JP5863539B2 - Metal complex and method for producing α-olefin and (meth) acrylic acid ester copolymer using the same - Google Patents

Description

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

A method of copolymerizing ethylene and vinyl acetate or (meth) acrylic acid ester which is a polar group-containing vinyl monomer by radical polymerization at high temperature and high pressure is well known. However, this method has a drawback in that the strength of the obtained copolymer is low because a copolymer having low crystallinity is formed by a large number of branch formations.
Brookhart et al. Reported that a copolymer of ethylene and an acrylate ester can be produced using a palladium complex using an α-diimine ligand as a catalyst.
However, the obtained copolymer is rich in a branched structure, and the branch has various carbon numbers including a methyl group and an ethyl group, and the number of branches is very large. 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, so-called a SHOP-based catalyst can be used for ethylene polymerization in a polar solvent, and a linear polymer with few branches can be obtained. It is known. In anticipation of such polar group resistance of the SHOP catalyst, copolymerization of ethylene and a polar monomer using the SHOP catalyst has been attempted.
However, it has been reported that the copolymerization with ethylene proceeds only when the polar group in the polar monomer is separated from the olefin, and the (meth) acrylic in which the polar group is directly bonded to the olefin. No examples of copolymerization of an acid ester and an α-olefin have been reported (for example, see 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 8), but biscyclohexane is used as a catalyst component. Octadiene nickel (Ni (COD) ₂ ) is required as a phosphine scavenger, and methyl methacrylate is present only at the end of the polymer and is not incorporated into the main chain other than the end.

On the other hand, a method of copolymerizing ethylene and an unsaturated carboxylic acid ester with a catalyst comprising a combination of a similar SHOP-based nickel (zero-valent) chelate complex and an aluminoxane is disclosed (for example, see Patent Document 2). . In the example of Patent Document 2, an example of copolymerization of ethylene and methyl acrylate is described, but since the amorphous polymer is by-produced, the amorphous polymer is removed by acetone extraction. There was a need. Moreover, about the obtained copolymer, there is only description regarding a methyl acrylate content, and there is no description regarding a structure other than that.
Pugh et al. (For example, see Non-patent Document 5), Nozaki et al. (For example, see Non-Patent Document 6), and Goodall et al. (For example, see Patent Document 3) have phosphinosulfonic acid ligands. It has been reported that a copolymer of ethylene and methyl acrylate can be obtained by using a palladium complex as a catalyst.
However, the catalyst used in these known documents is a scarce resource and uses expensive palladium, so that there is a great problem for industrial applications.

As described above, development of useful transition metal catalyst technology for copolymerizing olefin and acrylate ester is required. Generally, when polymerizing olefin with a single site catalyst, compared to conventional Ziegler-Natta catalyst. , The molecular weight tends to be difficult to increase.
For this reason, development is also demanded for a technique relating to a catalyst that improves the molecular weight of an olefin polymer or an olefin / acrylic acid ester copolymer and has a relatively high activity.

US Pat. No. 4,698,403 JP-A 64-14217 US Patent Application Publication No. 2007/0049712

S. Mecking et al. , J .; Am. Chem. Soc. 1998, 120, 888. S. D. Itel et al. , Chem. Rev. 2000, 100, 1169. P. Braunstein et al. , J .; Organomet. Chem. 1989, 367, 117. S. E. Baauaud et al. Inorg. Chem. 1986, 25, 3765. E. Drent et al. , Chem. Commun. 2002, 744. T. T. et al. Kochi et al. Dalton Trans. 2006, 25. U. Klabunde et al. , J .; Polym. Sci. : Part A: Polym. Chem. 1987, 25, 1989. V. C. Gibson, Chem. Commun. 2001, 1964.

  In view of the problems of the prior art described above, the object of the present invention is to produce an α-olefin / (meth) acrylate copolymer having few branches and crystallinity, particularly a polymer having a relatively high molecular weight. An object of the present invention is to provide an active catalyst component and a method for producing an α-olefin / (meth) acrylic acid ester copolymer using the same.

As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that a ligand having an aryl group as a host nucleus, phosphorus, arsenic, or antimony bonded to the aryl group (in the present invention, E ¹ and Description) Both of the two substituents R ⁴ and R ⁵ above contain two or more hetero atom-containing groups, and at least one of R ⁴ and R ⁵ is two or more hetero atom-containing groups. And a transition metal complex having a specific structure in which the substituent R ¹¹ is a halogen atom, an electron-withdrawing substituent such as CF ₃ or CN, as a catalyst component, It has been found that a copolymer having an extremely high polymerization activity and a high molecular weight can be obtained by copolymerizing an α-olefin and a (meth) acrylic acid ester, and the present invention has been completed based on these findings. It was.

  That is, according to 1st invention of this invention, the metal complex represented with the following general formula (A) is provided.

[Wherein, M represents nickel or palladium . R ³ represents a hydrogen atom or a hydrocarbon group that may contain a C 1-20 hetero atom. L ¹ represents a ligand coordinated to M. 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 are each independently a hydrocarbon group optionally containing a hetero atom having 1 to 40 carbon atoms, and R ⁴ and R ⁵ are selected from the group consisting of an alkoxy group and an aryloxy group. 2 or more selected oxygen atom-containing groups are contained, and both R ⁴ and R ⁵ are substituted with the oxygen atom-containing group at the 2-position and the 6-position, and at least one of R ⁴ and R ⁵ is at the 2-position and 6-position. Represents an aromatic hydrocarbon group substituted with an oxygen atom-containing group at a different position . R ¹⁰ , R ¹² and R ¹³ are each independently a hydrogen atom, a halogen atom, a hydrocarbon group which may contain a C 1-30 hetero atom, OR ² , CO ₂ R ² , CO ₂ M ', C (O) N (R ¹ ) ₂ , C (O) R ² , SR ² , SO ₂ R ² , SOR 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 ) ₂ M ′ or an epoxy-containing group, R ¹¹ is a halogen atom, a hydrocarbon group containing one or more hetero atoms having 1 to 30 carbon atoms, CO ₂ R ² , CO ₂ M ′, C (O) N (R ¹ ) ₂ , SO ₂ R ² , SOR ² , CN, NO ₂ , SO ₃ M ′, PO ₃ M ′ ₂ or P (O) (OR ² ) ₂ M ′ (wherein R ¹ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, R ² represents a hydrocarbon group having 1 to 20 carbon atoms, M 'represents an alkali metal, of ammonium, quaternary ammonium or phosphonium, x represents an integer of 0 to 3, y is 0-2 Represents an integer.) In addition, a plurality of groups appropriately selected from R ⁴ , R ⁵ , R ¹⁰ , R ¹² or R ¹³ are connected to each other and contain an alicyclic ring, an aromatic ring, or a heteroatom selected from oxygen, nitrogen or sulfur The number of ring members may be 5 to 8, and it may or may not have a substituent on the ring. ]

According to the second invention of the present invention, in the first invention , in the general formula (A), R ¹¹ is an electron-attracting substituent with respect to the aryl group which is the mother nucleus. A metal complex is provided.
Furthermore, according to the third invention of the present invention, in the first or second invention , in general formula (A), R ¹¹ is a fluorine atom, a perfluoromethyl group, a perfluorophenyl group, or CN. A featured metal complex is provided.

