it has poor low modulus and mechanical properties, and its application range is limited not only when used alone but also as a composition with other resins. It was.

On the other hand, in the olefin polymer production method using a metallocene catalyst generally used in the past, when copolymerizing ethylene and a polar group-containing monomer, it was said that the catalyst polymerization activity was reduced and the copolymerization was difficult. There has been reported a method of copolymerizing with an olefin after reacting an organoaluminum compound or an organozinc compound with a polar comonomer (masking a polar functional group) (Patent Documents 3 and 4). However, this method has a problem that a large amount of metal salt precipitates simultaneously with the formation of the copolymer, and is not widespread from the viewpoint of the cost of the organoaluminum compound.
By the way, in recent years, attempts to copolymerize olefins and polar comonomers without using masking agents such as organoaluminum compounds using so-called post metallocene, a late transition metal complex catalyst, have been energetically advanced. It has been. Up to now, while having a feature 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), vinyl ether (Non-Patent Document 1) Patent Document 2) has been reported.

Japanese Patent No. 2792982 JP-A-3-229713 JP 2003-327627 A Japanese Patent Laid-Open No. 03-207707 Special table 2002-521534 gazette JP-A-6-184214 Japanese Patent Laid-Open No. 2008-223011 JP 2010-150246 A JP 2010-150532 A JP 2010-202647 A

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 that are 1,1-disubstituted olefins are less copolymerizable with olefins because they are less polymerizable by late transition metal complex catalysts than vinyl compounds that are monosubstituted olefins. It was difficult to polymerize.
In view of such 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.

In order to solve the above-described problems of the present invention, the present inventors have made various searches in the production of polar group-containing olefin copolymers.
As a result, the inventors have found that the above problems can be solved by using a specific structure polymerization catalyst and a specific vinylidene comonomer, and have completed the invention. Based on these results, the following invention is provided.

In the above, the background of the creation of the present invention and the basic configuration and features of the invention have been described in general. Here, the overall configuration of the present invention will be summarized and summarized as follows. ] To [16].
Here, the polar group-containing olefin copolymer having a specific structure in [1] is constituted as a basic invention [1], and [2] the following inventions add an additional requirement to the basic invention, or The embodiment is shown. The inventions [4] to [16] define additional requirements for the production method of the polar group-containing olefin copolymer having the 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 comprising 20 to 0.001 mol% of a structural unit derived from at least one selected from the group consisting of polar group-containing monomers represented by the following general formulas (1), (2) and (3) A copolymer,
And,
A polar group-containing olefin copolymer, wherein the degree of methyl branching calculated by ¹³ C-NMR analysis is a linear random copolymer of 20 or less per 1,000 carbons of the copolymer.

[In the 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 an alkyl group having 1 to 20 carbon atoms. An alkylthio group, a substituted amino group having a hydrocarbon group having 1 to 20 carbon atoms, a cyano group, a carboxyl group, an ester group having a hydrocarbon group having 1 to 20 carbon atoms, or a hydrocarbon having 1 to 20 carbon atoms 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, and may form 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], wherein

[4]
It is a manufacturing method of the polar group content olefin copolymer given in any 1 paragraph of [1]-[3],
A method for producing a polar group-containing olefin copolymer, wherein polymerization is performed using a compound containing a group 8-10 transition metal.

[5]
The compound containing a group 8-10 transition metal is a metal complex obtained by reacting a carbene precursor compound with a complex precursor of a group 8-10 transition metal compound, [4] The manufacturing method of polar group containing olefin copolymer as described in any one of.

[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 represents 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) represents a _{^{(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 represents 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. And y represents an integer of 0 to 2). R ¹ and R ² are each independently a hydrocarbon group having 1 to 40 carbon atoms which 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 which may contain a hydrogen atom or a hetero atom, and may be condensed with a part of the ring consisting of X ¹ . A ⁻ represents a counter anion and represents an arbitrary 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. It may have a substituent on the ring X ² forms. 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 the general formula (8) or formula (9), R ⁵ to R ⁹ represents a halogen atom or a heteroatom-containing group or a hydrocarbon group of carbon atoms which may 1 to 40 contain heteroatoms. 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 General Formula (10) or 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 the 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]
The compound containing a group 8-10 transition metal is represented by the following general formula (12) or general formula (13), wherein the polar group-containing olefin copolymer according to [4] is produced. 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 each represent a ligand that is liganded to M ¹ , and each independently represents a C 1-20 hydrocarbon group 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 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 ′, and P (R ³ ) ₂ (O). (Here, R ³ and R ⁴ each independently represents 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. And y represents an integer of 0 to 2). R ¹ and R ² are each independently a hydrocarbon group having 1 to 40 carbon atoms which 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 which may contain a hydrogen atom or a hetero atom, and may be condensed with a part of the ring consisting of X ¹ . A ⁻ represents a counter anion and represents an arbitrary 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 counter cation and represents an arbitrary 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 group 8-10 transition metal is a metal complex represented by the following general formula (C1).

[In the 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 the number of carbon atoms that may be 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 described 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. Substituted with 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, or 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. R ¹⁶ or R ¹⁷ may be bonded to Y ¹ to form a ring structure.
L represents an electron donating ligand,
q is 0, 1/2, 1 or 2. ]

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

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

[In the 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 C1-C20 hydrocarbon group substituted with a silyl group or a halogen atom. M, X, R ¹⁵ , R ¹⁶ , R ¹⁷ , L and q represent the same meaning as described in the general formula (C1). ]
The manufacturing method of the polar group containing olefin copolymer as described in [13] which is a metal complex shown by these.

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

[In formula (C3), three R ¹¹⁶ each independently represents 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 represent the same meaning as described in the general formula (C2). ]
The manufacturing method of the polar group containing olefin copolymer as described in [15] which is a metal complex shown by these.

In the present invention, a novel polar group-containing olefin copolymer using a specific vinylidene comonomer is provided.
Moreover, in this invention, it is possible to manufacture a polar group containing olefin copolymer using the post-metallocene complex catalyst of 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 and the production method and use of the copolymer will be described specifically and in detail for each item.
[1] Polar group-containing monomer of the present invention (1) 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 the 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 an alkyl group having 1 to 20 carbon atoms. An alkylthio group, a substituted amino group having a hydrocarbon group having 1 to 20 carbon atoms, a cyano group, a carboxyl group, an ester group having a hydrocarbon group having 1 to 20 carbon atoms, or a hydrocarbon having 1 to 20 carbon atoms 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, and may form a cyclic structure with FG. good. ]

(2) Specific examples of polar group-containing monomer In formulas (1), (2) and (3), FG is preferably a halogen atom, an aryl group having 6 to 20 carbon atoms, or an alkyl 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 atom. An acyl group having an atom, an aryl group having 1 to 20 carbon atoms, an ester group having a hydrocarbon group having 1 to 20 carbon atoms, or a hydrocarbon group having 1 to 20 carbon atoms.

