JP6913051B2 - A metal complex and a method for producing an α-olefin / (meth) acrylic acid ester copolymer using the metal complex. - Google Patents

Description

The present invention relates to a metal complex and a method for producing an α-olefin / (meth) acrylic acid ester copolymer using the same.

A well-known method is to copolymerize ethylene with vinyl acetate or (meth) acrylic acid ester, which is a vinyl monomer containing a polar group, by radical polymerization at high temperature and high pressure. However, this method has a drawback that the strength of the obtained copolymer is low because a copolymer having low crystallinity is obtained by forming a large number of branches.
In addition, Brookhard et al. Have reported that a copolymer of ethylene and acrylic acid ester can be produced using a palladium complex using an α-diimine ligand as a catalyst. However, the obtained copolymer is rich in branched structure, and the branched has various carbon numbers including a methyl group and an ethyl group, and the number of branches is very large. As a result, the obtained copolymer is obtained. The obtained copolymer had low crystallinity (see, for example, Non-Patent Document 1).

A nickel catalyst using a ligand having phosphorus and oxygen as coordination atoms, and by using a so-called SHOP-based catalyst, ethylene polymerization is possible in a polar solvent, and a linear polymer with few branches can be obtained. It is known. Expecting such polar group resistance of SHOP-based catalysts, copolymerization of ethylene and polar monomers using SHOP-based catalysts has been attempted. However, it has been reported that copolymerization with ethylene proceeds only when the polar group in the polar monomer is separated from the olefin, and the polar group is directly bonded to the olefin (meth) acrylic. No example of copolymerization of an acid ester and an α-olefin has been reported (see, for example, Non-Patent Document 2 and Patent Document 1). Exceptionally, Gibson et al. Copolymerize ethylene and methyl methacrylate using a SHOP-based nickel complex (see, for example, Non-Patent Document 3), but biscyclooctadiene is used as a catalyst component. Nickel (Ni (COD) ₂ ) is required as a phosphine scavenger, and methyl methacrylate is present only at the ends of the polymer and is not incorporated into the main chain other than the ends.

On the other hand, a method of copolymerizing ethylene and an unsaturated carboxylic acid ester with a catalyst composed of a combination of a similar SHOP-based nickel (zero-valent) chelate complex and aluminoxane is disclosed (see, for example, Patent Document 2). .. In the examples of this patent document, an example of copolymerization of ethylene and methyl acrylate is described, but since an amorphous polymer is produced as a by-product, it is necessary to remove the amorphous polymer by acetone extraction. there were. In addition, regarding the obtained copolymer, there is only a description about the methyl acrylate content, and there is no other description about the structure.

Puch et al. (See, for example, Non-Patent Document 4), Nozaki et al. (See, for example, Non-Patent Document 5), Goodall et al. (See, for example, Patent Document 3) have described palladium complexes having phosphinosulfonic acid ligands. It has been reported that a copolymer of ethylene and methyl acrylate can be obtained by using it as a catalyst. However, since the catalysts used in these publicly known documents are rare resources and use expensive palladium, there is a big problem in industrial application.

As described above, the development of a useful transition metal catalyst technology for copolymerizing an olefin and an acrylic acid ester is required. Generally, when polymerizing an olefin with a single-site catalyst, it is compared with a conventional Ziegler-Natta catalyst. , The molecular weight tends to be difficult to increase. Therefore, development of a technique for improving the molecular weight of an olefin polymer or an olefin / acrylic ester copolymer is also required.
Against this background, we use a so-called SHOP system, a nickel catalyst with ligands with phosphorus and oxygen as coordination atoms, to produce linear ethylene and (meth) acrylic with few branches. It has been reported that an acid ester copolymer can be obtained (see Patent Document 4).

U.S. Pat. Nos. 4, 698, 403 Japanese Unexamined Patent Publication No. 64-14217 U.S. Patent Application Publication No. 2007/0049712 International Patent Publication No. 2010/50256

S. Marking et al. , "J. Am. Chem. Soc.", 1998, 120, 888. S. D. Ittel et al. , "Chem. Rev.", 2000, 100, 1169. V. C. Gibson, "Chem.Commun.", 2001, 1964. E. Drent et al. , "Chem.Commun.", 2002, 744. T. Kochi et al. , "Dalton Trans.", 2006, 25. U.S. Klabunde et al. , "J. Polymer. Sci .: Part A: Polymer. Chem.", 1987, 25, 1989.

However, the molecular weight of the copolymer, which is one of the important factors for determining the mechanical properties of the copolymer, is not yet sufficiently high, and there is much room for improvement. In general, it has been clarified that the molecular weight tends to decrease as the (meth) acrylic acid ester content of the copolymer increases, and there is a strong demand for the development of a catalyst that provides a copolymer having a high molecular weight and a high (meth) acrylic acid ester content. Has been done.
In view of such circumstances, an object of the present invention is to provide a catalyst that gives a copolymer having a high molecular weight and a high (meth) acrylic acid ester content, and a method for producing such a copolymer.

As a result of diligent research, the present inventors have found that when a transition metal complex using a ligand having a specific structure is used as a catalyst component, a copolymer having a high molecular weight and a high (meth) acrylic acid ester content can be obtained. The heading has reached the present invention. The present invention is based on such findings and can be realized in the following forms.

[1] A metal complex represented by the following general formula (A).

[In the formula, M represents nickel or palladium. R ³ represents a hydrocarbon group that may contain hydrogen or a heteroatom having 1 to 20 carbon atoms. L ¹ represents a ligand coordinated to M. Further, R ³ and L ¹ may be bonded to each other to form a ring. X ¹ represents oxygen or sulfur. E ¹ represents phosphorus, arsenic or antimony. R ⁴ and R ⁵ each independently represent a hydrocarbon group that may contain a heteroatom having 1 to 30 carbon atoms. R ^{6 to} R ⁸ are hydrocarbon groups that may independently contain hydrogen, halogen, and a heteroatom having 1 to 30 carbon atoms, OR ² , CO ₂ R ² , CO ₂ M', and C (O). ) N (R ¹ ) ₂ , C (O) R ² , SR ² , SO ₂ R ² , OSO ₂ R ² , P (O) (OR ² ) _2-y (R ¹ ) _y , CN, NHR ² , _{^{N (R 2) 2, Si}} (OR 1) 3-x (R 1) x, OSi (OR 1) 3-x (R 1) x, NO 2, SO 3 M ', PO 3 M' 2, P (O) (OR ² ) _{represents 2} M'or an epoxy-containing group. Here, R ¹ represents hydrogen or a hydrocarbon group having 1 to 20 carbon atoms. Further, R ² represents a hydrocarbon group having 1 to 20 carbon atoms. M'represents alkali metal, ammonium, quaternary ammonium or phosphonium, x represents an integer from 0 to 3, and y represents an integer from 0 to 2. R ^{9 to} R ¹³ are hydrogen, and substituents represented by the general formula (B) (R ¹⁴ and R ¹⁵ are hydrocarbon groups having 1 to 6 carbon atoms, which may independently have hydrogen or a heteroatom, respectively. ^{Aryl group having 6 to 12 carbon atoms, an adamantyl group, OR 2} , SR ² , or N (R ² _{) 2} which may have a substituent (which may be bonded to each other to form a ring). Represents. However, ^{at least one of R 9 to} R ¹³ is a substituent represented by the general formula (B), an aryl group having 6 to 12 carbon atoms which may have a substituent, an adamantyl group, OR ² , SR ² or N (R ² ) ₂ . R ^{9 to} R ¹³ do not ring with each other. ]

[2] At ^{least one of R 9 to} R ¹³ is a substituent represented by the general formula (B), an aryl group having 6 to 12 carbon atoms which may have a substituent, or an adamantyl group. The metal complex according to [1].

[3] R ⁹ and R ¹³ have a substituent represented by the general formula (B), an aryl group having 6 to 12 carbon atoms which may have a substituent, an adamantyl group, OR ² , SR ² , or The metal complex according to [1], which is N (R ² ) _2.

[4] R ⁹ and R ¹³ are a substituent represented by the general formula (B), an aryl group having 6 to 12 carbon atoms which may have a substituent, or an adamantyl group. The metal complex according to [3].

[5] An α-olefin / characterized in that an α-olefin and a (meth) acrylic acid ester are copolymerized in the presence of the metal complex according to any one of claims [1] to [4]. A method for producing a (meth) acrylic ester copolymer.

By using the complex of the present invention, a copolymer having a high (meth) acrylic acid ester content and a high molecular weight can be obtained.
According to the production method of the present invention, a copolymer having a high (meth) acrylic acid ester content and a high molecular weight can be obtained.

It is a graph which shows the relationship between the content of t-butyl acrylate unit and Mw in the copolymer of Example and Comparative Example.

The present invention is a reaction product obtained by reacting a specific compound (C) and / or (D) described later with a transition metal complex (G) containing a transition metal of nickel or palladium, that is, a general formula ( A metal complex represented by A) (hereinafter, also referred to as a metal complex (A)), and using it as a catalyst component, (a) α-olefin and (b) (meth) in the presence of the catalyst component. ) A method for producing an α-olefin / (meth) acrylic acid ester copolymer that copolymerizes with an acrylic acid ester. Hereinafter, the constituent monomers of the polymer, the catalyst components, the production method, and the like will be described in detail.
In the following description, the term "polymerization" is a general term for homopolymerization of one type of monomer and copolymerization of a plurality of types of monomers, and is a general term when it is not necessary to distinguish between the two. Is simply described as "polymerization".

1. 1. Polymer Constituent Monomer (a) α-olefin The component (a) in the present invention is an α-olefin represented by _{the general formula CH 2} = CHR ^16. Here, R ¹⁶ is hydrogen or a hydrocarbon group having 1 to 20 carbon atoms, and may have a branched, ring, and / or unsaturated bond. When the ^{number of carbon atoms of R 16} is larger than 20, sufficient polymerization activity tends not to be exhibited. Therefore, among them, the preferable component (a) ^{is α-olefin in which R 16} is hydrogen or a hydrocarbon group having 1 to 10 carbon atoms.
Further preferable components (a) include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 3-methyl-1-butene, 4-methyl-1-pentene and vinyl. Cyclohexene and styrene can be mentioned. In addition, a single component (a) may be used, or a plurality of components (a) may be used in combination.