On the other hand, according to the fourth invention of the present invention, an α-olefin and a (meth) acrylic acid ester are copolymerized in the presence of the metal complex according to any one of the first to third inventions. A method for producing an α-olefin / (meth) acrylic acid ester copolymer is provided.

  The polymerization catalyst using the metal complex of the present invention is highly active, and by using the metal complex of the present invention as a polymerization catalyst, (meth) acrylic acid ester and α-olefin can be easily produced industrially. And the resulting copolymer has a high molecular weight. In general, the molecular weight is one of the dominant factors in polymer properties. By increasing the molecular weight, the interaction between polymer chains is strengthened. Therefore, the copolymer obtained by the present invention has mechanical and thermal properties. And is applicable as a useful molded body. Further, in the present invention, a nickel-centered catalyst can be used in place of rare and expensive palladium. Thus, the present invention provides a method for producing such an α-olefin / (meth) acrylic acid ester copolymer, which is very useful from an industrial viewpoint.

The present invention relates to a compound represented by the following general formula (B) or (C) and a transition metal belonging to Group 9, 10 or 11 of the periodic table such as nickel, palladium, cobalt, copper or rhodium. A reaction product obtained by bringing the transition metal complex (D) into contact therewith, that is, a metal complex represented by the general formula (A) (hereinafter also referred to as metal complex (A)), and Is a method for producing an α-olefin / (meth) acrylic acid ester copolymer in which α-olefin and (meth) acrylic acid ester are copolymerized in the presence of the catalyst component.
Hereinafter, the constituent monomer, catalyst component, production method and the like of the copolymer will be described in detail.
In the following description, the term “polymerization” is a generic term for homopolymerization of one type of monomer and copolymerization of a plurality of types of monomers. Simply referred to as “polymerization”.

1. Component monomer of copolymer (a) α-olefin The component (a) in the present invention is an α-olefin represented by the general formula: CH ₂ = CHR ⁷ . Here, R < ⁷ > is a hydrogen atom or a C1-C20 hydrocarbon group, and may have a branch, a ring, and / or an unsaturated bond. When the carbon number of R ⁷ is larger than 20, there is a tendency that sufficient polymerization activity is not expressed. For this reason, among them, preferable examples of the component (a) include α-olefins in which R ⁷ is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms.
More preferable component (a) is ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 3-methyl-1-butene, 4-methyl-1-pentene, vinyl. Examples thereof include cyclohexene and styrene. In addition, a single component (a) may be used, or a plurality of components (a) may be used in combination.

(B) (Meth) acrylic acid ester Component (b) in the present invention is a (meth) acrylic acid ester represented by the general formula: CH ₂ ═C (R ⁸ ) CO ₂ (R ⁹ ). Here, R < ⁸ > is a hydrogen atom or a C1-C10 hydrocarbon group, and may have a branch, a ring, and / or an unsaturated bond. R ⁹ is a hydrocarbon group having 1 to 30 carbon atoms, and may have a branch, a ring, and / or an unsaturated bond. Further, it may contain a hetero atom at an arbitrary position in R ⁹ .
When the carbon number of R ⁸ is 11 or more, there is a tendency that sufficient polymerization activity is not expressed. Accordingly, R ⁸ is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, but as a preferred component (b), R ⁸ is a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms (meth). An acrylic ester is mentioned. More preferable component (b) includes a methacrylic acid ester in which R ⁸ is a methyl group or an acrylate ester in which R ⁸ is a hydrogen atom. Similarly, when the carbon number of R ⁹ exceeds 30, the polymerization activity tends to decrease. Therefore, R ⁹ has 1 to 30 carbon atoms, but R ⁹ preferably has 1 to 12 carbon atoms, and more preferably 1 to 8 carbon atoms.
In addition, examples of the hetero atom that may be contained in R ⁹ include oxygen, sulfur, selenium, phosphorus, nitrogen, silicon, fluorine, and boron. Of these heteroatoms, oxygen, silicon and fluorine are preferred, and oxygen is more preferred. R ⁹ preferably does not contain a hetero atom.

  More preferable components (b) include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, (meth ) Isobutyl acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate Nonyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, phenyl (meth) acrylate, toluyl (meth) acrylate, benzyl (meth) acrylate, hydroxyethyl (meth) acrylate , Dimethylaminoethyl (meth) acrylate, diethylamino (meth) acrylate Ethyl, (meth) acrylic acid-2-aminoethyl, (meth) acrylic acid-2-methoxyethyl, (meth) acrylic acid-3-methoxypropyl, (meth) acrylic acid glycidyl, (meth) acrylic acid ethylene oxide, (Meth) acrylic acid trifluoromethyl, (meth) acrylic acid-2-trifluoromethylethyl, (meth) acrylic acid perfluoroethyl, (meth) acrylamide, (meth) acryldimethylamide, (meth) acrylic acid 2- Examples thereof include hydroxybutyl 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).

[Wherein M represents a transition metal belonging to Group 9, 10 or 11 of the periodic table. R ³ represents a hydrogen atom or a hydrocarbon group that may contain a C 1-20 hetero atom. L ¹ represents a ligand coordinated to M. 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 are each independently a hydrocarbon group that may contain a heteroatom having 1 to 40 carbon atoms, and both R ⁴ and R ⁵ are two or more heteroatom-containing groups. And at least one of R ⁴ and R ⁵ represents a hydrocarbon group containing two or more hetero atom-containing groups. R ¹⁰ , R ¹² and R ¹³ are each independently a hydrogen atom, a halogen atom, a hydrocarbon group which may contain a C 1-30 hetero atom, OR ² , CO ₂ R ² , CO ₂ M ', C (O) N (R ¹ ) ₂ , C (O) R ² , SR ² , SO ₂ R ² , SOR 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 ) ₂ M ′ or an epoxy-containing group, R ¹¹ is a halogen atom, a hydrocarbon group containing one or more hetero atoms having 1 to 30 carbon atoms, CO ₂ R ² , CO ₂ M ′, C (O) N (R ¹ ) ₂ , SO ₂ R ² , SOR ² , CN, NO ₂ , SO ₃ M ′, PO ₃ M ′ ₂ or P (O) (OR ² ) ₂ M ′ (wherein R ¹ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, R ² represents a hydrocarbon group having 1 to 20 carbon atoms, M ′ represents an alkali metal, an alkaline earth metal, ammonium, quaternary ammonium or phosphonium, x represents an integer of 0 to 3, y Represents an integer of 0 to 2). In addition, a plurality of groups appropriately selected from R ⁴ , R ⁵ , R ¹⁰ , R ¹² or R ¹³ are connected to each other and contain an alicyclic ring, an aromatic ring, or a heteroatom selected from oxygen, nitrogen or sulfur The number of ring members may be 5 to 8, and it may or may not have a substituent on the ring. ]

In the present invention, M is a transition metal belonging to Group 9, Group 10 or Group 11 of the Periodic Table, but preferably Group 10 nickel, palladium, platinum, Group 9 cobalt, rhodium and Group 11 copper. More preferably, they are group 10 nickel, palladium, and platinum, and most preferably group 10 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, the number of charges remaining on the atom of the element is indicated. 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, nickel is phosphorus, oxygen, a phenyl group carbon, When a bond is formed with nitrogen of pyridine, the formal oxidation number of nickel, that is, the valence of nickel is divalent. This is because, based on the above definition, in these bonds, the electron pair is assigned to phosphorus, oxygen, carbon, and nitrogen, which have a higher electronegativity than nickel, and the charges are 0 for phosphorus, -1 for oxygen, and phenyl. This is because the group is -1, the pyridine is 0, and the complex is electrically neutral as a whole, so that the charge remaining on the nickel is +2.
As the divalent transition metal, for example, nickel (II), palladium (II), platinum (II), and cobalt (II) are preferable, and copper (I) or rhodium (III) is also preferable other than divalent.