Here, the FG will be described in detail.
The halogen atom is not particularly limited. The halogen atom is preferably chlorine, fluorine, bromine or iodine.

  Specific examples of the aryl group having 6 to 20 carbon atoms include phenyl group, methylphenyl group, n-propylphenyl group, i-propylphenyl group, n-butylphenyl group, i-butylphenyl group, and s-butyl. Preferred examples include a phenyl group, a t-butylphenyl group, an n-hexylphenyl group, a trimethylphenyl group, a pentamethylphenyl group, a biphenyl group, and a naphthyl group.

  Specific examples of the alkoxy group having 1 to 20 carbon atoms include methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy, s-butoxy, t-butoxy, n-pentoxy, n- Preferable examples include hexoxy, cyclopropoxy, cyclopentoxy, cyclohexoxy, n-octoxy, n-deoxy and the like.

  Specific 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. A group, a decylthio group, a dodecylthio group and the like can be preferably exemplified.

  Specific examples of the substituted amino group having a hydrocarbon group having 1 to 20 carbon atoms include 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 group, a diphenylamino group, a bis (trimethylsilyl) amino group, a morpholinyl group, and the like.

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

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

Next, R will be described in detail.
In the 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, an annular structure may be formed with the FG.
Specifically, R which is an alkyl group having 1 to 10 carbon atoms is 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, 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, 2-propylheptyl, 2-octyl, 3-nonyl, cyclopropyl, cyclobutyl, cyclopentyl, methylcyclopentyl, cyclohexyl, methyl Cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclododecyl group, 1-adamantyl group, and suitably a 2-adamantyl group.
R, which is an alkyl group having 1 to 10 carbon atoms substituted with a halogen atom, preferably includes a structure in which the aforementioned hydrocarbon group having 1 to 20 carbon atoms is substituted with a halogen atom. A specific preferred example is a trifluoromethyl group.
Preferable specific examples of R which is a halogen atom are fluorine, chlorine and bromine. Of 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 an α-olefin having 3 to 10 carbon atoms. Preferable specific examples include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 3-methyl-1-butene and 4-methyl-1-pentene. A specific example is ethylene. Moreover, one type of α-olefin may be used, or a plurality of α-olefins may be used in combination.

[3] Copolymer composition (composition of polar group-containing olefin copolymer)
In the polar group-containing olefin copolymer in 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 preferable to select in the range of 0.010-5.000 mol%.
The amount of the structural unit can be controlled by selecting the catalyst, the amount of polar group-containing monomer added during polymerization, and the pressure and temperature during polymerization. As specific means to increase the amount of structural units derived from polar group-containing monomers in the copolymer, increasing the amount of polar group-containing monomers added during polymerization, reducing the olefin pressure during polymerization, and increasing the polymerization temperature are effective. is there. For example, it is required to adjust these factors to control the target copolymer region.

In the polar group-containing olefin copolymer in the present invention, the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) determined by gel permeation chromatography (GPC) is in the range of 1.5 to 3.5. Preferably there is. Among these, the range of 1.6 to 3.3 is more preferable, and the range of 1.7 to 3.0 is particularly preferable.
When Mw / Mn satisfies this range, various processability including the molding of the laminate is sufficient, and the adhesive strength is excellent. Mw / Mn can be controlled by selecting a catalyst to be 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. Of these, 60 ° C to 135 ° C is particularly preferable, and 70 ° C to 135 ° C is more preferable. When this range is satisfied, heat resistance and adhesiveness are excellent.
This melting point can be controlled by selection of the catalyst to be 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, reduction of the polar group-containing monomer amount added during polymerization, increase of the olefin pressure during polymerization, and reduction of the polymerization temperature are effective. For example, it is required to adjust these factors to control the target copolymer region.

The polar group-containing olefin copolymer in the present invention is a linear random copolymer having a methyl branching degree calculated by ¹³ C-NMR analysis of 20 or less per 1,000 carbons of the copolymer. This degree of methyl branching is preferably 18 or less per 1,000 carbons of the copolymer.
When the methyl branch satisfies this value, the elastic modulus is high and the mechanical strength of the molded body is also high.
The degree of methyl branching can be controlled by selecting the catalyst to be used and the polymerization temperature. As a specific means for reducing the degree of methyl branching of the copolymer, it is effective to lower the polymerization temperature. For example, it is required to adjust these factors to control the target copolymer region.

[4] Compound containing transition metal As an example of the method for producing the polar group-containing olefin copolymer of the present invention, there is a method of polymerizing using a compound containing a group 8-10 transition metal.
Specific examples of preferred transition metals include vanadium atom, niobium atom, tantalum atom, chromium atom, molybdenum atom, tungsten atom, manganese atom, iron atom, ruthenium atom, cobalt atom, rhodium atom, nickel atom, palladium atom and the like. . Among these, vanadium atom, iron atom, cobalt atom, nickel atom and palladium atom are preferable, and nickel atom and palladium atom are particularly preferable. These metals may be single or plural.

  The compound containing a group 8-10 transition metal is preferably a metal complex obtained by reacting a carbene precursor compound with a complex precursor of a group 8-10 transition metal compound.

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

In the general formula (4) and the 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, 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 ', represent a _{^{P (R 3) 2 (O}} ). (Here, R ³ and R ⁴ each independently represents 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. And y represents an integer of 0 to 2). R ¹ and R ² are each independently a hydrocarbon group having 1 to 40 carbon atoms which 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 which may contain a hydrogen atom or a hetero atom, and may be condensed with a part of the ring consisting of X ¹ . A ⁻ represents a counter anion and represents an arbitrary 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 having two nitrogen atoms (5-membered imidazole). The 5-membered ring is condensed with the other ring, and the condensed ring contains one nitrogen atom to form a carbene at the carbon atom of the condensed 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 carbene, and the ring structure is connected so as to include a nitrogen atom in the 5-membered ring structure that generates carbene. ing.

  In the N-heterocyclic carbene precursor represented by the general formula (4) or the general formula (5), a ring fused to a 5-membered ring may be further condensed. It is represented by 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. It may have a substituent on the ring X ² forms. A ⁻ , Z, R ¹ , R ² , X ¹ , E ¹ and E ² are as described in the general formula (4) or the general formula (5).

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

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

  Specific examples of the precursor compound represented by the general formula (8) or the general formula (9) are shown below together with the synthesis method thereof. Detailed contents are described in JP-A-2006-135777.