(B) (Meta) Acrylic Acid Ester The component (b) in the present invention is a (meth) acrylic acid ester represented by _{the general formula CH 2} = C (R ¹⁷ ) CO ₂ (R ^18). Here, R ¹⁷ is hydrogen or a hydrocarbon group having 1 to 10 carbon atoms, and may have a branched, ring, and / or unsaturated bond. R ¹⁸ is a hydrocarbon group having 1 to 30 carbon atoms and may have a branched, ring, and / or unsaturated bond. Furthermore, it may contain a hetero atom at any position within R ^18.
When the ^{number of carbon atoms of R 17} is 11 or more, sufficient polymerization activity tends not to be exhibited. Therefore, R ¹⁷ is hydrogen or a hydrocarbon group having 1 to 10 carbon atoms, but the preferred component (b) ^{is a (meth) acrylic acid ester in which R 17} is hydrogen or a hydrocarbon group having 1 to 5 carbon atoms. Can be mentioned. More preferable component (b) includes a methacrylic acid ester in which ^{R 17} is a methyl group or an acrylic acid ester in which ^{R 17 is hydrogen.} Similarly, when the ^{number of carbon atoms of R 18} exceeds 30, the polymerization activity tends to decrease. Therefore, R ¹⁸ has 1 to 30 carbon atoms, but R ¹⁸ preferably has 1 to 12 carbon atoms, and more preferably 1 to 8 carbon atoms.
Examples of the heteroatom that may be contained in R ¹⁸ include oxygen, sulfur, selenium, phosphorus, nitrogen, silicon, fluorine, and boron. Of these heteroatoms, oxygen, silicon and fluorine are preferred, and oxygen is even more preferred. Further, ^{it is preferable that R 18} does not contain a hetero atom.

Further preferable components (b) include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, and (meth). ) Isobutyl acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate , (Meta) nonyl acrylate, (meth) decyl acrylate, (meth) dodecyl acrylate, phenyl (meth) acrylate, toluyl (meth) acrylate, benzyl (meth) acrylate, hydroxyethyl (meth) acrylate , (Meta) dimethylaminoethyl acrylate, (meth) diethylaminoethyl acrylate, -2-aminoethyl (meth) acrylate, -2-methoxyethyl (meth) acrylate, -3-methoxypropyl (meth) acrylate , (Meta) glycidyl acrylate, (meth) ethylene oxide, (meth) trifluoromethyl acrylate, (meth) -2-trifluoromethyl ethyl acrylate, (meth) perfluoroethyl acrylate, (meth) Examples thereof include acrylamide, (meth) acrylic dimethylamide, 2-hydroxybutyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate. In addition, a single component (b) may be used, or a plurality of components (b) may be used in combination.

2. Metal Complex The reaction product of the present invention, that is, the metal complex is represented by the following general formula (A).

[In the formula, M represents nickel or palladium. R ³ represents a hydrocarbon group that may contain hydrogen or a heteroatom having 1 to 20 carbon atoms. L ¹ represents a ligand coordinated to M. Further, R ³ and L ¹ may be bonded to each other to form a ring. X ¹ represents oxygen or sulfur. E ¹ represents phosphorus, arsenic or antimony. R ⁴ and R ⁵ each independently represent a hydrocarbon group that may contain a heteroatom having 1 to 30 carbon atoms. R ^{6 to} R ⁸ are hydrocarbon groups that may independently contain hydrogen, halogen, and a heteroatom having 1 to 30 carbon atoms, OR ² , CO ₂ R ² , CO ₂ M', and C (O). ) N (R ¹ ) ₂ , C (O) R ² , SR ² , SO ₂ R ² , OSO ₂ R ² , P (O) (OR ² ) _2-y (R ¹ ) _y , CN, NHR ² , _{^{N (R 2) 2, Si}} (OR 1) 3-x (R 1) x, OSi (OR 1) 3-x (R 1) x, NO 2, SO 3 M ', PO 3 M' 2, P (O) (OR ² ) _{represents 2} M'or an epoxy-containing group. Here, R ¹ represents hydrogen or a hydrocarbon group having 1 to 20 carbon atoms. Further, R ² represents a hydrocarbon group having 1 to 20 carbon atoms. M'represents alkali metal, ammonium, quaternary ammonium or phosphonium, x represents an integer from 0 to 3, and y represents an integer from 0 to 2. R ^{9 to} R ¹³ are hydrogen, and substituents represented by the general formula (B) (R ¹⁴ and R ¹⁵ are hydrocarbon groups having 1 to 6 carbon atoms, which may independently have hydrogen or a heteroatom, respectively. ^{Aryl group having 6 to 12 carbon atoms, an adamantyl group, OR 2} , SR ² , or N (R ² _{) 2} which may have a substituent (which may be bonded to each other to form a ring). Represents. However, ^{at least one of R 9 to} R ¹³ is a substituent represented by the general formula (B), an aryl group having 6 to 12 carbon atoms which may have a substituent, an adamantyl group, OR ² , SR ² or N (R ² ) ₂ . R ^{9 to} R ¹³ do not ring with each other. ]

In the present invention, it is M nickel or palladium.
The valence of M is preferably divalent. Here, the valence of M means a formal oxidation number used in organometallic chemistry. That is, when an electron pair in a bond involving an element is assigned to an element having a high electronegativity, it refers to the number of charges remaining on the atom of that element. For example, in the general formula (A) of the present invention, E ¹ is phosphorus, X ¹ is oxygen, M is nickel, R ³ is a phenyl group, L ¹ is pyridine, and nickel is phosphorus, oxygen, and phenyl group carbon. When bonded to the nitrogen of pyridine, the formal oxidation number of nickel, i.e. the valence of nickel, is divalent. Because, based on the above definition, in these bonds, the electron pair is assigned to phosphorus, oxygen, carbon, and nitrogen, which have higher electronegativity than nickel, and the charge is 0 for phosphorus, -1, for oxygen, and phenyl group. This is because -1, pyridine is 0, and the complex is electrically neutral as a whole, so the charge remaining on nickel is +2.

R ³ in the present invention represents hydrogen or heteroatom hydrocarbon group which may contain 1 to 20 carbon atoms. It is considered that the polymerization or copolymerization reaction in the present invention is started by inserting the component (a) or the component (b) in the present invention into the bond ^{between M and R 3.} Therefore, the number of carbon atoms of R ³ is excessively large, there is a tendency that the initiation reaction is inhibited. Thus, preferred ^{R 3,} 1 to 16 carbon atoms, more preferably from 1 to 10 carbon atoms.
Specific examples of R ³ include hydride group, a methyl group, an ethyl group, n- propyl group, an isopropyl group, n- butyl group, an isobutyl group, n- hexyl, n- octyl group, n- decyl group, Examples thereof include an n-dodecyl group, a cyclopentyl group, a cyclohexyl group, a phenyl group, a p-methylphenyl group, a trimethylsilyl group, a triethylsilyl group, a triphenylsilyl group and the like.

In the present invention, L ¹ represents a ligand coordinated with M. Ligand L ¹ in the present invention, as coordination bondable atom, an oxygen, nitrogen, a hydrocarbon compound having 1 to 20 carbon atoms having a sulfur. Further, as L ¹ , a hydrocarbon compound having a carbon-carbon unsaturated bond that can be coordinated to the transition metal (which may contain a hetero atom) can also be used. Preferably, L ¹ has 1 to 16 carbon atoms, and more preferably 1 to 10 carbon atoms. ^{Further, as L 1} to coordinate-bond with M in the general formula (A), a compound having no electric charge is preferable.
L ¹ forms a coordinate bond with M, but in the present invention, a compound that removes ^{L 1} from M in order to promote the polymerization of the component (a) and the copolymerization of the component (a) and the component (b). There is no need to use (scavenger).

In the so-called SHOP type metal complex, instead of L ¹ in the present invention, phosphine, for example, be used trimethylphosphine and triphenylphosphine, it can be synthesized similar complexes with the present invention. However, when such a ligand is used, it is known that it is essential to use a scavenger that removes the ligand from M in order to express the polymerizable ability of the olefin (Non-Patent Document 6). The scavenger used for such _{purpose, Ni (COD) 2 (COD} : _{cyclooctadiene), B (C 6 F 5} ) 3, aluminoxanes, rhodium complex are known.

Preferred L ¹ in the present invention, pyridines, piperidines, alkyl ethers, aryl ethers, alkylaryl ethers, cyclic ethers, alkyl nitriles derivatives, aryl nitrile derivatives, alcohols, amides, fatty esters , Aromatic esters, amines, cyclic unsaturated hydrocarbons and the like. Further preferable L ¹ includes pyridines, cyclic ethers, aliphatic esters, aromatic esters, and cyclic olefins, and particularly preferable L ¹ is pyridine, lutidine (dimethylpyridine), picoline (methylpyridine). , R ¹ CO ₂ R ² ( ^{the definitions of R 1} and R ² are as described above).
In addition, R ³ and L ¹ may be bonded to each other to form a ring. An example of such is the cycloocta-1-enyl group, which is also a preferred mode in the present invention.
In the present invention, X ¹ represents oxygen or sulfur. Of these, oxygen is preferred. Further, in the present invention, E ¹ represents phosphorus, arsenic or antimony. Of these, phosphorus is preferred.

In the present invention, R ⁴ and R ⁵ are hydrocarbon groups that may independently contain a heteroatom having 1 to 30 carbon atoms, but more specifically, they contain a hydrogen or a heteroatom. It contains a linear hydrocarbon group that may contain a heteroatom, a branched chain hydrocarbon group that may contain a heteroatom, an alicyclic hydrocarbon group that may contain a heteroatom, and a heteroatom. Also good aryl groups are mentioned. R ⁴ and R ⁵ are preferably bulky. Therefore, among these, an alicyclic hydrocarbon group which may contain a heteroatom or an aryl group which may contain a heteroatom is preferable, and an aryl group which may contain a heteroatom is preferable. Most preferable. Examples of such an aryl group include a phenyl group, a naphthyl group, an anthracenyl group and the like.

^{In R 4} and R ⁵ of the present invention, when the above-mentioned heteroatom-containing group is bonded to the aromatic skeleton of these aryl groups, the heteroatom-containing group may be directly bonded to the aromatic skeleton as a bonding mode. , May be attached to the aromatic skeleton via a spacer such as a methylene group. When a heteroatom-containing group is bonded to an aromatic skeleton via a methylene group, the number of methylene groups is preferably one. Further, as the substitution position, among the aromatic skeletons in ^{R 4} and R ⁵ , the ortho position is preferable with respect to the carbon bonded to ^{E 1.} By doing so, the heteroatoms in R ⁴ and R ⁵ can take the spatially arrayed so as to interact with M.