In the present invention, R ³ represents a hydrogen atom or a hydrocarbon group that may contain a C 1-20 hetero atom. The polymerization or copolymerization reaction in the present invention is considered to be initiated by the insertion of the component (a) or component (b) in the present invention into the bond between M and R ³ . Therefore, when the number of carbon atoms in R ³ is excessively large, this initiation reaction tends to be inhibited. For this reason, as preferable R < ³ >, it is C1-C16, More preferably, it is C1-C10.
Specific examples of R ³ include hydride group, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, n-hexyl group, 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 benzyl group, a trimethylsilyl group, a triethylsilyl group, and a triphenylsilyl group.

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

In the so-called SHOP metal complex, a complex similar to that of the present invention can be synthesized by using phosphine such as trimethylphosphine or triphenylphosphine instead of L ^{1 in} the present invention. However, when such a ligand is used, it is known that the use of a scavenger that removes the ligand from M is essential for the expression of the olefin polymerization ability (for example, see Non-Patent Document 7). .) As scavengers used for such purposes, Ni (COD) ₂ (COD: cyclooctadiene), B (C ₆ F ₅ ) ₃ , aluminoxanes, rhodium complexes and the like are known.

Preferred L ¹ in the present invention includes pyridines, piperidines, alkyl ethers, aryl ethers, alkylaryl ethers, cyclic ethers, alkyl nitrile derivatives, aryl nitrile derivatives, alcohols, amides, aliphatic esters. , Aromatic esters, amines, cyclic unsaturated hydrocarbons and the like. More preferred L ¹ includes pyridines, cyclic ethers, aliphatic esters, aromatic esters, cyclic olefins and the like, and particularly preferred 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).

R ³ and L ¹ may be bonded to each other to form a ring. Examples of such include a cyclooct-1-enyl group, which is also a preferred embodiment in the present invention.

In the present invention, X ¹ represents oxygen or sulfur. Of these, oxygen is preferred. 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 each independently a hydrocarbon group optionally containing a hetero atom having 1 to 40 carbon atoms, and both R ⁴ and R ⁵ are hetero atom-containing groups. And at least one of R ⁴ and R ⁵ represents a hydrocarbon group containing two or more hetero atom-containing groups. In the present invention, the term “species” includes a case in which a group of substituents having different chemical properties is pointed out and a case in which a chemical structure indicates a different substituent. For example, when referring to a group of substituents having different chemical properties, a combination of an alkoxy group and an aryloxy group, and the like, and when indicating a substituent having a different chemical structure, a methoxy group and an alkoxy group A combination with an ethoxy group is applicable.
R ⁴ and R ⁵ are in the vicinity of the metal M and interact with M sterically and / or electronically. In order to exert such effects, R ⁴ and R ⁵ are preferably bulky. R ⁴ and R ⁵ preferably have 6 to 40 carbon atoms, more preferably 8 to 40 carbon atoms.
In R ⁴ and R ⁵ , examples of the hetero atom contained in the hetero atom-containing group include oxygen, nitrogen, phosphorus, sulfur, selenium, silicon, fluorine, and boron. Of these heteroatoms, oxygen, sulfur, nitrogen, phosphorus and silicon are preferred. Examples of the heteroatom-containing group containing these heteroatoms include oxygen-containing groups such as alkoxy groups, aryloxy groups, acyl groups, aroyl groups, and carboxylate groups, and nitrogen-containing groups include amino groups and imino groups. Groups, amide groups, etc., sulfur-containing groups include thioalkoxy groups and thioaryloxy groups, phosphorus-containing substituents include phosphano groups, and silicon-containing groups include trialkyls. Examples thereof include a silyl group, a dialkylarylsilyl group, and an alkyldiarylsilyl group. Of these heteroatom-containing groups, the most preferred is an amino group, an alkoxy group, or an aryloxy group.

As the hetero atom-containing group, those having an electron donating property and capable of coordinating with a transition metal are preferable. Specific examples of such heteroatom-containing groups include the following.
That is, as an oxygen-containing group, methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, t-butoxy group, phenoxy group, p-methylphenoxy group, p-methoxyphenoxy group, acetyl group, Examples thereof include a benzoyl group, an acetoxy group, an ethyl carboxylate group, a t-butyl carboxylate group, and a phenyl carboxylate group. Examples of the nitrogen-containing group include a dimethylamino group, a diethylamino group, a di-n-propylamino group, and a cyclohexylamino group. Examples of the sulfur-containing group include a thiomethoxy group, a thioethoxy group, a thio-n-propoxy group, a thioisopropoxy group, a thio-n-butoxy group, a thio-t-butoxy group, a thiophenoxy group, a p-methylthiophenoxy group, Examples thereof include a p-methoxythiophenoxy group. Furthermore, examples of the phosphorus-containing substituent include a dimethylphosphino group, a diethylphosphino group, a di-n-propylphosphino group, and a cyclohexylphosphino group.

Both R ⁴ and R ⁵ contain two or more hetero atom-containing groups, and at least one of R ⁴ and R ⁵ represents a hydrocarbon group containing two or more hetero atom-containing groups.
In the present invention, R ⁴ and R ⁵ are each independently a hydrocarbon group containing a hetero atom having 1 to 40 carbon atoms, more specifically, a branched chain hydrocarbon group containing a hetero atom. , An alicyclic hydrocarbon group containing a hetero atom, and an aryl group containing a hetero atom. As described above, R ⁴ and R ⁵ are preferably bulky. Therefore, among these, an alicyclic hydrocarbon group containing a hetero atom or an aryl group containing a hetero atom is preferable, and an aryl group containing a hetero atom is most preferable. Examples of such an aryl group include a phenyl group, a naphthyl group, and an anthracenyl group.

In R ⁴ and R ⁵ of the present invention, when the hetero atom-containing group described above is bonded to the aromatic skeleton of these aryl groups, the bonding mode may be that the hetero atom-containing group is directly bonded to the aromatic skeleton. , And may be bonded to the aromatic skeleton via a spacer such as a methylene group. In addition, when a hetero atom containing group couple | bonds with an aromatic skeleton through a methylene group, the number of methylene groups is preferable. As the substitution position, among the aromatic skeleton in R ⁴ and R ^5, ortho position is preferred to the carbon bonded to E ^1. By doing so, it is possible to take a spatial arrangement so that the heteroatoms in R ⁴ and R ⁵ interact with M.