The precursor compound (b) is 2- (2,6-diisopropylphenyl) imidazo [1,5-a] quinolinium-9-olate.

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

  Another example of the N-heterocyclic carbene precursor represented by the general formula (4) or the general formula (5) is represented by the following general formula (10) or the general formula (11).

In General Formula (10) or General Formula (11), R ¹⁰ represents a halogen atom, a heteroatom-containing group, or a hydrocarbon group having 1 to 40 carbon atoms that 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, typical examples of the carbene precursor compound of the present invention are as follows.

In the 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 ', represent a _{^{P (R 3) 2 (O}} ).

Specific examples of Z _{are, 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 = _{CHCH 3, N = CHCH 2 CH} 3, N = CH (Dip), CH = NH, CH = NCH 3, CH = NCH 2 CH 3, CH = N (Dip), C (CH 3) = 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 , CO ₂ CH ₃ , CO ₂ CH ₂ CH ₃ , CO ₂ K, C (O) NH ₂ , C (O) N (CH ₃ ) ₂ , C (O) N (CH ₂ CH ₃ ) ₂ , C ( _{O) H, C (O)} CH 3, C (O) CH 2 CH 3, SO 2 H, S _{2 CH 3, SO 2 CH 2} CH 3, SOH, SOCH 3, SOCH 2 CH 3, OSO 2 H, OSO 2 CH 3, OSO 2 CH 2 CH 3, P (O) (OH) (CH 3), P (O) (OCH ₃ ) (CH ₃ ), SO ₃ Na, SO ₃ K, PO ₃ Na ₂ , PO ₃ K ₂ , P (O) (OH) ₂ Na, P (O) (OCH ₃ ) ₂ K ^{_{, P (t Bu) 2 (}} O), P (i Pr) 2 (O), such as _PPh 2 (O) are exemplified. Here, Dip 2,6-diisopropylphenyl group, Ph refers to a phenyl ^group, i Pr is an isopropyl ^group, t Bu denotes a tertiary butyl group.

R ¹ and R ² are each independently a hydrocarbon group having 1 to 40 carbon atoms which may contain a hydrogen atom or a hetero atom. Here, specific examples of the hydrocarbon group having carbon atoms of 1 to 40 also contain _{heteroatoms, 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, and is an alkyl group, a cycloalkyl group, or an aryl group. Preferred specific examples are 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- 4-methylphenyl group and the like.

Ra is a hydrocarbon group having 1 to 10 carbon atoms which may contain a hydrogen atom or a hetero _{atom, CH 3, CH 2 CH 3} , C (O) CH 3, C (O) CH 2 CH 3, CH ₂ OCH ₃ , CH ₂ OCH ₂ CH ₃ , CH ₂ NH ₂ , CH ₂ CH ₂ NH _{2 and the} like are exemplified.
A ⁻ represents a counter anion, and examples of optional anions include COO ⁻ , Cl ⁻ and Br ⁻ . Some of the foregoing the Z is a substituted group that is negatively charged monovalent out leaving groups, in this case to become electrically neutral in the molecule, A ^- does not require.

In the general formulas (8) to (11), examples of the halogen atom, the hetero atom-containing group, or the hydrocarbon group having 1 to 40 carbon atoms that may contain a hetero atom include a fluorine atom, a chlorine atom, and a bromine atom. _{, CH 3, CH 2 CH 3} , C (O) CH 3, C (O) CH 2 CH 3, CH 2 OCH 3, CH 2 OCH 2 CH 3, CH 2 NH 2, CH 2 CH 2 NH 2, NO ₂ etc. are illustrated.
More specifically, the hydrocarbon group is preferably a hydrocarbon group having 1 to 30 carbon atoms, and is an alkyl group, a cycloalkyl group, or an aryl group. Preferred specific examples are 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, Examples include tricyclohexylmethyl group, 1,1-dimethyl-2-phenylethyl group, isopropyl group, 1-dimethylpropyl group, phenyl group, biphenyl group, anthracenyl group, 2,4,6-trimethylphenyl group.

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

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

Formula (12) or the general formula (13), ^{M 1} represents a transition metal belonging to Group 8 to Group 10 of the periodic table. L ¹ and L ² each represent a ligand that is liganded to M ¹ , and each independently represents a C 1-20 hydrocarbon group 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 the general formula (4) or the general formula (5). A ⁺ represents a counter cation, and examples of arbitrary cations include K ⁺ and Na ⁺ . Depending on the valence of M ¹ and the type of Z, L ¹ and L ² , the whole complex may be negatively charged, in which case the counter cation 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 the general formula (12) or the general formula (13) include Fe, Co, Ni, Pd, and Pt. Examples of L ¹ and L ² of the ligand include a halogen atom, a methyl group, a phenyl group, a benzyl group, pyridine, and 2,6-lutidine.

Examples of the metal complex represented by the general formula (12) or the general formula (13) are shown below together with the synthesis method thereof. Detailed contents are described in JP-A-2006-135777.
The complex synthesis reaction may be performed in a reactor used for polymerization or copolymerization of α-olefin, or may be performed in a container different 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 isolation.

  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 derived from 2- (2,6-diisopropylphenyl) imidazo [1,5-a] quinolinium-9-oleate and Ni (cod) ₂ (cod is 1,5-cyclooctadiene). 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 2nd example of a metal complex is shown 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), Y ¹ represents a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, carbon Represents a divalent hydrocarbon group having 1 to 70 carbon atoms which may be substituted with one or more groups selected from an ester group having 2 to 10 atoms, a silyl group, and a halogen atom, and 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 described 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. Substituted with 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, or 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. R ¹⁶ or R ¹⁷ may be bonded to Y ¹ to form a ring structure.
L represents an electron-donating ligand, and q is 0, 1/2, 1 or 2.
In the present specification, “hydrocarbon” includes saturated and unsaturated aliphatic hydrocarbons and aromatic hydrocarbons. Moreover, a chain structure and a cyclic structure are included.

Hereinafter, the structure of the general formula (C1) will be described.
M represents a metal atom of Group 10 of the periodic table. Examples of the metal atom of Group 10 of the periodic table include Ni, Pd, and Pt. Ni and Pd are preferable, and Pd is more preferable from the viewpoint of catalytic activity and the molecular weight of the obtained polymer.
X is a phosphorus atom (P) or an arsenic atom (As), and is coordinated to the central metal M by two electrons. X is preferably P 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. Substituted with 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, or an amide group having 2 to 10 carbon atoms. Substitution 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.