Specific examples of preferred R ⁴ and R ⁵ are 2,6-dimethoxyphenyl group, 2,4,6-trimethoxyphenyl group, 4-methyl-2,6-dimethoxyphenyl group, 4-t-butyl-. 2,6-dimethoxyphenyl group, 1,3-dimethoxy-2-naphthyl group, 2,6-diethoxyphenyl group, 2,4,6-triethoxyphenyl group, 4-methyl-2,6-diethoxyphenyl Group, 4-t-butyl-2,6-diethoxyphenyl group, 1,3-diethoxy-2-naphthyl group, 2,6-diphenoxyphenyl group, 2,4,6-triphenoxyphenyl group, 4- Methyl-2,6-diphenoxyphenyl group, 4-t-butyl-2,6-diphenoxyphenyl group, 1,3-diphenoxy-2-naphthyl group, 2,6-di (methoxymethyl) phenyl group, 2 , 4,6-tri (methoxymethyl) phenyl group, 4-methyl-2,6-di (methoxymethyl) phenyl group, 4-t-butyl-2,6-di (methoxymethyl) phenyl group, 1,3 -Di (methoxymethyl) -2-naphthyl group, 2,6-di (phenoxymethyl) phenyl group, 2,4,6-tri (phenoxymethyl) phenyl group, 4-methyl-2,6-di (phenoxymethyl) ) Phenyl group, 4-t-butyl-2,6-di (phenoxymethyl) phenyl group, 1,3-di (phenoxymethyl) -2-naphthyl group, 2,6-di (2-methoxyethyl) phenyl group , 2,4,6-tri (2-methoxyethyl) phenyl group, 4-methyl-2,6-di (2-methoxyethyl) phenyl group, 4-t-butyl-2,6-di (2-methoxy) Ethyl) phenyl group, 1,3-di (2-methoxyethyl) -2-naphthyl group, 2,6-di (2-phenoxyethyl) phenyl group, 2,4,6-tri (2-phenoxyethyl) phenyl Group, 4-methyl-2,6-di (2-phenoxyethyl) phenyl group, 4-t-butyl-2,6-di (2-phenoxyethyl) phenyl group, 1,3-di (2-phenoxyethyl) ) -2-Naphtyl group and the like can be mentioned.

Of these, preferred are 2,6-dimethoxyphenyl group, 2,4,6-trimethoxyphenyl group, 4-methyl-2,6-dimethoxyphenyl group, 4-t-butyl-2,6- Dimethoxyphenyl group, 2,6-diethoxyphenyl group, 2,4,6-triethoxyphenyl group, 4-methyl-2,6-diethoxyphenyl group, 4-t-butyl-2,6-diethoxyphenyl Group, 2,6-diphenoxyphenyl group, 2,4,6-triphenoxyphenyl group, 4-methyl-2,6-diphenoxyphenyl group, 4-t-butyl-2,6-diphenoxyphenyl group, 2,6-di (methoxymethyl) phenyl group, 2,4,6-tri (methoxymethyl) phenyl group, 4-methyl-2,6-di (methoxymethyl) phenyl group, 4-t-butyl-2, 6-di (methoxymethyl) phenyl group, 2,6-di (phenoxymethyl) phenyl group, 2,4,6-tri (phenoxymethyl) phenyl group, 4-methyl-2,6-di (phenoxymethyl) phenyl Groups, 4-t-butyl-2,6-di (phenoxymethyl) phenyl group, and particularly preferred are 2,6-dimethoxyphenyl group, 2,4,6-trimethoxyphenyl group, 4-. Methyl-2,6-dimethoxyphenyl group, 4-t-butyl-2,6-dimethoxyphenyl group, 2,6-diphenoxyphenyl group, 2,4,6-triphenoxyphenyl group, 4-methyl-2, Examples thereof include 6-diphenoxyphenyl group and 4-t-butyl-2,6-diphenoxyphenyl group.

R ^{6 to} R ⁸ are hydrocarbon groups that may independently contain hydrogen, halogen, and a heteroatom having 1 to 30 carbon atoms, OR ² , CO ₂ R ² , CO ₂ M', and C (O). ) N (R ¹ ) ₂ , C (O) R ² , SR ² , SO ₂ R ² , OSO ₂ R ² , P (O) (OR ² ) _2-y (R ¹ ) _y , CN, NHR ² , _{^{N (R 2) 2, Si}} (OR 1) 3-x (R 1) x, OSi (OR 1) 3-x (R 1) x, NO 2, SO 3 M ', PO 3 M' 2, P (O) (OR ² ) _{represents 2} M'or an epoxy-containing group. Here, R ¹ represents hydrogen or a hydrocarbon group having 1 to 20 carbon atoms. Further, R ² represents a hydrocarbon group having 1 to 20 carbon atoms. M'represents alkali metal, ammonium, quaternary ammonium or phosphonium, x represents an integer from 0 to 3, and y represents an integer from 0 to 2.
Of these, preferred are hydrogen atom, fluorine atom, chloro atom, bromo atom, methyl group, ethyl group, isopropyl group, phenyl group, trifluoromethyl group, pentafluorophenyl group, trimethylsilyl group, methoxy group and ethoxy. Groups, phenoxy groups, nitrile groups, trimethoxysilyl groups, triethoxysilyl groups, trimethylsiloxy groups, trimethoxysiloxy groups, sodium sulfonate, potassium sulfonate, sodium phosphate, potassium phosphate and the like are particularly preferable. Examples include hydrogen atom, fluorine atom, methyl group, phenyl group, trifluoromethyl group, pentafluorophenyl group, trimethylsilyl group, methoxy group, phenoxy group, trimethoxysilyl group, triethoxysilyl group, trimethylsiloxy group, and trimethoxy. Examples thereof include siloxy group, sodium sulfonate, sodium phosphate and the like.

R ^{9 to} R ¹³ are hydrogen, and substituents represented by the general formula (B) (R ¹⁴ and R ¹⁵ are hydrocarbon groups having 1 to 6 carbon atoms, which may independently have hydrogen or a heteroatom, respectively. ^{Aryl group having 6 to 12 carbon atoms, an adamantyl group, OR 2} , SR ² , or N (R ² _{) 2} which may have a substituent (which may be bonded to each other to form a ring). Represents. However, ^{at least one of R 9 to} R ¹³ is a substituent represented by the general formula (B), an aryl group having 6 to 12 carbon atoms which may have a substituent, an adamantyl group, OR ² , SR ² or N (R ² ) ₂ . R ^{9 to} R ¹³ do not ring with each other.
The preferred substituent represented by the general formula (B), which can be at least one of R ^{9 to} R ¹³ , is a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, or an isobutyl group. , N-hexyl group, cyclohexyl group and the like.
Preferred of the aryl group having 6 to 12 carbon atoms which may have a substituent which can be at least one of R ^{9 to} R ^{13 are a phenyl group, a 2,6-dimethylphenyl group, 2,4.} Examples thereof include a 6-trimethylphenyl group, a 2,6-dimethoxyphenyl group and a 2,4,6-trimethoxyphenyl group.
^{Preferred of OR 2 which} can be at least one of R ^{9 to} R ¹³ includes a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group and the like.
Preferable examples of the SR ² which may be on at least one of R ⁹ to R _^13, like SCH 3, _SC 2 _{H 5.}
^{Preferable N (R 2} ) _{2 which} can be at least one of R ^{9 to} R ¹³ includes a dimethylamino group, a diethylamino group, a methylethylamino group and the like.

Hereinafter, the metal complex (A) of the present invention will be exemplified below, but the present invention is not limited to the following examples. In the following examples, each R in the above general formula (A) is shown in Table 1, and the metal complex (A) is specifically shown by this.
In the compounds shown in Table 1, M is nickel, E ¹ is phosphorus, X ¹ is oxygen, L ¹ and R ³ are cycloocta-1-enyl groups, and R ⁶ and R ⁷ are hydride groups.
In Table 1, Me is a methyl group, Et is an ethyl group, nPr is a normal propyl group, iPr is an isopropyl group, nBu is a normal butyl group, tBu is a tertiary butyl group, and Cy is a cyclohexyl group. , Ph indicates a phenyl group, and Ad indicates an adamantyl group (the same applies to Table 2).

3. 3. Method for Producing Metal Complex The metal complex of the present invention can be obtained by contacting a compound represented by the following general formula (C) or (D) with a transition metal complex (G) containing nickel or palladium. ..

[In the formula (C) or (D), Z represents a hydrogen atom or a leaving group, and m represents the valence of Z. X ¹ , E ¹ , R ^{4 to} R ¹³ are as described above. ]

In the general formulas (C) and (D), Z is a hydrogen atom or a leaving group, but specifically, a hydrogen atom and R ¹ SO ₂ groups (where R ¹ is as described above). ), _{2 CF 3} SOs, etc.

Although the general formula (D) is represented in the form of an anion, any counter cation can be used as long as it does not inhibit the reaction with the transition metal complex (G) according to the present invention. Specific examples of the counter cation include ammonium, quaternary ammonium or phosphonium, and metal ions of Groups 1 to 14 of the Periodic Table. Of these, NH ₄ ⁺ , R ¹ ₄ N ⁺ (where R ¹ is as described above, and the four R ^1s may be the same or different), R ¹ ₄ P ⁺ (here). in ^{R 1} is as described above, the four ^{R 1} may be the same or ^{different), Li +, Na +,} K +, Mg 2+, Ca 2+, an ^{Al 3+,} more preferably, R ¹ ₄ N ⁺ (wherein ^{R 1} is as described above, the four ^{R 1} may be the same or ^different), Li ^+, Na +, a ^{K +.}

The substances represented by the general formulas (C) and (D) can be synthesized based on a known synthetic method. The metal complex represented by the general formula (A) is a reaction product of the compound represented by the general formula (C) or (D) and the transition metal complex component (G) containing the metal M according to the present invention. include.

As the transition metal complex component (G) used in the present invention, a compound capable of reacting with a compound represented by the general formula (C) or (D) to form a complex having a polymerizable ability is used. These are sometimes also called precursors.
For example, as the transition metal complex (G) containing nickel, a complex represented by bis (1,5-cyclooctadiene) nickel (0), general formula: (CH ₂ CR ¹⁹ H ₂ ) ₂ Ni [here. R ¹⁹ is a hydrocarbon group which may contain a hydrogen atom, a halogen atom, or a hetero atom having 1 to 30 carbon atoms, OR ²⁰ , CO ₂ R ²⁰ , CO ₂ M', C (O) N (R ^21). ) ₂ , C (O) R ²⁰ , SR ²⁰ , SO ₂ R ²⁰ , SOR ²⁰ , OSO ₂ R ²⁰ , P (O) (OR ²⁰ ) _2-y (R ²¹ ) _y , CN, NHR ²⁰ , N ( ^{_{R 20) 2, Si (OR}} 21) 3-x (R 21) x, OSi (OR 21) 3-x (R 21) x, NO 2, SO 3 M ', PO 3 M' 2, P (O ) (OR ²⁰ ) ₂ M'or an epoxy-containing group (where R ²⁰ represents a hydrocarbon group having 1 to 20 carbon atoms and R ²¹ is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. , M'represents an alkali metal, an alkaline earth metal, ammonium, a quaternary ammonium or a phosphonium, x represents an integer of 0 to 3, and y represents an integer of 0 to 2). ], Bis (cyclopentadienyl) nickel (II), the general ^{_{formula: Ni (CH 2 SiR 19 3}} ) complex represented by ^{2 L} _{1 2} (wherein ^R 19, ^{L 1} is as described herein is as), the general ^formula:.. _NiR 19 complex represented by ^{2 L} _{1 2} (wherein ^R 19, ^{L 1} are as described herein) and the like can be used.
For the transition metal complex (G) containing the transition metals of Group 9, Group 10, or Group 11, the general formula: MR ¹⁹ _p L ¹ _q (where M is the transition of Group 9, Group 10, or Group 11). Metals, R ¹⁹ and L ¹ are as described herein, and p and q are integers greater than or equal to 0 that satisfy the valence of M).