As specific examples of preferable R ⁴ and R ⁵ , as a hydrocarbon group containing two or more of one kind of heteroatom-containing group, 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-dimethoxymethylphenyl group, 2,4,6-trimethoxymethylphenyl group, 4-methyl-2,6-dimethoxymethylphenyl group, 4-t-butyl-2,6-dimethoxy Methylphenyl group, 1,3-dimethoxymethyl-2-naphthyl group, 2,6-diphenoxymethylphenyl group, 2,4,6-triphenoxymethylphenyl group, 4-methyl-2,6-diphenoxymethylphenyl Group, 4-t-butyl-2,6-diphenoxymethylphenyl group, 1,3-diphenoxymethyl-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-methoxyethyl) phenyl 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 -A naphthyl group etc. can be mentioned. Moreover, as a hydrocarbon group containing 2 or more types of hetero atom containing groups, 2-methoxy-6-phenoxyphenyl group, 4-t-butyl-2-methoxy-6-phenoxyphenyl group, 1-methoxy-3- Phenoxy-2-naphthyl group, 3-methoxy-1-phenoxy-2-naphthyl group, 2-ethoxy-6-phenoxyphenyl group, 4-t-butyl-2-ethoxy-6-phenoxyphenyl group, 1-ethoxy- A 3-phenoxy-2-naphthyl group, a 3-ethoxy-1-phenoxy-2-naphthyl group, and the like can be given.

R ¹⁰ , R ¹² and R ¹³ are each independently a hydrogen atom, a halogen atom, a hydrocarbon group which may contain a C 1-30 hetero atom, OR ² , CO ₂ R ² , CO ₂ M ', C (O) N (R ¹ ) ₂ , C (O) R ² , SR ² , SO ₂ R ² , SOR 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 ) ₂ M ′ or an epoxy-containing group, R ¹¹ is a halogen atom, a hydrocarbon group containing one or more hetero atoms having 1 to 30 carbon atoms, CO ₂ R ² , CO ₂ M ′, C (O) N (R ¹ ) ₂ , SO ₂ R ² , SOR ² , CN, NO ₂ , SO ₃ M ′, PO ₃ M ′ ₂ or P (O) (OR ² ) ₂ M ′ (wherein R ¹ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, R ² represents a hydrocarbon group having 1 to 20 carbon atoms, M ′ represents an alkali metal, an alkaline earth metal, ammonium, quaternary ammonium or phosphonium, x represents an integer of 0 to 3, y Represents an integer of 0 to 2).
In addition, a plurality of groups appropriately selected from R ⁴ , R ⁵ , R ¹⁰ , R ¹² or R ¹³ are connected to each other and contain an alicyclic ring, an aromatic ring, or a heteroatom selected from oxygen, nitrogen or sulfur The number of ring members may be 5 to 8, and it may or may not have a substituent on the ring.

Among these, R ¹¹ is preferably an electron-withdrawing substituent with respect to the aryl group as the mother nucleus, because it tends to give a highly active polymerization catalyst. Specific examples of R ¹¹ include a halogen atom, a hydrocarbon group which may contain a C 1-30 hetero atom, OR ² , CO ₂ R ² , CO ₂ M ′, C (O). N (R ¹ ) ₂ , C (O) R ² , SR ² , SO ₂ R ² , SOR 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 ) ₂ M ′, or an epoxy-containing group, fluorine, chlorine, bromine, iodine, heteroatom-containing hydrocarbon group as a halogen atom, perfluoromethyl group, perfluoroethyl group, Fluoropropyl group, perfluorobutyl group, perfluorophenyl group, -Fluoronaphthyl group, difluorophenyl group, trifluorophenyl group, nitrophenyl group, dinitrophenyl group, cyanophenyl group, trimethylsilyl group, triethylsilyl group, tripropylsilyl group, triphenylsilyl group, dimethylphenylsilyl group, methyldiphenyl A silyl group, or an isomer thereof can be exemplified.
Among these, particularly preferred R ¹¹ includes fluorine, a perfluoromethyl group, a perfluorophenyl group, and CN.

As for R ¹³ , an electron-attracting substituent and a bulky substituent with respect to the aryl group which is the mother nucleus is preferable because it tends to give a highly active polymerization catalyst. Specific examples of R ¹³ include halogen, fluorine, chlorine, bromine and iodine. The hydrocarbon group which may contain a hetero atom includes perfluoromethyl group, perfluoroethyl. Group, perfluoropropyl group, perfluorobutyl group, perfluorophenyl group, perfluoronaphthyl group, difluorophenyl group, trifluorophenyl group, nitrophenyl group, dinitrophenyl group, cyanophenyl group, anthracenyl group, pyridyl group, pyrrolyl Group, carbazolyl group, trimethylsilyl group, triethylsilyl group, tripropylsilyl group, triphenylsilyl group, or isomers thereof.
Among these, particularly preferred R ¹³ includes a perfluoroisopropyl group, a perfluoro-t-butyl group, a perfluorophenyl group, and a 9-carbazolyl group.
R ⁴ , R ⁵ , R ¹¹ , and R ¹³ are as described above. Table 1 shows particularly preferable combinations of R ⁴ , R ⁵ , R ¹¹ , and R ¹³ .

  Hereinafter, although the metal complex (A) of this invention is illustrated below, it is not limited to the following illustration. In the following examples, Me represents a methyl group, and Ph represents a phenyl group.

  Depending on the ligand structure and complex formation conditions, stereoisomers of the complex represented by the general formula (A) may be formed. Further, it is possible that M takes a coordination number other than 4. This is also a kind of isomer. The complex of the present invention may be such an isomer or a mixture of such isomers. Hereinafter, an example is shown for the case where M has a coordination number of 5.

3. Method for Producing Metal Complex The metal complex of the present invention is a transition metal complex (D) comprising a compound represented by the following general formula (B) and / or (C) and a transition metal of group 9, 10 or 11 Can be obtained by bringing them into contact with each other.

[In formula (B) or (C), Z represents a hydrogen atom or a leaving group, and m represents the valence of Z. X ¹ , E ¹ , R ⁴ , R ⁵ , R ¹⁰ , R ¹¹ , R ¹² and R ¹³ are as described above. ]
Z is a hydrogen atom or a leaving group, and specific examples include a hydrogen atom, an R ¹ SO ₂ group (where R ¹ is as described above), a CF ₃ SO ₂ group, and the like. it can.

Although the general formula (C) is expressed 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 (D) of the present invention.
Specific examples of the counter cation include ammonium, quaternary ammonium, phosphonium, and metal ions of Groups 1 to 14 of the periodic table. Of these, preferably NH ₄ ⁺ , R ¹ ₄ N ⁺ (wherein R ¹ is as described above, and four R ₁ may be the same or different), and R ¹ ₄ P ⁺ (here R ¹ is as described above, and four R ^{1 s} may be the same or different), Li ⁺ , Na ⁺ , K ⁺ , Mg ²⁺ , Ca ²⁺ , Al ³⁺ , more preferably R ¹ ₄ N ⁺ (wherein R ¹ is as described above, and four R ¹ may be the same or different), Li ⁺ , Na ⁺ , K ⁺ .