Preferable specific examples of the halogen atom represented by R ¹⁵ are a fluorine atom, a chlorine atom and a bromine atom. Of 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. A group or an aryl group.
Preferred examples are 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, 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, methylcyclo Nthyl 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 -An ethylphenyl group etc. are mentioned.
Among these, more preferred substituents are a methyl group and a benzyl group, and particularly preferred is a methyl group.

The hydrocarbon group having 1 to 30 carbon atoms that is substituted with a halogen atom represented by R ¹⁵ is preferably a substitution in which the aforementioned hydrocarbon group having 1 to 30 carbon atoms is substituted with a fluorine atom, a chlorine atom, or a bromine atom Specific examples of preferred groups include a trifluoromethyl group and a pentafluorophenyl group.

The hydrocarbon group having 2 to 30 carbon atoms substituted by the alkoxy group having 1 to 10 carbon atoms represented by R ¹⁵ is preferably a methoxy group, an ethoxy group, or the above-described hydrocarbon group having 1 to 30 carbon atoms. It is a substituent substituted with an isopropoxy group, 1-propoxy group, 1-butoxy group, or t-butoxy group. More preferably, it is a C2-C6 hydrocarbon group substituted by a methoxy group or an ethoxy group, and specifically includes 1- (methoxymethyl) ethyl group, 1- (ethoxymethyl) ethyl group, 1- (Phenoxymethyl) ethyl group, 1- (methoxyethyl) ethyl group, 1- (ethoxyethyl) ethyl group, di (methoxymethyl) methyl group, di (ethoxymethyl) methyl group, di (phenoxymethyl) methyl group It is done. Particularly preferred are 1- (methoxymethyl) ethyl group and 1- (ethoxymethyl) ethyl group.

The hydrocarbon group having 7 to 30 carbon atoms that is substituted with the aryloxy group having 6 to 20 carbon atoms represented by R ¹⁵ is preferably a phenoxy group or 4 to 4 hydrocarbon group having 1 to 30 carbon atoms. -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 C1-C6 hydrocarbon group substituted with a phenoxy group or a 2,6-dimethylphenoxy group, and particularly preferred is a 1- (phenoxymethyl) ethyl group or 1- (2,6 -A dimethylphenoxy group methyl) ethyl group.

The hydrocarbon group having 3 to 30 carbon atoms substituted by the amide group having 2 to 10 carbon atoms represented by R ¹⁵ is preferably an acetamide group or propionylamino group having the above-described hydrocarbon group having 1 to 30 carbon atoms. Group, a butyrylamino group, an isobutyrylamino group, a valerylamino group, an isovalerylamino group, a pivaloylamino group, and 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 a preferable specific example thereof is a methoxy group, An ethoxy group, an isopropoxy group, a 1-propoxy group, a 1-butoxy group, a t-butoxy group, and the like. Among these, a more preferred substituent is a methoxy group, an ethoxy group, or an isopropoxy group, and particularly preferably a 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 preferred specific examples are phenoxy group, 4-methylphenoxy group, 4-methoxyphenoxy group. 2,6-dimethylphenoxy group, and 2,6-di-t-butylphenoxy group. Among these, a more preferable substituent is a phenoxy group or a 2,6-dimethylphenoxy group, and a phenoxy group is particularly preferable.

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 preferred specific examples are acetyloxy group, propionyloxy group, butyryloxy group, isobutyryloxy group. , Valeryloxy group, isovaleryloxy group, pivaloyloxy group, 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 preferable groups as R ¹⁵ , more preferably, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 2 to 30 carbon atoms substituted with an alkoxy group, and an alkoxy having 1 to 20 carbon atoms. Particularly preferred specific 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. R ¹⁶ or R ¹⁷ may combine with Y ¹ to form a ring structure.

The alkoxy group represented by R ¹⁶ and R ¹⁷ is preferably an alkoxy group having 1 to 20 carbon atoms, and examples thereof include a methoxy group, an ethoxy group, a propoxy group, and an isopropoxy group. As the aryloxy group represented by R ¹⁶ and R ¹⁷ , those having 6 to 24 carbon atoms are preferable, and examples thereof include a phenoxy group. Examples of the silyl group represented by R ¹⁶ and R ¹⁷ include a 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, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, 1-adamantyl, trifluoro Tyl 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, 3,5-dimethoxy Phenyl 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 ′, 6′-triisopropyl -2-biphenyl group and the like.

R ¹⁶ and R ¹⁷ may be the same or different. R ¹⁶ and R ¹⁷ may be bonded to form a ring structure. R ¹⁶ and / or R ¹⁷ may combine 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. The alkyl group having 1 to 10 carbon atoms is preferably a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, or a t-butyl group. 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 like. A cycloalkyl group represented by the following general formula (5) can be used. Particularly preferred.

In the formula, R represents an optionally substituted alkylene group having 1 to 14 carbon atoms, and R ¹⁹ , R ¹¹⁰ and R ¹¹¹ each independently represent a hydrogen atom, an alkoxy group, an aryloxy group, silyl group, an amino group or a halogen atom, a hydrocarbon group of 1 or more carbon atoms which may be substituted with group 1 to 30 selected from alkoxy and aryloxy radicals, R ⁹ and R ^10, At least one of them is not a hydrogen atom, but R ¹⁹ , R ¹¹⁰ , R ¹¹¹ and the alkylene group R may be bonded to each other to form a ring structure. In the formula, a bond between a carbon atom and X in the general formula (C1) is also shown.

Furthermore, it is preferable that both of R ¹⁶ and R ¹⁷ are cycloalkyl groups represented by the general formula (5) for ease of synthesis.

As described above, in the general formula (5), at least one of R ¹⁹ and R ¹¹⁰ is not a hydrogen atom. It is considered that the substituent R ¹⁹ or R ^{110 that} is not a hydrogen atom suppresses the chain transfer of the polymer due to β-hydrogen elimination during the polymerization reaction and improves the molecular weight of the resulting polymer. R ¹⁹ , R ¹¹⁰ and R ¹¹¹ represent an alkoxy group, an aryloxy group, a silyl group, an amino group, or a carbon atom which may be substituted with one or more groups selected from a halogen atom, an alkoxy group and an aryloxy group Specific examples of the hydrocarbon group having 1 to 30 include those similar to the specific examples of R ¹⁶ and R ¹⁷ described above.
As the alkylene group R, those having 2 to 6 carbon atoms are preferable, and those having 4 carbon atoms are more preferable.

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. Further, at least one of R ¹⁹ and R ¹¹⁰ is preferably an isopropyl group.

Hereinafter, specific examples of the X—R ¹⁶ or X—R ¹⁷ moiety when R ¹⁶ or R ¹⁷ represents a group represented by the general formula (5) will be given. Me represents a methyl group, and the bond between X and M, and X and Y ¹ is omitted.