Among these transition metal complexes (G), those preferably used are complexes represented by bis (1,5-cyclooctadiene) nickel (0), general formula: (CH ₂ CR ¹⁹ CH ₂ ) ₂ Ni. (wherein ^{R 19} is as described herein.), the general ^{_{formula: Ni (CH 2 SiR 19 3}} ) 2 L 1 2 in complex represented (wherein ^R 19, ^{L 1} is present is as described herein), the general ^{_{formula:.. NiR 19 2 L 1}} 2 in complex represented (wherein ^R 19, ^{L 1} are as described herein), Pd (dba ) ₂ , Pd ₂ (dba) ₃ , Pd ₃ (dba) ₄ (where dba stands for dibenzylideneacetone), Pd (OCOCH ₃ ) ₂ , (1,5-cyclooctadiene) Pd (methyl) ) (Chloride).
Particularly preferably, bis (1,5-cyclooctadiene) nickel (0), (CH ₂ CHCH ₂ ) ₂ Ni, (CH ₂ CMeCH ₂ ) ₂ Ni, Ni (CH ₂ SiMe ₃ ) ₂ (Py) ₂ ( Hereinafter, Py represents pyridine), Ni (CH ₂ SiMe ₃ ) ₂ (Lut) ₂ (hereinafter Lu stands for 2,6-rutidine), NiPh ₂ (Py) ₂ , Ni (Ph) ₂ ( Lut) _2, Pd (dba) ₂ , Pd ₂ (dba) ₃ , Pd ₃ (dba) ₄ (where dba stands for dibenzylideneacetone), Pd (OCOCH ₃ ) ₂ , (1,5- Cyclooctadiene) Pd (methyl) (chloride).

In the reaction product of the present invention, the compound represented by the above-mentioned general formula (C) or (D) and the above-mentioned transition metal complex (G) are used, for example, (C) + (D) :( G) = 1. : 99 to 99: 1 (molar ratio) can be obtained by contacting the mixture in an organic solvent such as toluene or benzene at 0 to 100 ° C. for 1 to 86400 seconds under reduced pressure to pressurized pressure. When a toluene or benzene solution of bis (1,5-cyclooctadiene) nickel (0) (Ni (COD) ₂ ) is used as (G), the color of the solution changes from yellow to, for example, red. Therefore, the formation of the reaction product can be confirmed.

After this reaction, the components constituting (G) other than the transition metal of (G) are replaced by the portion of the component (C) excluding Z and the component (D), and the present invention A metal complex represented by the general formula (A) of (A) is formed. It is preferable that this substitution reaction proceeds quantitatively, but in some cases, it does not have to proceed completely. After completion of the reaction, other components derived from (C), (D) and (G) coexist in addition to the complex represented by the general formula (A), but when the polymerization reaction or copolymerization reaction of the present invention is carried out. In addition, these other components may or may not be removed. In general, it is preferable to remove these other components because high activity can be obtained.
Note that for the reaction may be allowed to coexist L ¹ according to the present invention. In the present invention, as M, since use of nickel and palladium, by the coexistence of L ¹ Lewis basic in the system, there is a case where stability of the purified complex (A) is increased, in such a case , as long as the L ¹ does not inhibit the polymerization reaction or copolymerization reaction of the present invention, it is preferable to coexist a L ^1.

In the present invention, the reaction is carried out in advance in a container different from the reactor used for copolymerization of the α-olefin and the (meth) acrylic acid ester, and the obtained complex (A) is obtained from the α-olefin. It may be subjected to polymerization or copolymerization of an α-olefin and a (meth) acrylic acid ester, or the reaction may be carried out in the presence of these monomers. Further, the reaction may be carried out in a reactor used for copolymerization of an α-olefin and a (meth) acrylic acid ester. At this time, these monomers may or may not be present. Further, for the components represented by the general formulas (C) to (D), a single component may be used, or a plurality of types of components may be used in combination. In particular, the combined use of these plurality of types is useful for the purpose of expanding the molecular weight distribution and the comonomer content distribution.

Hereinafter, (C) that can be used in the present invention is illustrated in Table 2, but is not limited to the following examples. In the compounds of Table 2, E ¹ is phosphorus, X ¹ is oxygen, and R ⁶ and R ⁷ are hydride groups.

4. Polymerization reaction In the present invention, the metal complex represented by the general formula (A) can be used as a catalyst component for copolymerization. As described above, the metal complex represented by the general formula (A) can be formed by the reaction of the general formula (C) or (D) with the transition metal complex component (G). When the metal complex represented by the general formula (A) is used as a catalyst component, an isolated one may be used, or one supported on a carrier may be used. In a reactor used for the polymerization of such a supported α-olefin or the copolymerization of an α-olefin and a (meth) acrylic acid ester, the reaction may be carried out in the presence or absence of these monomers, or the reactor. It may be carried out in a separate container.

As the carrier that can be used, 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 thereof include SiO ₂ , Al ₂ O ₃ , MgO, ZrO ₂ , TiO ₂ , B ₂ O ₃ , CaO, ZnO, BaO, ThO _2, etc. 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, etc. mixed oxides can also be used, and inorganic silicates, polyethylene carriers, polypropylene carriers, etc. Polystyrene carriers, polyacrylic acid carriers, polymethacrylic acid carriers, polyacrylic acid ester carriers, polyester carriers, polyamide carriers, polyimide carriers and the like can be used. As for these carriers, the particle size, particle size distribution, pore volume, specific surface area and the like are not particularly limited, and any carrier can be used.

As the inorganic silicate, clay, clay mineral, zeolite, diatomaceous earth and the like can be used. These may be synthetic products or naturally occurring minerals. Specific examples of clay and clay minerals include alofene groups such as allophen, kaolin groups such as dikite, nacrite, kaolinite, and anokisite, halloysite groups such as metahaloysite and halloysite, and vermiculite such as chrysotile, lizardite, and antigolite. Smectite such as stones, montmorillonite, zauconite, biderite, nontronite, saponite, hectrite, vermiculite minerals such as vermiculite, mica minerals such as illite, serisite, and sea green stone, attapargite, sepiolite, paigolskite, bentonite, wood section. Examples include clay, gairome clay, hisingel stone, pyrophyllite, and rhokuday stones. These may form a mixed layer. Examples of the artificial compound include synthetic mica, synthetic hectorite, synthetic saponite, synthetic teniolite and the like. Of these specific examples, preferred are kaolins such as dikite, nacrite, kaolinite and anokisite, halosites such as metahalosite and halosite, vermiculite such as chrysotile, lysardite and antigolite, and montmorillonite. Examples include smectites such as zauconite, biderite, nontronite, saponite and hectorite, vermiculite minerals such as vermiculite, mica minerals such as illite, serpentine and seagreen stone, synthetic mica, synthetic hectorite, synthetic saponite and synthetic teniolite. Particularly preferred are smectites such as montmorillonite, zauconite, biderite, nontronite, saponite and hectorite, vermiculite minerals such as vermiculite, synthetic mica, synthetic hectorite, synthetic saponite and synthetic teniolite.

These carriers may be used as they are, but can be treated with acid such as hydrochloric acid, nitrate, sulfuric acid and / or LiCl, NaCl, KCl, CaCl ₂ , MgCl ₂ , Li ₂ SO ₄ , dsm ₄ , ZnSO ₄ , Ti ( Salt treatment such as SO ₄ ) ₂ , Zr (SO ₄ ) ₂ , Al ₂ (SO ₄ ) _{3 may be performed.} In the treatment, the corresponding acid and base may be mixed to form a salt in the reaction system for the treatment. Further, shape control such as crushing and granulation and drying treatment may be performed.

The polymerization reaction in the present invention includes hydrocarbon solvents such as propane, n-butane, isobutane, n-hexane, n-heptane, toluene, xylene, cyclohexane and methylcyclohexane, liquids such as liquefied α-olefins, and diethyl ether. It is carried out in the presence or absence of polar solvents such as ethylene glycol dimethyl ether, tetrahydrofuran, dioxane, ethyl acetate, methyl benzoate, acetone, methyl ethyl ketone, formamide, acetonitrile, methanol, isopropyl alcohol, ethylene glycol and the like. Moreover, you may use the mixture of the liquid compound described here as a solvent. In addition, ionic liquids can also be used as solvents. The above-mentioned hydrocarbon solvent and ionic liquid are more preferable in order to obtain high polymerization activity and high molecular weight.

In the present invention, the polymerization reaction can be carried out in the presence or absence of a known additive. As the additive, a polymerization inhibitor that prohibits radical polymerization and an additive that has an action of stabilizing the produced copolymer are preferable. For example, quinone derivatives and hindered phenol derivatives are examples of preferred additives. Specifically, monomethyl ether hydroquinone, 2,6-di-t-butyl4-methylphenol (BHT), a reaction product of trimethylaluminum and BHT, a reaction product of tetravalent titanium alcoxide and BHT, etc. Can be used. Inorganic and / or organic fillers may be used as additives, and the polymerization may be carried out in the presence of these fillers. Further, it may be used L ¹ and an ionic liquid according to the present invention as an additive.

A Lewis base is mentioned as a preferable additive in the present invention. By selecting an appropriate Lewis base, the activity, molecular weight, and copolymerizability of the acrylic acid ester can be improved. The amount of Lewis base is 0.0001 equivalent to 1000 equivalent, preferably 0.1 equivalent to 100 equivalent, and more preferably 0.3 equivalent, relative to the transition metal M in the catalyst component present in the polymerization system. ~ 30 equivalents. The method for adding the Lewis base to the polymerization system is not particularly limited, and any method can be used. For example, it may be added by mixing with the catalyst component of the present invention, may be added by mixing with a monomer, or may be added to the polymerization system independently of the catalyst component and the monomer. Moreover, you may use a plurality of Lewis bases in combination. Further, the ^{same Lewis base as L 1 according} to the present invention may be used, or may be different.