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

As the transition metal complex component (D) used in the present invention, those capable of reacting with the compound represented by the general formula (B) or (C) to form a complex having a polymerization ability are used. These are sometimes called precursors (precursors).
For example, as the transition metal complex (D) containing nickel, bis (1,5-cyclooctadiene) nickel (0), a complex represented by the general formula: (CH ₂ CR ¹ CH ₂ ) ₂ Ni (here R ¹ is as described above), bis (cyclopentadienyl) nickel (II), the general ^{_{formula:. Ni (CH 2 SiR 1}} 3) 2 L 1 2 in complex represented (wherein ^R 1, L ¹ are as described herein), the general ^formula:. _NiR 1 ^{2 L} _{1 2} in complex represented (wherein ^R 1, ^{L 1} are as described herein. ) Etc. can be used.

The transition metal complex (D) containing a Group 9, 10 or 11 transition metal is represented by the general formula: MR ¹ _p L ¹ _q (where M is a Group 9, 10 or 11 transition). And R ¹ and L ¹ are as described herein, and p and q are integers of 0 or more that satisfy the valence of M.).

Among these transition metals, bis (1,5-cyclooctadiene) nickel (0), a complex represented by the general formula: (CH ₂ CR ¹ CH ₂ ) ₂ Ni (here R ¹ are as described herein), the general ^{_{formula:. Ni (CH 2 SiR 1}} 3) R 1, L 1 complex represented by ^{2 L} _{1 2} (in this case, as described herein A complex represented by the general formula: NiR ¹ ₂ L ¹ ₂ (where R ¹ and L ¹ are as described in the present specification), Pd (dba) ₂ , Pd ₂ (dba) ₃ , Pd ₃ (dba) ₄ (where dba represents dibenzylideneacetone), Pd (OCOCH ₃ ) ₂ , (1,5-cyclooctadiene) Pd (methyl) (chloride) It is.

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, Lut represents 2,6-lutidine), NiPh ₂ (Py) ₂ , Ni (Ph) ₂ ( _{lut) 2, Pd (dba)} 2, Pd 2 (dba) 3, Pd 3 (dba) 4 ( wherein, dba is. representing _{dibenzylideneacetone), Pd (OCOCH 3) 2} , (1,5- Cyclooctadiene) Pd (methyl) (chloride).

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

After this reaction, the component constituting (D), which is a component other than the transition metal of (D), is substituted with the portion other than Z of component (B) or component (C), and the present invention. A metal complex represented by the general formula (A) is generated. This substitution reaction preferably proceeds quantitatively, but may not proceed completely in some cases. After completion of the reaction, in addition to the complex represented by the general formula (A), other components derived from (B), (C) and (D) coexist, but when performing the polymerization reaction or copolymerization reaction of the present invention. In addition, these other components may or may not be removed. Generally, 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. When nickel or palladium is used as M according to the present invention, the stability of the purified complex (A) may be increased by allowing Lewis basic L ¹ to coexist in the system. in this 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 L ^1.

  In the present invention, the reaction is carried out in a separate container from the reactor used for the polymerization of α-olefin and the copolymerization of α-olefin and (meth) acrylate, and the complex (A ) May be subjected to polymerization of α-olefin, copolymerization of α-olefin and (meth) acrylic acid ester, or the reaction may be performed in the presence of these monomers. Moreover, you may perform reaction in the reactor used for the superposition | polymerization of (alpha) -olefin polymerization and (alpha) -olefin, and (meth) acrylic acid ester. In this case, these monomers may exist or may not exist. Moreover, about a component shown by general formula (B)-(C), each independent component may be used, respectively, and multiple types of component may be used together, respectively. Particularly, for the purpose of widening the molecular weight distribution and the comonomer content distribution, a combination of these plural types is useful.

  Hereinafter, (B) that can be used in the present invention is exemplified, but the present invention is not limited to the following examples. In the following examples, Me represents a methyl group, and Ph represents a phenyl group.

4). Polymerization Reaction In the present invention, the metal complex represented by the general formula (A) can be used as a catalyst component for polymerization or copolymerization. As described above, the metal complex represented by the general formula (A) can be formed by the reaction of the general formula (B) or (C) with the transition metal complex component (D). 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. Such loading may be carried out in the presence or absence of these monomers in a reactor used for polymerization of α-olefin or copolymerization of α-olefin and (meth) acrylate, You may carry out in a container different from a vessel.

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.

As the inorganic silicate, clay, clay mineral, zeolite, diatomaceous earth and the like can be used. A synthetic product may be used for these, and the mineral produced naturally may be used. Specific examples of clays and clay minerals include allophanes such as allophane, kaolins such as dickite, nacrite, kaolinite and anorcite, halloysites such as metahalloysite and halloysite, and serpentine such as chrysotile, lizardite and antigolite. Stone group, montmorillonite, sauconite, beidellite, nontronite, saponite, hectorite, etc. Examples include clay, gyrome clay, hysingelite, pyrophyllite, and ryokdeite group. These may form a mixed layer. Examples of the artificial compound include synthetic mica, synthetic hectorite, synthetic saponite, and synthetic teniolite.
Of these specific examples, preferably, kaolins such as dickite, nacrite, kaolinite, anorcite, halosites such as metahalosite, halosite, chrysotile, lizardite, serpentine such as antigolite, montmorillonite, Smectites such as soconite, beidellite, nontronite, saponite, hectorite, vermiculite minerals such as vermiculite, mica minerals such as illite, sericite, sea chlorite, synthetic mica, synthetic hectorite, synthetic saponite, synthetic teniolite Particularly preferred are montmorillonite, sauconite, beidellite, nontronite, saponite, smectite such as hectorite, vermiculite mineral such as vermiculite, synthetic mica, synthetic hectorite, synthetic saponite, synthetic Taeniolite.

These carriers may be used as they are, but may be treated with hydrochloric acid, nitric acid, sulfuric acid, etc. and / or LiCl, NaCl, KCl, CaCl ₂ , MgCl ₂ , Li ₂ SO ₄ , MgSO 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 produce a salt in the reaction system. Further, shape control such as pulverization and granulation and drying treatment may be performed.

  The polymerization reaction in the present invention is a liquid such as a hydrocarbon solvent such as propane, n-butane, isobutane, n-hexane, n-heptane, toluene, xylene, cyclohexane and methylcyclohexane, a liquefied α-olefin, diethyl ether, The reaction is carried out in the presence or absence of a polar solvent 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. Furthermore, an ionic liquid can also be used as a solvent. In addition, in order to obtain high polymerization activity and high molecular weight, the above-mentioned hydrocarbon solvent and ionic liquid are more preferable.

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 inhibits radical polymerization and an additive that has an action of stabilizing the produced copolymer are preferable. Examples of preferable additives include quinone derivatives and hindered phenol derivatives.
Specifically, monomethyl ether hydroquinone, 2,6-di-t-butyl 4-methylphenol (BHT), reaction product of trimethylaluminum and BHT, reaction product of alkoxide of tetravalent titanium and BHT, etc. 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. Further, it may be used L ¹ and an ionic liquid according to the present invention as an additive.