Among these, R ¹⁶ and R ¹⁷ are preferably 2-isopropyl-5-methylcyclohexyl group (menthyl group) represented by the following formula. More preferably, R ¹⁶ and R ¹⁷ are both menthyl groups.

In General Formula (C1), Q is represented by -S (= O) ₂ -O-, -C (= O) -O-, -P (= O) (-OH) -O-, or -S-. This is a moiety that coordinates one electron to M. The left side of each formula is bound to Y ^1, the right side is bonded to M. Among these, -S (= O) _2- O- is particularly preferable from the viewpoint of catalytic activity.

In the Y ¹ -Q site, an oxygen atom or sulfur atom having a high electronegativity is coordinated to the metal atom M by one electron. Bonding electrons between Y ¹ -Q-M is ^formally, can be indicated as a ^Y 1 -Q anion state, the M cation state.

In 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 be present.
Examples of the silyl group as a substituent on Y ¹ include a trimethylsilyl group, a triethylsilyl group, a tripropylsilyl group, a tributylsilyl group, a triisopropylsilyl group, a t-butyldimethylsilyl group, and a t-butyldiphenylsilyl group. In particular, a trimethylsilyl group and a triethylsilyl group are preferable.
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. Preferable specific examples include methoxy group, ethoxy group, isopropoxy group, phenoxy group and the like, and methoxy group and phenoxy group are particularly preferable.
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 are a methoxycarbonyl group, an ethoxycarbonyl group, and n-propoxycarbonyl. Group, isopropoxycarbonyl group, n-butoxycarbonyl group, t-butoxycarbonyl group, (4-hydroxybutoxy) carbonyl group, (4-glycidylbutoxy) carbonyl group, phenoxycarbonyl group, succinic anhydride group, succinimide Groups. Preferred are a methoxycarbonyl group, an ethoxycarbonyl group, a (4-hydroxybutoxy) carbonyl group, and a succinic anhydride group, and particularly preferred are a methoxycarbonyl group and a succinic anhydride group.
Examples of the halogen atom as a substituent on Y ¹ include fluorine, chlorine, bromine and the like, and fluorine and chlorine are particularly preferable.
The hydrocarbon group having 1 to 70 carbon atoms is preferably a hydrocarbon group having 1 to 12 carbon atoms, preferably an alkylene group or an arylene group, and an arylene group is particularly preferable.

Y ¹ is a cross-linking site that binds X and Q sites. Specific examples of Y ¹ in which X is a P atom are shown below. Here, the plurality of R ¹⁰⁴ may be the same or different, and 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, or 6 to 20 carbon atoms. Represents an aryloxy group, a silyl group, or a hydrocarbon group having 1 to 20 carbon atoms substituted with 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 described for Y ¹ . Examples of the hydrocarbon group having 1 to 20 carbon atoms represented by R ¹⁰⁴ and the hydrocarbon group having 1 to 20 carbon atoms substituted with a halogen atom include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, n- Butyl, isobutyl, sec-butyl, t-butyl, n-pentyl, 2-pentyl, 3-pentyl, neopentyl, n-hexyl, 2-hexyl, 3-hexyl, cyclo Propyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclododecyl group, 1-adamantyl group, 2-adamantyl group, exo-norbornyl group, endo-norbornyl group, menthyl group, neomenthyl group, Trifluoromethyl group, benzyl group, 4′-trifluoromethylbenzyl group, phenyl group, 2-methylphenyl Nyl group, 3-methylphenyl group, 4-methylphenyl group, 2,6-dimethylphenyl group, 3,5-dimethylphenyl group, 2,4,6-trimethylphenyl group, 2-isopropylphenyl group, 3-isopropyl Phenyl 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 (trifluoromethyl) phenyl group, 1-naphthyl group, 2-naphthyl group, 2-furyl group, 2-biphenyl A group, 2′-methyl-2-biphenyl group, 2 ′, 4 ′, 6′-triisopropyl-2-biphenyl group, Group, an allyl group, a butenyl group, a cyclohexenyl group, a cinnamyl group, a styryl group, an anthracenyl group, and a fluorenyl group.

The substituent R ¹⁶ or R ¹⁷ may be bonded to the Y ¹ site to form a ring structure. Specific examples include the following structures. In the following example, 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 preferable.

In the 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 C1-C20 hydrocarbon group substituted with a silyl group or a halogen atom. Specific examples thereof are the same as those described in ^R104 . M, X, R ¹⁵ , R ¹⁶ , R ¹⁷ , L and q represent the same meaning as described in the general formula (C1).

In the general formula ^(C2), those represented by the following formula ^{R 12} is a silyl group (C3) is preferred.

In the formula, each of three independent R ¹¹⁶ may be the same or different and represents 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 represent the same meaning as described in the general formula (C2).

In the 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 metal complex of the catalyst represented by the general formula (C1) can be synthesized by a method similar to the method 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 the general formula (C1).

In the compounds represented by general formula (C2) and general formula (C3), Y ¹ and Q in general formula (C1) should be specific groups corresponding to general formula (C2) and general formula (C3). Can be synthesized.

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

The divalent M source is (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) dimethyl palladium _(II): PdMe 2 (TMEDA), bis (acetylacetonato) palladium _{(II): Pd (acac)} 2 (acac = acetylacetonate), (trifluoromethanesulfonate palladium (II) : Pd (OSO ₂ CF ₃ ) ₂ is di As nickel sources, (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), nickel trifluoromethanesulfonate (II): Ni (OSO ₂ CF ₃ ) ₂ .

The metal complex represented by the general formula (C1) can be used after being isolated, but this can be obtained by contacting a metal source containing M and a ligand precursor in the reaction system without isolating the complex. Can also be subjected to polymerization in situ. In particular, when R ¹⁵ in the general formula (C1) is a hydrogen atom, after reacting a metal source containing zero-valent M with a ligand precursor, the polymer can be directly subjected to polymerization without isolation of the complex. preferable.

  In this case, the ligand precursor is represented by the general formula (C1):

(The symbols in the formula have the same meaning as described above.)
Indicated by

  The ratio ((C1 ligand) / M) of the M source (M) and the ligand precursor (C1-1) (C1 ligand) in the general formula (C1) is 0.5 to 2.0. It is preferable to select in the range of 1.0 to 1.5.

  When isolating the metal complex of the general formula (C1), it is also possible to use one that has been previously stabilized by coordination with the electron donating ligand (L). 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. In addition, when q is 0, it means that there is no ligand.