Lewis bases include aromatic amines, aliphatic amines, alkyl ethers, aryl ethers, alkyl aryl ethers, cyclic ethers, alkyl nitriles, aryl nitriles, alcohols, amides, aliphatic esters. , Aromatic esters, phosphates, phosphites, thiophenes, thianslens, thiazoles, oxazoles, morpholines, cyclic unsaturated hydrocarbons and the like. Of these, particularly preferable Lewis bases are aromatic amines, aliphatic amines, cyclic ethers, aliphatic esters, and aromatic esters, and among them, preferred Lewis bases are pyridine derivatives, pyrimidine derivatives, and piperidine. Derivatives, imidazole derivatives, aniline derivatives, piperidine derivatives, triazine derivatives, pyrrole derivatives, furan derivatives.

Specific Lewis base compounds include pyridine, pentafluoropyridine, 2,6-lutidine, 2,4-lutidine, 3,5-lutidine, pyrimidine, N, N-dimethylaminopyridine, N-methylimidazole, 2, 2'-bipyridine, aniline, piperidine, 1,3,5-triazine, 2,4,6-tris (trifluoromethyl) -1,3,5-triazine, 2,4,6-tris (2-pyridyl) -S-triazine, quinoline, 8-methylquinolin, phenazine, 1,10-phenanthroline, N-methylpyrol, 1,8-diazabicyclo- [5.4.0] -undec-7-ene, 1,4 -Diazabicyclo- [2,2,2] -octane, triethylamine, benzonitrile, picolin, triphenylamine, N-methyl-2-pyrrolidone, 4-methylmorpholin, benzoxazole, benzothiazole, furan, 2,5- Dimethylfuran, dibenzofuran, xanthene, 1,4-dioxane, 1,3,5-trioxane, dibenzothiophene, thianthrene, triphenylphosphonium cyclopentadienide, triphenylphosphite, triphenylphosphate, tripyrolidinophos Fins, tris (pyrrolidino) borane, etc. can be mentioned.

In the present invention, the polymerization form is not particularly limited. Slurry polymerization in which at least a part of the produced polymer becomes a slurry in a medium, bulk polymerization using the liquefied monomer itself as a medium, vapor phase polymerization performed in a vaporized monomer, or a polymer produced in a monomer liquefied at high temperature and high pressure. High-pressure ion polymerization or the like in which at least a part of the above is dissolved is preferably used. Further, any of batch polymerization, semi-batch polymerization, and continuous polymerization may be used. Further, it may be a living polymerization, or the polymerization may be carried out while causing chain transfer. Further, a so-called chain transfer agent (CSA) may be used in combination to perform chain switching or coordinate transfer chain transfer polymerization (CCTP).

The unreacted monomer or medium may be separated from the produced copolymer and recycled for use. Upon recycling, these monomers and media may be purified and reused, or may be reused without purification. Conventionally known methods can be used for separating the produced copolymer from the unreacted monomer and the medium. For example, methods such as filtration, centrifugation, solvent extraction, and reprecipitation using a poor solvent can be used.
The polymerization temperature, polymerization pressure and polymerization time are not particularly limited, but usually, the optimum setting can be made from the following ranges in consideration of productivity and process capacity. That is, the polymerization temperature is usually −20 ° C. to 290 ° C., preferably 0 ° C. to 250 ° C., the copolymerization pressure is 0.1 MPa to 300 MPa, preferably 0.3 MPa to 250 MPa, and the polymerization time is 0.1 minutes. It can be selected from the range of 10 to 10 hours, preferably 0.5 minutes to 7 hours, and more preferably 1 minute to 6 hours.

In the present invention, the polymerization is generally carried out in an inert gas atmosphere. For example, a nitrogen, argon, or carbon dioxide atmosphere can be used, and a nitrogen atmosphere is preferably used. A small amount of oxygen or air may be mixed.
The supply of the catalyst and the monomer to the polymerization reactor is not particularly limited, and various supply methods can be adopted depending on the purpose. For example, in the case of batch polymerization, it is possible to take a method in which a predetermined amount of monomer is supplied to the polymerization reactor in advance and a catalyst is supplied to the polymerization reactor. In this case, additional monomers and additional catalysts may be supplied to the polymerization reactor. Further, in the case of continuous polymerization, a method can be adopted in which a predetermined amount of monomer and catalyst are continuously or intermittently supplied to the polymerization reactor to carry out the polymerization reaction continuously.

Regarding the control of the composition of the copolymer, a method of supplying a plurality of monomers to the reactor and controlling the composition by changing the supply ratio can be generally used. In addition, there are a method of controlling the copolymer composition by utilizing the difference in the monomer reactivity ratio due to the difference in the structure of the catalyst, and a method of controlling the copolymer composition by utilizing the polymerization temperature dependence of the monomer reactivity ratio. ..
A conventionally known method can be used for controlling the molecular weight of the polymer. That is, a method of controlling the molecular weight by controlling the polymerization temperature, a method of controlling the molecular weight by controlling the monomer concentration, a method of controlling the molecular weight using a chain transfer agent, and a method of controlling the ligand structure in the transition metal complex. And so on. When a chain transfer agent is used, a conventionally known chain transfer agent can be used. For example, hydrogen, metal alkyl and the like can be used.
Further, when the component (b) itself is a kind of chain transfer agent, the molecular weight can be adjusted by controlling the ratio of the component (b) to the component (a) and the concentration of the component (b). be. By controlling the ligand structure of the transition metal complex, in case of performing a molecular weight modifier, wherein the R ^4, types of heteroatom-containing group in R ^5, number, or to control the placement, bulk around the metal M or to place high substituent by or to introduce a heteroatom in R ⁸ described above, can be utilized tend to generally increase the molecular weight. It is preferable to arrange the electron donating group with respect to the metal M so that the electron donating group such as an aryl group or a heteroatom-containing substituent can interact with the metal M. Whether or not such an electron-donating group can interact with the metal M can generally be determined by measuring the distance between the electron-donating group and the metal M by a molecular model or molecular orbital calculation.

The copolymer produced by the present invention has good paintability, printability, antistatic property, inorganic filler dispersibility, adhesiveness with other resins, and with other resins due to the effect based on the polar group of the copolymer. The compatibility ability and the like are exhibited. Taking advantage of these properties, this copolymer can be used for various purposes. For example, it can be used as a film, a sheet, an adhesive resin, a binder, a compatibilizer, a wax and the like.

The present invention will be described in more detail in the following Examples and Comparative Examples, but the present invention is not limited thereto. In the following synthesis examples, unless otherwise specified, the operation was carried out in a purified nitrogen atmosphere, and the solvent used was dehydrated and deoxidized.

1. 1. Evaluation method (1) Tm, Tc: Obtained by the following DSC measurement.
Using a PerkinElmer PYRIS Diamond DSC differential scanning calorimetry device, the sample (about 5 mg) is thawed at 210 ° C. for 5 minutes, then cooled to -20 ° C. at a rate of 10 ° C./min and at -20 ° C for 5 minutes. After holding, the temperature was raised to 210 ° C. at a rate of 10 ° C./min to obtain a melting curve. The peak top temperature of the main exothermic peak in the temperature lowering stage was defined as the crystallization temperature Tc. Further, the peak top temperature of the main endothermic peak in the final temperature rising step performed to obtain the melting curve was defined as the melting point Tm.
(2) Weight average molecular weight Mw, number average molecular weight Mn and molecular weight distribution Mw / Mn: Obtained by the following GPC measurement.
A sample (about 20 mg) was collected in a vial for the high temperature GPC pretreatment device PL-SP 260VS manufactured by Polymer Laboratory, and o-dichlorobenzene (BHT concentration = 0.5 g / L) containing BHT as a stabilizer was used. In addition, the polymer concentration was adjusted to 0.1 (% by weight). The polymer was dissolved by heating to 135 ° C. in the above-mentioned pretreatment device for high temperature GPC PL-SP 260VS, and filtered through a glass filter to prepare a sample. In the GPC measurement in the present invention, no polymer was trapped in the glass filter. Next, GPC measurement was performed using TSKgel GMH-HT (30 cmx4) manufactured by Tosoh Corporation and HLC-8321 GPC / HT manufactured by Tosoh Corporation equipped with an RI detector as a column. As the measurement conditions, a sample solution injection amount: about 300 μl, a column temperature: 135 ° C., a solvent: o-dichlorobenzene, and a flow rate: 1.0 ml / min were adopted. The molecular weight was calculated as follows. That is, a commercially available monodisperse polystyrene is used as a standard sample, a calibration curve regarding the retention time and the molecular weight is created from the viscosity formula of the polystyrene standard sample and the ethylene polymer, and the molecular weight is calculated based on the calibration curve. rice field. As the viscosity formula, [η] = KxM ^α is used, K = 1.38E ^-4 and α = 0.70 are used for polystyrene, and K = 4. 77E- ⁴ , α = 0.70 was used.

2. Synthesis of ligand and complex (Synthesis Example 1): Synthesis of ligand B-423 Ligand B-423 was synthesized according to the following scheme.

(I) Synthesis of Compound 2 Synthesis was performed according to Patent Document WO2010 / 050256.

(Ii) Synthesis of Compound 3 i-PrMgCl (2M, 5.25 ml) was added to a solution of Compound 2 (2.64 g, 10.0 mmol) in THF (5.0 ml) at 0 ° C. After stirring the reaction mixture at 25 ° C. for 1 hour, _{PCL 3} (618 mg, 4.50 mmol) was added at −78 ° C. The reaction mixture was heated to 25 ° C. over 3 hours to give a yellow suspension. The solvent was distilled off under reduced pressure to obtain a yellow solid. This mixture was used in the next reaction without purification.

(Iii) Synthesis of Compound 5 n-BuLi (2.5 M, 96 ml) was added to a solution of Compound 3 (30 g, 220 mmol) in THF (250 ml) at 0 ° C., and the mixture was stirred at 30 ° C. for 1 hour. The solution _{^{B (O i Pr) 3 (}} 123g, 651mmol) was added at -78 ° C., to give a white suspension was stirred for 2 hours at 30 ° C.. Hydrochloric acid (1M) was added to adjust the pH to 6-7, and the organic layer was concentrated to give a mixture. The resulting mixture was washed with petroleum ether (80 ml) to give 26 g of compound 5.

(Iv) Synthesis of Compound 7 Compound 5 (5.00 g, 27.5 mmol), Compound 6 (4.42 g, 18.3 mmol), Pd ₂ (dba) ₃ (168 mg, 0.183 mmol), s-Phos (376 mg). , 0.916 mmol), K ₃ PO ₄ (7.35 g, 34.6 mmol) was weighed into a reaction vessel and toluene (40 ml) was added. The solution was reacted at 110 ° C. for 12 hours to give a black suspension. H ₂ O (50ml) was added, and extracted with EtOAc (55mlx3). The organic layer was washed with saline (20 ml) and dehydrated with _{Na 2} SO _4. The organic layer was filtered to distill off the solvent under reduced pressure, and then purified by a silica gel column to obtain 1.3 g of an oily substance.