A preferred additive in the present invention is Lewis base. By selecting an appropriate Lewis base, the activity, molecular weight, and copolymerizability of the acrylate ester can be improved. The amount of the Lewis base is 0.0001 equivalent to 1000 equivalents, preferably 0.1 equivalents to 100 equivalents, more preferably 0.3 equivalents to the transition metal M in the catalyst component present in the polymerization system. 30 equivalents. There is no restriction | limiting in particular about the method of adding a Lewis base to a polymerization system, Arbitrary methods can be used. For example, it may be mixed with the catalyst component of the present invention, added with a monomer, or added to the polymerization system independently of the catalyst component or the monomer. A plurality of Lewis bases may be used 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, alkylaryl ethers, cyclic ethers, alkyl nitriles, aryl nitriles, alcohols, amides, aliphatic esters , Aromatic esters, phosphates, phosphites, thiophenes, thianthrenes, thiazoles, oxazoles, morpholines, cyclic unsaturated hydrocarbons, and the like.
Among these, particularly preferred Lewis bases are aromatic amines, aliphatic amines, cyclic ethers, aliphatic esters, aromatic esters, and among them, preferred Lewis bases are pyridine derivatives, pyrimidine derivatives, 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-methylquinoline, phenazine, 1,10-phenanthroline, N-methylpyrrole, 1,8-diazabicyclo- [5.4.0] -undec-7-ene, 1,4 -Diazabicyclo- [2,2,2] -octane, triethylamine, benzonitrile, picoline, triphenylamine, N-methyl-2-pyrrolidone 4-methylmorpholine, benzoxazole, benzothiazole, furan, 2,5-dimethylfuran, dibenzofuran, xanthene, 1,4-dioxane, 1,3,5-trioxane, dibenzothiophene, thianthrene, triphenylphosphonium cyclo Examples thereof include pentadienide, triphenyl phosphite, triphenyl phosphate, tripyrrolidinophosphine, and tris (pyrrolidino) borane.

  In the present invention, the polymerization mode is not particularly limited. Slurry polymerization in which at least a part of the generated polymer in the medium becomes a slurry, bulk polymerization using the liquefied monomer itself as a medium, gas phase polymerization performed in a vaporized monomer, or a polymer generated 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, any of batch polymerization, semi-batch polymerization, and continuous polymerization may be used. Moreover, living polymerization may be sufficient and it may superpose | polymerize, combining chain transfer. Furthermore, so-called chain transfer agent (CSA) may be used in combination, and chain shuffling or coordinative chain transfer polymerization (CCTP) may be performed.

  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. A conventionally known method can be used to separate 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, optimum settings can be made in consideration of productivity and process capability from the following ranges. 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 200 MPa, and the polymerization time is 0.1 minutes to It can be selected from the range of 10 hours, preferably 0.5 minutes to 7 hours, more preferably 1 minute to 6 hours.

In the present invention, the polymerization is generally performed 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.
There are no particular restrictions on the supply of catalyst and monomer to the polymerization reactor, and various supply methods can be used 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 polymerization reactor in advance and a catalyst is supplied thereto. In this case, an additional monomer or an additional catalyst may be supplied to the polymerization reactor. In the case of continuous polymerization, a method can be used in which a predetermined amount of monomer and catalyst are continuously or intermittently supplied to the polymerization reactor to continuously carry out the polymerization reaction.

  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 polymer. 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 molecular weight by controlling the ligand structure in the transition metal complex. For example. 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 addition, when the component (b) itself becomes 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). is there. When the molecular weight is adjusted by controlling the ligand structure in the transition metal complex, the type, number, and arrangement of the hetero atom-containing groups in R ⁴ described above are controlled, and bulky substituents around the metal M In general, the tendency to improve the molecular weight can be utilized by arranging a hetero atom in the above-described R ^{10 to} R ¹³ . In addition, it is preferable to arrange | position an electron-donating group with respect to the metal M so that electron-donating groups, such as an aryl group and a hetero atom containing substituent, can interact. Whether or not such an electron-donating group can interact with the metal M can be generally determined by measuring the distance between the electron-donating group and the metal M by a molecular model or molecular orbital calculation.

  The copolymer of the present invention has good paintability, printability, antistatic properties, inorganic filler dispersibility, adhesion to other resins, and compatibility with other resins due to the effects based on the polar groups of the copolymer. Etc. are expressed. Utilizing these properties, the copolymer of the present invention can be used for various applications. For example, it can be used as a film, sheet, adhesive resin, binder, compatibilizing agent, wax, and the like.

In the following examples and comparative examples, the present invention will be described in more detail, but the present invention is not limited thereto. In addition, the evaluation method used by the Example and the comparative example is as follows. In addition, the synthesis example shows the ligand used for the contact product and the method for producing the complex used in the comparative example.
In the following synthesis examples, unless otherwise specified, the operation was performed in a purified nitrogen atmosphere, and the solvent used was dehydrated and deoxygenated.

1. Evaluation Method (1) Tm, Tc:
It calculated | required by the following DSC measurements.
Using a Perkin Elmer PYRIS Diamond DSC differential scanning calorimeter, a sample (about 5 mg) was 210 °
10 ° after melting for 5 minutes at C
-20 ° at a rate of C / min
Decrease to C, -20 °
10 ° after holding at C for 5 minutes
210 ° at a rate of C / min
A melting curve was obtained by raising the temperature to C. The peak top temperature of the main exothermic peak in the temperature lowering stage was defined as the crystallization temperature Tc. In addition, the peak top temperature of the main endothermic peak in the final temperature increase stage 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:
It calculated | required by the following GPC measurement.
First, about 20 mg of a sample was collected in a vial for a high temperature GPC pretreatment device PL-SP260VS manufactured by Polymer Laboratories, and o-dichlorobenzene containing BHT as a stabilizer (BHT concentration = 0.5 g / L). ) Was added to adjust the polymer concentration to 0.1 (% by weight). The polymer was dissolved by heating to 135 ° C. in the pretreatment apparatus for high temperature GPC PL-SP260VS, and filtered through a glass filter to prepare a sample.
In the GPC measurement in the present invention, no polymer was captured by the glass filter.
Next, GPC measurement was performed using Tosoh's TSKgel GMH-HT (30 cm × 4) and a Waters GPCV2000 equipped with an RI detector. As measurement conditions, sample solution injection amount: 524.5 (μl), column temperature: 135 ° C., solvent: o-dichlorobenzene, flow rate: 1.0 (ml / min) were employed. The molecular weight was calculated as follows. That is, a commercially available monodispersed polystyrene is used as a standard sample, a calibration curve relating to the retention time and molecular weight is created from the polystyrene standard sample and the viscosity formula of the ethylene polymer, and the molecular weight is calculated based on the calibration curve. went.
In addition, as a viscosity formula, [η] = K × M ^α is used, for polystyrene, K = 1.38E ⁻⁴ , α = 0.70 is used, and for an ethylene polymer. , K = 4.77E ⁻⁴ , α = 0.70.

2. Ligand Synthesis [Synthesis Example 1]: (Synthesis of Ligand B-168)
Ligand B-168 was synthesized according to the following scheme.