The electron donating ligand (L) is a compound having an electron donating group and capable of coordinating to the metal atom M and stabilizing the metal complex.
As the electron donating ligand (L), dimethyl sulfoxide (DMSO) is exemplified as one having a sulfur atom. As a compound having a nitrogen atom, a trialkylamine having 1 to 10 carbon atoms in an alkyl group, a dialkylamine having 1 to 10 carbon atoms in an alkyl group, 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), Acetonitrile, benzonitrile, quinoline, 2-methylquinoline and the like can be mentioned. 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 an α-olefin such as ethylene and a (meth) acrylic acid ester or an allyl monomer, which has good catalytic activity, high molecular weight and high comonomer content. It is a catalyst that enables production.
This catalyst has the aforementioned metal complex as the main catalyst component (A), and as the component (B), a compound that reacts with the component (A) to form an ion pair or an ion-exchange layered silicate. If necessary, the organoaluminum compound of component (C) is used.

Specific examples of the component (B) include the following (B-1) to (B-3).
(B-1) Aluminum Oxy Compound (B-2) An ionic compound or Lewis acid capable of reacting with component (A) to convert component (A) into a cation (B-3) solid acid

  (B-1) In the aluminum oxy compound, it is well known that the aluminum oxy compound can activate the post metallocene complex. As such a compound, the following general formulas (II) to (IV) are specifically mentioned. The compound represented by these is mentioned.

In each of the above general formulas, R ^a represents a hydrogen atom or a hydrocarbon group, preferably ^a C 1-10 hydrocarbon group, particularly preferably ^a C 1-6 hydrocarbon group. Moreover, several ^Ra may be same or different, respectively. 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 compounds also referred to as aluminoxanes. Among these, methylaluminoxane or methylisobutylaluminoxane is preferable. The above aluminoxanes can be used in combination within a group and between groups. And said aluminoxane can be prepared on well-known various conditions.
The compound represented by the third general formula is 10: 1 to 1 type trialkylaluminum or two or more types of trialkylaluminum and alkylboronic acid represented by the general formula R ^b B (OH) ₂ . It can be obtained by a 1: 1 (molar ratio) reaction. 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 a Lewis acid capable of reacting with the component (A) to convert the component (A) into a cation. Examples of such an ionic compound include carbonium. Examples thereof include complexes of cations such as cations and ammonium cations with organic boron compounds such as triphenylboron, tris (3,5-difluorophenyl) boron, and tris (pentafluorophenyl) boron.
Examples of the Lewis acid as described above include various organic boron compounds such as tris (pentafluorophenyl) boron. Alternatively, metal halide compounds such as aluminum chloride and magnesium chloride are exemplified.
In addition, a certain thing of said Lewis acid can also be grasped | ascertained as an ionic compound which can react with a component (A) and can convert a 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 the general formulas (4) to (11), and a group 8 to 10 (late period type; Fe, Co, Ni, Pd, etc.). An α-olefin polymerization catalyst obtained by reacting with a transition metal compound.
In general, the synthesis of the catalyst composition can be carried out by bringing a group 8-10 transition metal compound and a novel carbene precursor compound or phosphorus sulfonic acid compound into contact in a solution or slurry.
The transition metal compound is preferably a Group 10 transition metal compound, and is bis (dibenzylideneacetone) palladium, tetrakis (triphenylphosphine) palladium, palladium sulfate, palladium acetate, bis (allyl palladium chloride), palladium chloride, 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 (methylethylenediamine) nickel, (cyclooctadiene) nickel (methyl) chloride, or the like.

The complex formation reaction may be performed in a reactor used for copolymerization with an α-olefin, or may be performed 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 isolation. Furthermore, it can be carried out in the presence of a porous carrier described later.
Moreover, the catalyst composition of this invention may be used individually by 1 type, and may use multiple types of catalyst composition together. Particularly, for the purpose of widening the molecular weight distribution and the comonomer content distribution, the combined use of such a plurality of catalyst compositions is useful.

The polymerization catalyst of the present invention may be used alone or may be used by being supported on a carrier. As a usable carrier, any carrier can be used as long as the gist of the present invention is not impaired.
In general, inorganic oxides and polymer carriers can be preferably used. Specific examples include SiO ₂ , Al ₂ O ₃ , MgO, ZrO ₂ , TiO ₂ , B ₂ O ₃ , CaO, ZnO, BaO, ThO ₂ , or a mixture thereof, 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 silicate, polyethylene carrier, polypropylene carrier, A polystyrene carrier, polyacrylic acid carrier, polymethacrylic acid carrier, polyacrylic acid ester carrier, polyester carrier, polyamide carrier, polyimide carrier and the like can be used.
These carriers are not particularly limited in particle size, particle size distribution, pore volume, specific surface area, etc., and any one can be used.

The catalyst for olefin polymerization of the present invention can be prepared by bringing the components (A) and (B) into contact with each other in the presence or absence of the monomer to be polymerized inside and outside the polymerization tank.
That is, the components (A) and (B) and the component (C) may be separately introduced into the polymerization tank as necessary, or the components (A) and (B) are introduced into the polymerization tank after contacting them in advance. May be. Further, the component (C) may be impregnated with the mixture of the components (A) and (B) and then introduced into the polymerization tank.
The above-mentioned contact of each component may be performed in an inert hydrocarbon solvent such as pentane, hexane, heptane, toluene and xylene in an inert gas such as nitrogen. 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 thus prepared may be used without washing after preparation, or may be used after washing. Furthermore, you may use it combining a component newly as needed after preparation.

  The catalyst component may be prepolymerized in the presence of olefin in the polymerization tank or outside the polymerization tank. Olefin means a hydrocarbon containing at least one carbon-carbon double bond, and examples thereof include ethylene, propylene, 1-butene, 1-hexene, 3-methylbutene-1, styrene, divinylbenzene, and the like. There is no restriction | limiting, You may use the mixture of these and another olefin. Preferred are olefins having 2 or 3 carbon atoms. The olefin can be supplied by any method, such as a supply method for maintaining the olefin at a constant speed or in a constant pressure state, a combination thereof, or a stepwise change.

[7] Copolymerization reaction The copolymerization reaction in the present invention may be carried out using hydrocarbon solvents such as propane, n-butane, isobutane, n-hexane, n-heptane, toluene, xylene, cyclohexane, methylcyclohexane, and liquefied α-olefins. Liquid, 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 such a polar solvent. Moreover, you may use the mixture of the liquid compound described here as a solvent. In order to obtain high polymerization activity and high molecular weight, the above hydrocarbon solvents are more preferable.