(V) Synthesis of Compound 8 n-BuLi (2.5 M, 9.15 ml) was added dropwise to a solution of Compound 7 (6.5 g, 22 mmol) in THF (40 ml) at 0 ° C., and the temperature was raised to 30 ° C. to 1 Stirred for hours. The reaction solution was cooled to −78 ° C., CuCN (2.1 g, 23 mmol) was added, and the mixture was stirred at 30 ° C. for 1 hour. The reaction solution was cooled to −78 ° C., a solution of Compound 3 (6.7 g, 20 mmol) in THF (40 ml) was added, and the mixture was stirred at 30 ° C. for 12 hours to obtain a white suspension. Addition of H ₂ O (50 ml) to the suspension resulted in a white precipitate. The white precipitate was collected by filtration, dissolved in dichloromethane (20 ml), aqueous ammonia (80 ml) was added, and the mixture was stirred for 3 hours. The product was extracted with dichloromethane (50 ml x 3), _{dehydrated with Na 2} SO ₄ , and then concentrated to give a yellow oily substance. This oily substance was purified on a silica gel column to obtain 2.9 g of Compound 8.

(Vi) Synthesis of B-423 HCl / EtOAc (4M, 50 ml) was added to a solution of compound 8 (2.9 g, 4.8 mmol) in dichloromethane (20 ml) at 0 ° C., and the mixture was stirred at 30 ° C. for 2 hours to give a pale yellow color. A solution was obtained. After distilling off the solvent under reduced pressure, dichloromethane (50 ml) was added. Washing with saturated _{aqueous NaHCO 3} solution (100 ml) gave 2.5 g of B-423.
^{1 1} H NMR (CDCl ₃ , δ, ppm): 7.49 (t, 1H), 7.33 (t, 1H), 7.22 (m, 4H), 6.93 (d, 1H), 6. 81 (t, 1H), 6.49 (dd, 4H), 6.46 (br, 1H), 3.56 (s, 12H), 2.63 (sept, 2H), 1.05 (d, 6H) ), 1.04 (d, 6H); ³¹ P NMR (CDCl ₃ , δ, ppm): -61.6 (s).

(Synthesis Example 2): Synthesis of Ligand B-443 Ligand B-443 was synthesized according to the following scheme.

(I) Synthesis of Compound 10 Compound 5 (11.8 g, 64.8 mmol), Compound 9 (8.0 g, 43 mmol), Pd (dba) ₂ (249 mg, 0.432 mol), s-Phos (887 mg, 2. 16 mmol), K ₃ PO ₄ (17.3 g, 81.7 mmol) was weighed into a reaction vessel and toluene (80 ml) was added. The mixture was reacted at 110 ° C. for 24 hours to give a black suspension. The suspension was cooled to 30 ° C., H ₂ O (250 ml) was added, and the suspension was extracted with dichloromethane (250 ml x 3). After drying with Na ₂ SO ₄ , the solvent was distilled off under reduced pressure. Purification was performed on a silica gel column, and the obtained oily substance was dried under reduced pressure at 80 ° C. for 1 hour to obtain 6.6 g of Compound 10 as a yellow oily substance.

(Ii) Synthesis of Compound 11 n-BuLi (2.5 M, 18.2 ml) was added to a solution of Compound 10 (10 g, 41 mmol) in THF (40 ml) at 0 ° C., the temperature was raised to 30 ° C., and the mixture was stirred for 1 hour. .. CuCl (4.49 g, 45.4 mmol) was added to this suspension at 0 ° C., the temperature was raised to 30 ° C., and the mixture was stirred for 1 hour. A solution of compound 3 (13.9 g, 40.9 mmol) in THF (80 ml) was slowly added dropwise to this suspension at −78 ° C., and the mixture was stirred at 66 ° C. for 16 hours to obtain a yellow suspension. The reaction mixture was filtered and concentrated, dichloromethane (150 ml) and aqueous ammonia (50 ml) were added, and the mixture was stirred at 30 ° C. for 2 hours. The extraction operation was carried out with dichloromethane (50 ml x 3), and the obtained organic layer was _{dried over Na 2} SO ₄ , filtered and concentrated to obtain a crude product. Purification by silica gel column, petroleum ether: EtOAc = 5: 1 mixed solution (150 ml) was added, concentrated to 40 ml and filtered to give compound 11 as a white solid.

Synthesis of (iii) B-443 HCl / EtOAc (4M, 83 ml) was added to a solution of compound 11 (5.0 g, 9.2 mmol) in dichloromethane (50 ml) and stirred at 30 ° C. for 2.5 hours. The solvent was distilled off under reduced pressure until precipitation occurred, and a degassed _{aqueous solution of NaHCO 3} (60 ml) was added to adjust the pH to 6.5-7.0. The product was extracted with dichloromethane (60 mlx3) and the solvent was evaporated under reduced pressure to give 4.5 g of B-443 as a white solid.
^{1 1} H NMR (CDCl ₃ , δ, ppm): 7.46 (br, 1H), 7.25-7.05 (br, 5H), 6.92 (br, 1H), 6.84 (be, 1H) ), 6.50 (br, 4H), 3.57 (s, 12H), 2.02 (s, 6H) ,; ^{31 1} P NMR (CDCl ₃ , δ, ppm): -61.6 (s).

(Synthesis Example 3): Synthesis of Ligand B-444 Ligand B-444 was synthesized according to the following scheme.

(I) Synthesis of Compound 13 Compound 12 (10 g, 67 mmol) was added to HBr (106 g, 525 mmol), and the mixture was vigorously stirred to obtain a pale pink suspension. The suspension was cooled to −50 ° C., NaNO ₂ (7.9 g, 110 mmol) was added over 50 minutes and the mixture was stirred for 1 hour to obtain a yellow suspension. The temperature of the solution was -18 ° C. by slowly adding pre-cooled Et _{2 O (100 ml).} When the amount of gas generated decreased, the orange mixture was cooled to -50 ° C again, H ₂ O (8.3 ml) and Na ₂ CO ₃ (14.2 g, 134 mmol) were added, the temperature was raised to 30 ° C, and then 12 Stirring for hours gave a yellow suspension. _{H 2} O (150 ml) was added to this suspension. The product was extracted with EtOAc (150 mlx3) and the resulting organic layer was _{dried over Na 2} SO ₄ , filtered and concentrated to give a yellow liquid. By purifying this with a silica gel column, 8.2 g of Compound 13 was obtained as a pale yellow liquid.

(Ii) Synthesis of Compound 14 Compound 5 (7.7 g, 42 mmol), Compound 13 (8.2 g, 38 mmol), Pd (dba) ₂ (443 mg, 0.770 mmol), s-Phos (632 mg, 1.54 mmol). , K ₃ PO ₄ (16.3 g, 77.0 mmol) was weighed into a reaction vessel and toluene (80 ml) was added. The mixture was reacted at 110 ° C. for 14 hours to give a yellow suspension. The solvent was distilled off under reduced pressure and then purified by a silica gel column to obtain 1.7 g of Compound 14 as a yellow oily substance.

(Iii) Synthesis of Compound 15 n-BuLi (2.5 M, 11.4 ml) was added to a solution of Compound 14 (7.0 g, 26 mmol) in THF (50 ml) at 0 ° C., and the mixture was stirred at 30 ° C. for 1 hour. The suspension was cooled to −78 ° C., CuCl (2.82 g, 28.5 mmol) was added, and the mixture was stirred at 30 ° C. for 1 hour. The mixture was cooled to −78 ° C., a solution of Compound 3 (8.8 g, 26 mmol) in THF (100 ml) was added, and the mixture was stirred at 66 ° C. for 16 hours to obtain a blue suspension. The suspension was filtered and washed with dichloromethane (150 mlx3), and then the solvent was distilled off under reduced pressure to obtain a crude product. Dichloromethane (200 ml) and aqueous ammonia (200 ml) were added to the crude product, and the mixture was stirred under argon for 3 hours. It was filtered and extracted with dichloromethane (100 mlx3). The obtained organic layer was _{dried over Na 2} SO ₄ and then filtered and concentrated to obtain a yellow oily substance. Purification was performed on a silica gel column to obtain 6.4 g of compound 15 as a white solid.

(Iv) Synthesis of B-444 HCl / EtOAc (4M, 60 ml) was added to a solution of compound 15 (4.0 g, 7.0 mmol) in dichloromethane (20 ml) at 0 ° C. under argon and stirred at 30 ° C. for 2.5 hours. To obtain a colorless solution. The solvent was distilled off under reduced pressure to obtain a crude product. Degassed dichloromethane (100 ml) was added and washed with degassed saturated _{aqueous NaHCO 3} solution (100 ml). The obtained organic layer was concentrated to obtain 3.1 g of B-444 as a yellow solid.
^{1 1} H NMR (CDCl ₃ , δ, ppm): 7.46 (t, 1H), 7.25-7.19 (m, 3H), 7.13 (d, 2H), 6.93 (d, 1H) ), 6.81 (t, 1H), 6.48 (dd, 4H), 6.47 (br, 1H), 3.56 (s, 12H), 2.33 (m, 4H), 0.98 (T, 6H); ³¹ P NMR (CDCl ₃ , δ, ppm): -61.9 (s).

(Synthesis Example 4): Synthesis of Ligand B-449 Ligand B-449 was synthesized according to the following scheme.

(I) Synthesis of Compound 17 Compound 5 (20.1 g, 111 mmol), Compound 16 (20.0 g, 100 mmol), Pd (dba) ₂ (1.16 g, 2.01 mmol), s-Phos (1.65 g, 1.65 g, _{4.02mmol), K 3 PO 4 (} 42.7g, 201mmol) and was weighed in a reaction vessel was added toluene (150 ml). The mixture was reacted at 110 ° C. for 14 hours to give a yellow suspension. The solvent was distilled off under reduced pressure and then purified by a silica gel column to obtain 23.3 g of Compound 17 as a yellow oily substance.