(I) To a THF solution (30.0 mL) of compound 1 (7.86 g, 30.0 mmol), a hexane solution of n-butyllithium (2.5 M, 12.0 mL, 30.0 mmol) was added at 0 ° C. The mixture was stirred at room temperature for 2 hours to obtain a solution containing compound 2.
(Ii) To a THF solution (100 mL) of compound 3 (50.0 g, 0.250 mol), a hexane solution of n-butyllithium (2.5 M, 100 mL, 0.250 mol) was added at 0 ° C., and at room temperature. Stir for 2 hours. To this, iodine (63.5 g, 0.250 mol) was added in portions at 0 ° C., and then stirred at room temperature for 2 hours. Saturated aqueous sodium sulfite (100 mL) was added to quench the reaction, and the solvent was removed under reduced pressure. Ethyl acetate was added for extraction, and the organic layer was dried over sodium sulfate and concentrated. The crude product was purified on a silica gel column using petroleum ether as a developing solution to obtain Compound 4 as a white solid.
(Iii) A THF solution (2.0 M, 15.0 mL, 30.0 mmol) of isopropylmagnesium chloride was added to a THF solution (30.0 mL) of compound 4 (9.78 g, 30.0 mmol) at −30 ° C., and Stir at room temperature for 2 hours. Thereafter, phosphorus trichloride (6.5. 0 mL, 75.0 mmol) was added at -78 ° C, and the mixture was stirred at room temperature for 1 hour. After removing the solvent and excess phosphorus trichloride under reduced pressure, THF (30 mL) was added to obtain a solution containing compound 5. To this was added the THF solution of the previous compound 2 at −78 ° C., and the mixture was stirred at room temperature for 1 hour to obtain a solution containing compound 6.
(Iv) A THF solution (30 mL) of compound 7 (6.18 g, 30.0 mmol) was cooled to 0 ° C., and a hexane solution of n-butyllithium (2.5 M, 15.0 mL, 30.0 mmol) under an argon atmosphere. ) Was added dropwise and stirred at room temperature for 2 hours. To this was added dropwise the solution of Compound 6 at the previous stage at -78 ° C, and the mixture was stirred at room temperature for 16 hours. Ice water (100 mL) was added to stop the reaction, and the organic solvent was removed under reduced pressure, followed by extraction with ethyl acetate (300 mL), and the organic layer was dried over sodium sulfate and concentrated. The concentrated residue was purified by silica gel column chromatography (petroleum ether / ethyl acetate = 50/1) to obtain Compound 8.
(V) A THF solution (40 mL) of compound 8 (10.0 g, 14.4 mmol) was cooled to 0 ° C., and then a n-butyllithium hexane solution (2.5 M, 5.80 mL, 14.5 mmol) was added to argon. The solution was added dropwise under an atmosphere and stirred at room temperature for 2 hours. Next, hexafluorobenzene (6.70 g, 36.0 mmol) was added dropwise at 0 ° C., and the mixture was stirred at room temperature for 14 hours. Ice water (100 ml) was added to stop the reaction, and THF was removed under reduced pressure. The mixture was extracted with ethyl acetate (300 ml), and the organic layer was washed with saturated brine (50 mL), dried over sodium sulfate, and concentrated under reduced pressure. The concentrated residue was purified by silica gel column chromatography (petroleum ether / ethyl acetate = 80/1) to obtain Compound 9.
(Iv) Compound 9 (4.20 g, 4.87 mmol) was dissolved in ethyl acetate (30 mL), hydrochloric acid in ethyl acetate (4.00 M, 20.0 mL) was added at 0 ° C., and the mixture was gradually warmed to room temperature. After warming, the mixture was stirred for 3 hours. The solvent was removed under reduced pressure, the residue was neutralized with a saturated aqueous sodium bicarbonate solution, and extracted with ethyl acetate (300 mL). The oil phase was washed with saturated brine, dehydrated with sodium sulfate, and dried under reduced pressure to obtain Compound B-168 (2.50 g, 3.6 mmol, 75% yield).
¹ HNMR (CDCl ₃ , δ, ppm): 7.90 (dd, J = 9.6 Hz, 1.8 Hz, 1H), 7.67 (s, 1H), 7.28-7.13 (m, 9H) ), 7.03-6.98 (m, 3H), 6.68-6.56 (m, 9H), 6.46 (dd, J = 8.4 Hz, 3.6 Hz, 1H), 3.64. (S, 3H); ³¹ P NMR (CDCl ₃ , δ, ppm) -61.0 (s).

[Synthesis Example 2]: (Synthesis of Ligand B-169)
Ligand B-169 was synthesized according to the following scheme.

(I) To a THF solution (10 mL) of compound 4 (1.63 g, 5.00 mmol), a THF solution of isopropylmagnesium chloride (2.0 M, 2.5 mL, 5.0 mmol) was added at −30 ° C., and 15 Stir at 1 ° C. for 1 hour. Thereafter, phosphorus trichloride (2.1 mL, 15.0 mmol) was added at −78 ° C., and the mixture was stirred at −78 ° C. for 1 hour. After removing the solvent and excess phosphorus trichloride under reduced pressure, THF (15 mL) was added to the concentrated residue to obtain a solution containing Compound 5.
(Ii) To a THF solution (10 mL) of compound 1 (1.31 g, 5.00 mmol), a hexane solution of n-butyllithium (2.5 M, 2.0 mL, 5.0 mmol) was added at 0 ° C., and 15 The mixture was stirred at 0 ° C. for 2 hours to obtain a solution containing compound 2. The solution of compound 2 was slowly added to the THF solution of compound 5 at −78 ° C. and stirred at 15 ° C. for 1 hour to obtain a solution containing compound 6.
(Iii) THF (10 mL) was added to a hexane solution (2.5 M, 2.0 mL, 5.0 mmol) of n-butyllithium, and 2,2,6,6-tetramethylpiperidine (0.71 g, 5.0 mmol) was added. Was added dropwise at -78 ° C and stirred at -78 ° C for 1 hour to prepare a 2,2,6,6-lithium tetramethylpiperidide solution. Compound 7 (1.10 g, 6.7 mmol) was added thereto at −78 ° C., and the mixture was stirred at −78 ° C. for 1 hour. Further, a THF solution of compound 6 was added thereto at −78 ° C., and the mixture was stirred at 15 ° C. for 16 hours. Ice water (100 mL) was added to stop the reaction, and the solvent was removed under reduced pressure. Extracted with ethyl acetate (300 mL) and the organic phase was dried over sodium sulfate and concentrated. The concentrated residue was purified by silica gel column chromatography using petroleum ether / ethyl acetate (50/1) as a developing solution to obtain compound 8 as a white solid.
(Iv) THF (5 mL) was added to a hexane solution (2.5 M, 2.0 mL, 5.0 mmol) of n-butyllithium, and 2,2,6,6-tetramethylpiperidine (0.70 g, 5.0 mmol) was added. A THF solution (10 mL) was added dropwise at −78 ° C. and stirred at −78 ° C. for 1 hour to prepare a 2,2,6,6-lithium tetramethylpiperidide solution. To this, a THF solution of compound 8 (3.27 g, 5.0 mmol) was added at −78 ° C., and the mixture was stirred at −78 ° C. for 1 hour. Next, hexafluorobenzene (2.78 g, 15.0 mmol) was added dropwise at −78 ° C., and the mixture was stirred at 15 ° C. for 16 hours. Ice water (10 mL) was added to stop the reaction, and the organic solvent was removed under reduced pressure. Thereafter, the mixture was extracted with ethyl acetate (300 mL), and the organic phase was dehydrated with sodium sulfate and concentrated under reduced pressure. The concentrated residue was purified by silica gel column chromatography (petroleum ether / ethyl acetate = 50/1). Compound 9 was obtained using preparative HPLC.
(V) Compound 9 (2.40 g, 2.93 mmol) was dissolved in ethyl acetate (15 ml), and an ethyl acetate solution of hydrochloric acid (4.00 M, 5.00 mL) was added at 0 ° C., and gradually increased to 15 ° C. After raising the temperature, the mixture was stirred for 3 hours. The solvent was removed under reduced pressure, the residue was neutralized with a saturated aqueous sodium bicarbonate solution, and extracted with ethyl acetate (30 mL). The oil phase was washed with saturated brine, dehydrated with sodium sulfate, and dried under reduced pressure to obtain Compound B-169 (1.70 g, 2.2 mmol, 76% yield).
¹ H NMR (CDCl ₃ , δ, ppm): 7.84-7.82 (m, 3H), 7.28-7.14 (m, 9H), 7.06-6.99 (m, 3H), 6.67-6.57 (m, 9H), 6.47 (dd, J = 8.4 Hz, 3.6 Hz, 1H), 3.65 (s, 3H); ³¹ PNMR (CDCl ₃ , δ, ppm) ) -61.4 (s).