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

In the present invention, the polymerization mode is not particularly limited. Slurry polymerization in which at least a part of the produced polymer becomes a slurry in the medium, bulk polymerization using the liquefied monomer itself as a medium, gas phase polymerization carried out in the vaporized monomer, or polymer produced in a monomer liquefied at high temperature and high pressure High-pressure ionic polymerization in which at least a part 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. In recycling, these monomers and media may be purified and reused, or may be reused without purification. Conventionally known methods can be used to separate the produced copolymer from the unreacted monomer and medium. For example, methods such as filtration, centrifugation, solvent extraction, and reprecipitation using a poor solvent can be used.

There are no particular restrictions on the copolymerization temperature, copolymerization pressure, and copolymerization time, but usually optimum settings can be made in consideration of productivity and process capability from the following ranges.
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 0.00. It can be selected from the range of 1 minute to 50 hours, preferably 0.5 minutes to 40 hours, more preferably 1 minute to 30 hours.
In the present invention, the copolymerization is generally performed in an inert gas atmosphere. For example, a nitrogen or argon atmosphere can be used, and a nitrogen atmosphere is preferably used. A small amount of oxygen or air may be mixed.

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

Regarding the control of the copolymer composition, a method of controlling a copolymer by supplying a plurality of monomers to a reactor and changing the supply ratio thereof can be generally used. Other methods include controlling the copolymer composition using the difference in monomer reactivity ratio due to the difference in catalyst structure, and controlling the copolymer composition using the polymerization temperature dependence of the monomer reactivity ratio. .
A conventionally known method can be used for controlling the molecular weight of the copolymer. That is, a method for controlling the molecular weight by controlling the polymerization temperature, a method for controlling the molecular weight by controlling the monomer concentration, a method for controlling the molecular weight by using a chain transfer agent, and a control of the ligand structure in the transition metal complex. For example, controlling the molecular weight.
When a chain transfer agent is used, 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 described by way of examples to demonstrate the rationality, significance, usefulness, and superiority of the prior art of the configuration of the present invention.

[1] Method for Analyzing Polymer Structure [1-1] Comonomer Content of Copolymer The comonomer content of the copolymer obtained in the examples was determined by NMR analysis using Ascend 500 manufactured by Bruker. Using 1,1,2,2-tetrachloroethane-d ₂ as a solvent, the molar ratio of ethylene: comonomer was determined by ¹ H-NMR measurement at 120 ° C., and incorp. It was described in Table 1 with the notation (%). incorp. (%) Means comonomer content (mol%).
[1-2] Amount of methyl branch A 200 mg sample was mixed with o-dichlorobenzene / deuterated benzene bromide (C6D5Br) = 4/1 (volume ratio) 2.4 ml and hexamethyldisiloxane which is a chemical shift reference substance. The sample was placed in a 10 mmφ NMR sample tube, purged with nitrogen, sealed, heated and dissolved, and subjected to NMR measurement as a uniform solution. NMR measurement was carried out using an NMR apparatus AVANCE III400 manufactured by Bruker BioSpin Co., Ltd. equipped with a 10 mmφ cryoprobe.
The methyl branching amount is 20.0 ppm when the total integrated intensity of signals in the range of 10 to 180 ppm in a ¹³ C-NMR spectrum is normalized to 1,000, and the average integrated intensity of characteristic signals of 33.2 ppm is 1, It was determined as the number of methyl branches per 000C.

[2] Number average molecular weight (Mn) and weight average molecular weight (Mw)
Tosoh Co., Ltd., TSKgel, GMHHR-H (S) HT column (7.8 mm ID x 30 cm in series) equipped with Tosoh Co., Ltd. high-temperature GPC device, HLC-8121 GPC / HT, It was calculated by size exclusion chromatography (solvent: 1,2-dichlorobenzene, temperature: 145 ° C.) using monodisperse polystyrene as a molecular weight standard substance.
In Table 1, which will be described later, Mw / Mn is indicated by PDI.

Unless otherwise specified in the following synthesis examples, the operation was performed in a purified argon atmosphere, and the solvent was dehydrated and deoxygenated. The metal complex 1 and the metal complex 2 used as the catalyst are described in Non-Patent Document 3; Nozaki et al. , J .; Am. Chem. Soc. , 2015, 137, 10934-10937, Non-Patent Document 11; Japanese Patent Laid-Open No. 2014-219220. As comonomer, methyl methacrylate (MMA); α-methylstyrene (α-MS); TCI, β-methallyl chloride (MACl); TCI ), Methyl butenyl acetate (MBAc); Aldrich, methallyl phenyl ether (MAPE); Alfa Aesar. All of these comonomers were distilled. Among these comonomers, the structural formulas of methyl methacrylate (MMA), methylbutenyl acetate (MBAc), α-methylstyrene (α-MS), and methallyl phenyl ether (MAPE) are shown below.

[3] Synthesis of polar group-containing olefin copolymers of Examples 1, 2, 4, 5, 6, 8, 9, 10, 11, 12 A predetermined amount of the following catalyst (metal complex 1) was added in an argon atmosphere ( In a 50 mL autoclave manufactured by Pressure Glass Industrial Co., Ltd., including the amount described in Table 1, a predetermined amount (amount described in Table 1) of toluene and a predetermined amount (amount described in Table 1) of each comonomer (Table 1). Added). After filling a predetermined amount (the amount described in Table 1) of ethylene, the autoclave was stirred at a predetermined temperature (the temperature described in Table 1) for a predetermined time (the time described in Table 1). After cooling to room temperature, methanol (about 20 mL) was added to the autoclave. The resulting copolymer was recovered by filtration. The copolymer was dissolved in ODCB (ortho-dichlorobenzene) and then reprecipitated in methanol. Then, it was made to dry under reduced pressure and the copolymer was obtained.

[4] Synthesis of polar group-containing olefin copolymers of Examples 3 and 7 In a 50 mL autoclave manufactured by Pressure Glass Industrial Co., Ltd., containing a predetermined amount (amount described in Table 1) of metal complex 1 under an argon atmosphere. A fixed amount (amount described in Table 1) of toluene and a predetermined amount (amount described in Table 1) of each comonomer (described in Table 1) were added. After filling a predetermined amount (the amount described in Table 1) of ethylene, the autoclave was stirred at a predetermined temperature (the temperature described in Table 1) for a predetermined time (the time described in Table 1). After cooling to room temperature, methanol (about 20 mL) was added to the autoclave. The resulting copolymer was recovered by filtration. The copolymer was placed in a Soxhlet extractor and washed with methyl ethyl ketone for 5 days. Then, it was made to dry under reduced pressure and the copolymer was obtained.