(Ii) Synthesis of Compound 18 n-BuLi (2.5 M, 17.2 ml) was added to a solution of Compound 17 (10 g, 39 mmol) in THF (50 ml) at 0 ° C., and the mixture was stirred at 25 ° C. for 2 hours. The suspension was cooled to 0 ° C., CuCl (4.25 g, 42.9 mmol) was added, and the mixture was stirred at 25 ° C. for 1 hour. The suspension was cooled to −78 ° C., a solution of Compound 3 (13.3 g, 39.0 mmol) in THF (80 ml) was added, and the mixture was stirred at 66 ° C. for 16 hours to obtain a yellow solution. After filtration and washing with dichloromethane (50 ml x 3), the solvent was distilled off under reduced pressure to obtain a crude product. Purification on a silica gel column gave a yellow oily substance. Dichloromethane and aqueous ammonia were added to the obtained oily substance, and the mixture was stirred under argon for 12 hours. It was filtered and extracted with dichloromethane (100 ml x 3), _{dried over Na 2} SO ₄ , filtered and concentrated to give a white solid. N-BuLi (2.5 M, 4.64 ml) was added to a solution of this white solid (4.6 g, 4.6 mmol) in THF (20 ml) at 0 ° C., and the mixture was stirred at 25 ° C. for 12 hours. After adding H ₂ O (50ml), and extracted with EtOAc (50 ml x 3). The obtained organic layer was _{dried over Na 2} SO ₄ and filtered and concentrated to obtain a crude product. Purification with a silica gel column gave 0.7 g of Compound 18 as a yellow oily substance.

(Iii) Synthesis of B-449 HCl / EtOAc (4M, 69.7 ml) was added to a solution of compound 18 (2.35 g, 4.19 mmol) in dichloromethane (10 ml) at 0 ° C. under argon and 1.5 at 25 ° C. Stir for hours to give a yellow solution. The solvent was distilled off under reduced pressure to obtain a crude product. Degassed dichloromethane (100 ml) was added and washed with degassed saturated _{aqueous NaHCO 3} solution (100 ml). The obtained organic layer was concentrated to obtain 3.1 g of B-449 as a white solid.
^{1 1} H NMR (CDCl ₃ , δ, ppm): 7.48 (t, 1H), 7.36-7.30 (m, 2H), 7.23-7.12 (m, 4H), 7.02 (D, 1H), 6.81 (t, 1H), 6.56 (d, 1H), 6.48 (dd, 4H), 3.56 (s, 12H), 2.82 (sept, 1H) , 1.00 (d, 3H), 1.03 (d, 3H); ³¹ P NMR (CDCl ₃ , δ, ppm): -60.9 (s).

(Synthesis Example 5): Synthesis of Ligand B-450 Ligand B-450 was synthesized according to the following scheme.

(I) Synthesis of Compound 21 Compound 19 (1.66 g, 10.1 mmol), Compound 20 (2.0 g, 9.2 mmol), Pd (dba) ₂ (106 mg, 0.184 mmol), s-Phos (151 mg, 0.369 mmol), K ₃ PO ₄ (3.91 g, 18.4 mmol) was weighed into a reaction vessel and toluene (20 ml) was added. The mixture was reacted at 110 ° C. for 14 hours to give a yellow suspension. After distilling off the solvent under reduced pressure, the residue was purified on a silica gel column to obtain 2.3 g of Compound 21 as a yellow oily substance.

(Ii) Synthesis of Compound 22 n-BuLi (2.5 M, 3.95 ml) was added to a solution of Compound 21 (2.3 g, 9.0 mmol) in THF (10 ml) at 0 ° C., and the mixture was stirred at 25 ° C. for 2 hours. Obtained a blue solution. This solution was added to a solution of compound 3 (3.05 g, 8.96 mmol) in THF (30 ml) at −78 ° C. and stirred at 25 ° C. for 16 hours. _{H 2} O (50 ml) was added to this reaction solution, and an extraction operation was performed with EtOAc (50 ml x 3). The obtained organic layer was _{dried over Na 2} SO ₄ and filtered and concentrated to obtain a yellow oily substance. The obtained oily substance was purified by a silica gel column to obtain 2.36 g of Compound 22 as a white solid.

Synthesis of (iii) B-450 HCl / EtOAc (4M, 40 ml) was added to a solution of compound 22 (2.36 g, 4.21 mmol) in dichloromethane (15 ml) at 0 ° C. under argon and stirred at 25 ° C. for 1 hour. The solvent was distilled off under reduced pressure to obtain a set product. Degassed dichloromethane (100 ml) was added to this crude product, and degassed _{aqueous NaHCO 3} solution (100 ml) was added for washing. The organic layer was concentrated to give 2.0 g of B-450 as a white solid.
^{1 1} H NMR (CDCl ₃ , δ, ppm): 7.49 (d, 3H), 7.26-7.19 (m, 5H), 7.00 (br, 1H), 6.83 (t, 1H) ), 6.48 (dd, 4H), 3.54 (s, 12H), 2.92 (sept, 1H), 1.27 (d, 6H); ^{31 1} P NMR (CDCl ₃ , δ, ppm) :. -61.1 (s).

(Synthesis Example 6): Synthesis of Ligand B-424 Ligand B-424 was synthesized according to the following scheme.

(I) Synthesis of Compound 24 Compound 5 (9.00 g, 49 mmol), Compound 23 (8.71 g, 33.0 mmol), Pd (dba) ₂ (302 mg, 330 mmol), s-Phos (677 mg, 1.65 mmol). , K ₃ PO ₄ (13.2 g, 62.3 mmol) was weighed into a reaction vessel and toluene (50 ml) was added. The mixture was reacted at 110 ° C. for 12 hours to give a black suspension. _{H 2} O (50 ml) was added to this reaction solution, and an extraction operation was performed with EtOAc (55 ml x 3). The organic layer was washed with saturated brine, dried over Na ₂ SO ₄ , filtered, and the solvent was evaporated under reduced pressure. Purification was performed on the obtained crude product silica gel column to obtain 7.1 g of Compound 24 as a yellow oily substance.

(Ii) Synthesis of Compound 25 n-BuLi (2.5M, 2.1 ml) was added to a solution of Compound 24 (1.37 g, 5.00 mmol) in THF (10 ml) at 0 ° C., and the mixture was stirred at 25 ° C. for 1 hour. .. CuCl (520 mg, 5.25 mmol) was added to this reaction solution at −78 ° C., and the mixture was stirred at 30 ° C. for 1 hour. A solution of Compound 3 (1.70 g, 5.00 mmol) in THF (10 ml) was added to this reaction solution, the temperature was raised to 66 ° C., and the mixture was stirred for 16 hours to obtain a white suspension. Yellow solid occurs the addition of H ₂ O (50ml), filtered to collect the solid. Dichloromethane (20 ml) and aqueous ammonia (50 ml) were added to the recovered solid, and the mixture was stirred at 30 ° C. for 12 hours. Extraction work was carried out with dichloromethane (50 ml x 3), and the crude product was obtained by concentration. The crude product was purified on a silica gel column to give 700 mg of compound 25 as a white solid.

Synthesis of (iii) B-424 HCl / EtOAc (4M, 50 ml) was added to a solution of compound 25 (3.10 g, 5.36 mmol) in dichloromethane (20 ml) at 0 ° C. and stirred at 30 ° C. for 2 hours. The solvent was distilled off under reduced pressure to obtain a crude product. Degassed dichloromethane (100 ml) was added to this crude product, and degassed _{aqueous NaHCO 3} solution (100 ml) was added for washing. The organic layer was concentrated to give 2.0 g of B-424 as a white solid.
^{1 1} H NMR (CDCl ₃ , δ, ppm): 7.25-7.35 (m, 2H), 7.20 (t, 2H), 7.06 (d, 1H), 6.83 (t, 1H) ), 6.64 (d, 2H), 6.49 (dd, 4H), 6.35 (br, 1H), 3.68 (s, 6H), 3.55 (s, 12H); ^{31 1} P NMR (CDCl ₃ , δ, ppm): −59.2 (s).

(Synthesis Example 7): Synthesis of Ligand B-313 Ligand B-313 was synthesized according to the following scheme.

_{(I) Synthesis of Compound 28 Pd (PPh 3} ) ₂ Cl ₂ (0.110 g, 0.100 mmol _{) in a mixed solution of Dioxane (20 ml) and H 2} O (5 ml) of Compound 27 (0.360 g, 1.00 mmol). ), compound 26 _{(0.140 g,} 1.00 mmol), was added K 3 PO 4 (0.660g, 3.00mmol ) at 15 ° C.. The mixed solution was refluxed for 14 hours. Ice water (50 ml) was added to stop the reaction and extraction was performed with EtOAc (50 ml x 3). The obtained organic layer was washed with brine (50 ml), dried over Na ₂ SO ₄ , and filtered and concentrated to obtain a crude product. The crude product was purified on a silica gel column to give 0.100 g of compound 28 as a pale yellow solid.

(Ii) Synthesis of Compound 29 Compound 28 (5.60 g, 17.5 mmol) was added to a suspension of NaH (1.40 g, 35.0 mmol) in THF (30 ml) at 0 ° C., and the mixture was stirred for 1 hour. MOMCl (2.80 g, 35.0 mmol) was added to this solution at 0 ° C., and the mixture was stirred at 20 ° C. for 14 hours. Ice water (100 ml) was added to stop the reaction, and the extraction operation was carried out with EtOAc (100 ml x 3). The obtained organic layer was washed with brine (100 ml), dried over Na ₂ SO ₄ , and filtered and concentrated to obtain a crude product. The crude product was purified on a silica gel column to obtain 4.50 g of compound 29 as a white solid.

(Iii) Synthesis of Compound 30 n-BuLi (2.5 M, 5.6 ml) was added to a THF solution of Compound 29 (4.50 g, 14.0 mmol) at 0 ° C., and the mixture was stirred at 0 ° C. for 2 hours. A THF solution of Compound 3 (1.70 g, 5.00 mmol) was added to this reaction solution at −78 ° C., the temperature was raised to 20 ° C., and the mixture was stirred for 14 hours. After adding ice water (100 ml), an extraction operation was carried out with EtOAc (100 ml x 2), and the obtained organic layer was _{dried over Na 2} SO ₄ and concentrated to obtain a crude product. The crude product was purified on a silica gel column to obtain 1.80 g of compound 30 as a pale yellow solid.

(Iv) Synthesis of B-313 HCl / EtOAc (4M, 30 ml) was added to a solution of compound 30 (1.80 g, 2.68 mmol) in EtOAc (10 ml) at 0 ° C. and stirred at 15 ° C. for 1 hour. After neutralization by adding an aqueous solution of NaHCO ₃ (50 ml), an extraction operation was performed with EtOAc (50 ml x 2). The obtained organic layer was washed with brine (50 ml), dried over Na ₂ SO ₄ and concentrated to obtain 1.20 g of B-313 as a white solid.
^{1 1} H NMR (CDCl ₃ , δ, ppm): 7.44 (m, 1H), 7.31 (m, 2H), 7.23 (m, 2H), 7.16 (m, 5H), 7. 10 (m, 6H), 6.53 (m, 1H), 6.47 (dd, 5H), 3.43 (s, 12H); ^{31 1} P NMR (CDCl ₃ , δ, ppm): -65.5 (S).