[5] Synthesis of polar group-containing olefin copolymer of Example 13 In a 50 mL autoclave manufactured by Pressure Glass Industrial Co., Ltd. containing a predetermined amount (the amount described in Table 1) of the following catalyst (metal complex 2) under an argon atmosphere. A predetermined amount (amount described in Table 1) of toluene and a predetermined amount (amount described in Table 1) of each comonomer (described in Table 1) were added. After filling a predetermined amount (the amount described in Table 1) of ethylene, the autoclave was stirred at a predetermined temperature (the temperature described in Table 1) for a predetermined time (the time described in Table 1). After cooling to room temperature, methanol (about 20 mL) was added to the autoclave. The resulting copolymer was recovered by filtration. The copolymer was dissolved in ODCB (ortho-dichlorobenzene) and then reprecipitated in methanol. Then, it was made to dry under reduced pressure and the copolymer was obtained.

[6] Results and discussion Table 1 shows the experimental results. In any of the Examples, it was confirmed that a polar group-containing olefin copolymer was obtained. According to this example, a novel polar group-containing olefin copolymer that exhibits adhesive properties, printability, or compatible physical properties with a filler or the like is provided. Moreover, according to the present Example, a polar group containing olefin copolymer is efficiently manufactured.
In addition, it was confirmed that the methyl branching degree of the olefin copolymer calculated by ¹³ C-NMR analysis is a linear random copolymer having 20 or less per 1,000 carbons of the copolymer.

  The present invention is not limited to the embodiments described in detail above, and various modifications or 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 exhibits good adhesion and printability, or that exhibits good compatibility with fillers, etc. Since it is an olefin copolymer, it can be used for 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 for applications that require adhesion with other materials, printability, or compatibility with fillers.

Claims (16)

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

[In the 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 an alkyl group having 1 to 20 carbon atoms. An alkylthio group, a substituted amino group having a hydrocarbon group having 1 to 20 carbon atoms, a cyano group, a carboxyl group, an ester group having a hydrocarbon group having 1 to 20 carbon atoms, or a hydrocarbon having 1 to 20 carbon atoms 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, and may form 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 a polar group-containing olefin copolymer according to claim 1, which is an acyloxy group having a hydrocarbon group having 1 to 20 carbon atoms.   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 claim 2.   It is a manufacturing method of the polar group containing olefin copolymer of any one of Claims 1-3, Comprising: It superposes | polymerizes using the compound containing a 8-10 group transition metal, Polar group characterized by the above-mentioned. A method for producing a olefin copolymer.   The compound containing a group 8-10 transition metal is a metal complex obtained by reacting a carbene precursor compound with a complex precursor of a group 8-10 transition metal compound. 4. The method for producing a polar group-containing olefin copolymer according to 4, The said carbene precursor compound is represented by following General formula (4) or General formula (5), The manufacturing method of the polar group containing olefin copolymer of Claim 5 characterized by the above-mentioned.

[In General Formula (4) and General Formula (5), Z represents 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) represents a _{^{(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 represents 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. And y represents an integer of 0 to 2). R ¹ and R ² are each independently a hydrocarbon group having 1 to 40 carbon atoms which 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 which may contain a hydrogen atom or a hetero atom, and may be condensed with a part of the ring consisting of X ¹ . A ⁻ represents a counter anion and represents an arbitrary 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 said carbene precursor compound is represented by the following general formula (6) or general formula (7), The manufacturing method of the polar group containing olefin copolymer of Claim 6 characterized by the above-mentioned.

[In General Formula (6) or General Formula (7), X ² represents a saturated or unsaturated divalent hydrocarbon group having 3 to 9 carbon atoms. It may have a substituent on the ring X ² forms. A ⁻ , Z, R ¹ , R ² , X ¹ , E ¹ and E ² are as described in claim 6. ] The said carbene precursor compound is represented by the following general formula (8) or general formula (9), The manufacturing method of the polar group containing olefin copolymer of Claim 7 characterized by the above-mentioned.

[In the general formula (8) or formula (9), R ⁵ to R ⁹ represents a halogen atom or a heteroatom-containing group or a hydrocarbon group of carbon atoms which may 1 to 40 contain heteroatoms. A ⁻ , Z, R ¹ , R ² , E ¹ and E ² are as defined in claim 6. ] The method for producing a polar group-containing olefin copolymer according to claim 6, wherein the carbene precursor compound described above is represented by the following general formula (10) or general formula (11).

[In General Formula (10) or 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 6 or 8. ] In the 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) , characterized in that a _y, a manufacturing method of the polar group-containing olefin copolymer according to any one of claims 6-9. The said group 8-10 compound containing transition metal is represented by the following general formula (12) or general formula (13), The manufacture of the polar group containing olefin copolymer of Claim 4 characterized by the above-mentioned. 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 each represent a ligand that is liganded to M ¹ , and each independently represents a C 1-20 hydrocarbon group 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 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 ′, and P (R ³ ) ₂ (O). (Here, R ³ and R ⁴ each independently represents 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. And y represents an integer of 0 to 2). R ¹ and R ² are each independently a hydrocarbon group having 1 to 40 carbon atoms which 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 which may contain a hydrogen atom or a hetero atom, and may be condensed with a part of the ring consisting of X ¹ . A ⁻ represents a counter anion and represents an arbitrary 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 counter cation and represents an arbitrary cation. ] The method for producing a polar group-containing olefin copolymer according to claim 11, wherein M ¹ is a transition metal belonging to Group 10 of the periodic table. 5. The method for producing a polar group-containing olefin copolymer according to claim 4, wherein the compound containing a group 8-10 transition metal is a metal complex represented by the following general formula (C1).

[In the 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 the number of carbon atoms that may be 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 described 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. Substituted with 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, or 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. R ¹⁶ or R ¹⁷ may be bonded to Y ¹ to form a ring structure.
L represents an electron donating ligand,
q is 0, 1/2, 1 or 2. ] In the general formula (C1), Q is —S (═O) ₂ —O— (wherein S is bonded to Y ¹ and O is bonded to M). A method for producing an olefin copolymer. The compound represented by the general formula (C1) is represented by the general formula (C2).

[In the 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 C1-C20 hydrocarbon group substituted with a silyl group or a halogen atom. M, X, R ¹⁵ , R ¹⁶ , R ¹⁷ , L and q represent the same meaning as described in the general formula (C1). ]
The manufacturing method of the polar group containing olefin copolymer of Claim 13 which is a metal complex shown by these. The compound represented by the general formula (C2) is a compound represented by the general formula (C3) in which R ¹¹² is a silyl group.

[In formula (C3), three R ¹¹⁶ each independently represents 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 represent the same meaning as described in the general formula (C2). ]
The manufacturing method of the polar group containing olefin copolymer of Claim 15 which is a metal complex shown by these.