(Synthesis Example 8): Synthesis of Ligand B-27DM Ligand B-27DM was synthesized according to the contents described in Patent Document (International Patent Publication No. 2010/50256). The ligand B-27DM has the structure described in paragraph [0115] of this patent document.

(Synthesis Example 9): Synthesis of Ligand B-125 Ligand B-125 was synthesized according to the contents described in Patent Document (Patent No. 5863539). The ligand B-125 has the structure described in paragraph [0100] of this patent document.

3. 3. Preparation of α-olefin / (meth) acrylic acid ester copolymer (Example 1): Copolymerization of ethylene and t-butyl acrylate using ligand B-423 (i) Formation of complex (i) The following operation is performed. All were done in a nitrogen atmosphere. Hereinafter, bis-1,5-cyclooctadiene nickel (0) will be referred to as Ni (cod) ₂ .
Ni (cod) ₂ (53.8 mg, 0.196 mmol) was weighed in a two-necked eggplant flask, and toluene (19.6 ml) was added to prepare a 0.01 mol / l solution. 8.0 ml of this 0.01 mol / l toluene solution of Ni (cod) ₂ was added to the two-necked eggplant flask containing B-423 (44.9 mg, 0.0804 mmol) obtained in Synthesis Example 1 and added to 40 ° C. Was stirred for 30 minutes. The color of the reaction solution changed from yellow to orange.

(Ii) Copolymerization of ethylene and t-butyl acrylate In an inductively stirred autoclave with an internal volume of 2 L, dried toluene (1 L), t-butyl acrylate (23.0 ml, 158 mmol), and tri-n-octyl aluminum (0). .1 mmol) was introduced. After raising the temperature of the autoclave to 110 ° C. with stirring, ethylene was supplied to the autoclave to adjust the ethylene partial pressure to 3.0 MPa. After completion of the adjustment, the reaction solution (4.0 ml) obtained in (i) above was supplied to initiate copolymerization. After polymerization for 1 hour, 1,2-butanediol was introduced to terminate the reaction. After removing the unreacted gas, the autoclave was opened, ethanol was added to precipitate the copolymer, and the copolymer was filtered, washed, and dried by heating to obtain a copolymer. The polymerization results are shown in Table 3. In Table 3, tBA represents t-butyl acrylate. The activity represents the copolymer yield (g) per 1 mol of the complex used for the polymerization. The activity was calculated assuming that the ligand B-423 and Ni (cod) ₂ reacted one-to-one to form a nickel complex. The results of GPC and DSC measurements on the obtained copolymer are also shown in Table 3.

(Example 2): Copolymerization of ethylene and t-butyl acrylate using ligand B-443 (i) Formation of complex B-443 (65.1 mg, 0) obtained in Synthesis Example 2 as a ligand. A complex was formed in the same manner as in Example 1 except that .130 mmol) was used.
(Ii) Copolymerization of ethylene and t-butyl acrylate Copolymerization was carried out in the same manner as in Example 1 except that the reaction solution (8.0 ml) obtained in (i) above was used as the copolymer. The results are shown in Table 3.

(Example 3): Copolymerization of ethylene and t-butyl acrylate using ligand B-444 (i) Formation of complex B-444 (47.6 mg, 0) obtained in Synthesis Example 3 as a ligand. A complex was formed in the same manner as in Example 1 except that 0.0897 mmol) was used.
(Ii) Copolymerization of ethylene and t-butyl acrylate Copolymerization was carried out in the same manner as in Example 1 except that the reaction solution (2.0 ml) obtained in (i) above was used as the copolymer. The results are shown in Table 3.

(Example 4): Copolymerization of ethylene and t-butyl acrylate using ligand B-449 (i) Formation of complex B-449 (43.6 mg, 0) obtained in Synthesis Example 4 as a ligand. A complex was formed in the same manner as in Example 1 except that 0.0844 mmol) was used.
(Ii) Copolymerization of ethylene and t-butyl acrylate Copolymerization was carried out in the same manner as in Example 1 except that the reaction solution (4.0 ml) obtained in (i) above was used as the copolymer. The results are shown in Table 3.

(Example 5): Copolymerization of ethylene and t-butyl acrylate using ligand B-450 (i) Formation of complex B-450 (33.6 mg, 0) obtained in Synthesis Example 5 as a ligand. A complex was formed in the same manner as in Example 1 except that .0650 mmol) was used.
(Ii) Copolymerization of ethylene and t-butyl acrylate Copolymerization was carried out in the same manner as in Example 1 except that the reaction solution (4.0 ml) obtained in (i) above was used as the copolymer. The results are shown in Table 3.

(Example 6): Copolymerization of ethylene and t-butyl acrylate using ligand B-424 (i) Formation of complex B-424 (53.3 mg, 0) obtained in Synthesis Example 6 as a ligand. A complex was formed in the same manner as in Example 1 except that 0.0997 mmol) was used.
(Ii) Copolymerization of ethylene and t-butyl acrylate Copolymerization was carried out in the same manner as in Example 1 except that the reaction solution (8.0 ml) obtained in (i) above was used as the copolymer. The results are shown in Table 3.

(Example 7): Copolymerization of ethylene and t-butyl acrylate using ligand B-313 (i) Formation of complex B-313 (25.8 mg, 0) obtained in Synthesis Example 7 as a ligand. A complex was formed in the same manner as in Example 1 except that .0412 mmol) was used.
(Ii) Copolymerization of ethylene and t-butyl acrylate Copolymerization was carried out in the same manner as in Example 1 except that the reaction solution (2.0 ml) obtained in (i) above was used as the copolymer. The results are shown in Table 3.

(Comparative Example 1): Copolymerization of ethylene and t-butyl acrylate using ligand B-27DM (i) Formation of complex B-27DM (30.2 mg, 0) obtained in Synthesis Example 8 as a ligand. A complex was formed in the same manner as in Example 1 except that .0535 mmol) was used.
(Ii) Copolymerization of ethylene and t-butyl acrylate Copolymerization was carried out in the same manner as in Example 1 except that the reaction solution (2.0 ml) obtained in (i) above was used. The results are shown in Table 4.

(Comparative Example 2): Copolymerization of ethylene and t-butyl acrylate using ligand B-125 (i) Formation of complex B-125 (48.2 mg, 0) obtained in Synthesis Example 9 as a ligand. A complex was formed in the same manner as in Example 1 except that .0855 mmol) was used.
(Ii) Copolymerization of ethylene and t-butyl acrylate Copolymerization was carried out in the same manner as in Example 1 except that the reaction solution (2.0 ml) obtained in (i) above was used. The results are shown in Table 4.

4. Results and Discussion Tables 3 and 4 show the experimental results. FIG. 1 shows the relationship between the (meth) acrylic acid ester content and Mw in the copolymers obtained in Examples and Comparative Examples. In Tables 3, 4, and 1, "tBA" indicates the content of t-butyl acrylate in the copolymer.
In Examples 1-7, it was confirmed that a copolymer having a high content of t-butyl acrylate units and a high molecular weight could be obtained. On the other hand, Comparative Example 1-2 had a lower content of t-butyl acrylate units than Example 1-7.
As described above, according to the examples, it can be seen that a copolymer having a high (meth) acrylic acid ester content and a high molecular weight can be obtained.

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

According to the present invention, a copolymer having a high (meth) acrylic acid ester content and a high molecular weight is provided, and can be used in a wide range of applications. This copolymer can be produced by the production method of the present invention and has high industrial applicability.

Claims (5)

A metal complex represented by the following general formula (A).

[In the formula, M represents nickel or palladium. R ³ represents a hydrocarbon group that may contain hydrogen or a heteroatom having 1 to 20 carbon atoms. L ¹ represents a ligand coordinated to M. Further, R ³ and L ¹ may be bonded to each other to form a ring. X ¹ represents oxygen or sulfur. E ¹ represents phosphorus, arsenic or antimony. R ⁴ and R ⁵ each independently represent a hydrocarbon group that may contain a heteroatom having 1 to 30 carbon atoms. R ^{6 to} R ⁸ are hydrocarbon groups that may independently contain hydrogen, halogen, and a heteroatom having 1 to 30 carbon atoms, OR ² , CO ₂ R ² , CO ₂ M', and C (O). ) N (R ¹ ) ₂ , C (O) R ² , SR ² , SO ₂ R ² , OSO ₂ R ² , P (O) (OR ² ) _2-y (R ¹ ) _y , CN, NHR ² , _{^{N (R 2) 2, Si}} (OR 1) 3-x (R 1) x, OSi (OR 1) 3-x (R 1) x, NO 2, SO 3 M ', PO 3 M' 2, P (O) (OR ² ) _{represents 2} M'or an epoxy-containing group. Here, R ¹ represents hydrogen or a hydrocarbon group having 1 to 20 carbon atoms. Further, R ² represents a hydrocarbon group having 1 to 20 carbon atoms. M'represents alkali metal, ammonium, quaternary ammonium or phosphonium, x represents an integer from 0 to 3, and y represents an integer from 0 to 2. R ^{9 to} R ¹³ are hydrogen, and substituents represented by the general formula (B) (R ¹⁴ and R ¹⁵ are hydrocarbon groups having 1 to 6 carbon atoms, which may independently have hydrogen or a heteroatom, respectively. ^{Aryl group having 6 to 12 carbon atoms, an adamantyl group, OR 2} , SR ² , or N (R ² _{) 2} which may have a substituent (which may be bonded to each other to form a ring). Represents. However, ^{at least one of R 9 to} R ¹³ is a substituent represented by the general formula (B), an aryl group having 6 to 12 carbon atoms which may have a substituent, an adamantyl group, OR ² , SR ² or N (R ² ) ₂ . R ^{9 to} R ¹³ do not ring with each other. ] A claim characterized in that at least one of R ^{9 to} R ¹³ is a substituent represented by the general formula (B), an aryl group having 6 to 12 carbon atoms which may have a substituent, or an adamantyl group. Item 2. The metal complex according to Item 1. R ⁹ and R ¹³ have a substituent represented by the general formula (B), an aryl group having 6 to 12 carbon atoms which may have a substituent, an adamantyl group, OR ² , SR ² , or N (R). ²⁾ _2, metal complex according to claim 1, characterized in that a. 3. A third aspect of the present invention, wherein R ⁹ and R ¹³ are a substituent represented by the general formula (B), an aryl group having 6 to 12 carbon atoms which may have a substituent, or an adamantyl group. The metal complex according to. An α-olefin / (meth) acrylic acid ester, which comprises copolymerizing an α-olefin and a (meth) acrylic acid ester in the presence of the metal complex according to any one of claims 1 to 4. Method for producing a polymer.

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