[Synthesis Example 3]: (Synthesis of Ligand B-179)
Ligand B-179 was synthesized according to the following scheme.

(I) To a THF solution (15 mL) of compound 3 (3.26 g, 10.0 mmol), a THF solution of isopropylmagnesium chloride (2.00 M, 5.00 mL, 10.0 mmol) was added dropwise at −30 ° C., Stir at 20 ° C. for 2 hours. Thereafter, phosphorus trichloride (4.20 mL, 30.0 mmol) was added at -78 ° C, and the mixture was stirred at -78 ° C for 1 hour. After removing the solvent and excess phosphorus trichloride under reduced pressure, THF (15 mL) was added to obtain a solution containing compound 4.
(Ii) A THF solution (15 mL) of compound 1 (2.62 g, 10.0 mmol) was cooled to 0 ° C., and a hexane solution of n-butyllithium (2.5 M, 4.00 mL, 10.0 mmol) under an argon atmosphere. ) Was added dropwise and stirred at 30 ° C. for 2 hours to obtain a solution containing Compound 2. The solution of compound 2 was added dropwise to the solution of compound 4 at −78 ° C. and stirred at 30 ° C. for 1 hour to obtain a solution containing compound 5.
(Iii) Compound 6 (28.5 g, 100 mmol), carbazole (16.7 g, 100 mmol), copper (I) iodide (1.91 g, 10.0 mmol), tripotassium phosphate (65.4 g, 300 mmol) 1,2-Cyclohexanediamine (1.14 g, 10.0 mmol) was refluxed in dioxane (50 mL) at 110 ° C. for 24 hours. The solvent was removed under reduced pressure. Water was added to the residue, and the mixture was extracted with ethyl acetate (350 mL). The organic phase was dried over sodium sulfate and concentrated. The concentrated residue was purified by silica gel column chromatography and further purified by recrystallization (ethyl acetate / petroleum ether = 3/1) to obtain Compound 7 as a white solid.
(Iv) To a THF solution (15 mL) of Compound 7 (3.71 g, 10.0 mmol), a hexane solution of n-butyllithium (2.50 M, 4.00 mL, 10.0 mmol) was added dropwise at 0 ° C., and 30 Stir for 2 hours at ° C. A solution of compound 5 was added thereto at −78 ° C., and the mixture was stirred at 30 ° C. for 16 hours. Ice water (100 mL) was added to stop the reaction, and the organic solvent was removed under reduced pressure, followed by extraction with ethyl acetate (300 mL). The organic phase was dried over sodium sulfate and concentrated. The concentrated residue was purified by silica gel column chromatography using petroleum ether / ethyl acetate (50/1) as a developing solution to obtain Compound 8 as a white solid.
(V) Compound 8 (0.50 g, 0.58 mmol) was dissolved in ethyl acetate (10 mL), and an ethyl acetate solution of hydrochloric acid (4.00 M, 5.00 mL) was added at 0 ° C., and gradually 15 ° C. The mixture was heated up to 1 hour and stirred for 1 hour. The solvent was removed under reduced pressure, a saturated aqueous sodium bicarbonate solution was added for neutralization, ethyl acetate (50 mL) was added, and the aqueous phase was separated. The oil phase was washed with saturated brine, dried over sodium sulfate, and concentrated under reduced pressure. The concentrated residue was purified by silica gel column chromatography (petroleum ether / ethyl acetate = 10/1) to obtain Compound B-179 (0.300 g, 0.36 mmol, 62% yield).
¹ HNMR (CDCl ₃ , δ, ppm): 8.12-8.10 (m, 2H), 7.98 (d, J = 6.8 Hz, 1H), 7.48 (s, 1H), 7. 38-7.15 (m, 13H), 7.07-6.98 (m, 5H), 6.79-6.68 (m, 7), 6.57 (dt, J = 8.0 Hz, 2 .5 Hz, 1 H), 6.44 (dd, J = 8.4 Hz, 3.0 Hz, 1 H), 3.67 (s, 3 H); ³¹ P NMR (CDCl ₃ , δ, ppm) -59.4 (s ).

[Synthesis Example 4]: (Synthesis of Ligand B-187)
Ligand B-187 was synthesized according to the following scheme.

(I) To a THF solution (30 mL) of compound 3 (4.89 g, 15.0 mmol), a THF solution of isopropylmagnesium chloride (2.00 M, 7.50 mL, 15.0 mmol) was added dropwise at −30 ° C., Stir at 20 ° C. for 1 hour. Thereafter, phosphorus trichloride (3.9 mL, 45.0 mmol) was added at −78 ° C., and the mixture was stirred at −78 ° C. for 1 hour. After removing the solvent and excess phosphorus trichloride under reduced pressure, THF (30 mL) was added to obtain a solution containing compound 4.
(Ii) A THF solution (20 mL) of compound 1 (3.93 g, 15.0 mmol) was cooled to 0 ° C., and a hexane solution of n-butyllithium (2.50 M, 6.00 mL, 15.0 mmol) was added dropwise. The solution containing Compound 2 was obtained by stirring at 20 ° C. for 2 hours. The solution of compound 2 was added dropwise to the solution of compound 4 at −78 ° C. and stirred at 20 ° C. for 1 hour to obtain a solution containing compound 5.
(Iii) To a THF solution (30 mL) of compound 6 (5.73 g, 15.0 mmol), a hexane solution of n-butyllithium (2.50 M, 6.00 mL, 15.0 mmol) was added dropwise at 0 ° C., and 20 Stir for 2 hours at ° C. The solution of compound 5 was added thereto at −78 ° C., and the mixture was stirred at 20 ° C. for 16 hours. Ice water (20 mL) was added to stop the reaction, and the organic solvent was removed under reduced pressure, followed by extraction with ethyl acetate (100 mL). The organic layer was dried over sodium sulfate and concentrated. The concentrated residue was purified by silica gel column chromatography using petroleum ether / ethyl acetate (50/1) as a developing solution to obtain Compound 7 as a white solid.
(Iv) Compound 7 (0.200 g, 0.247 mmol) was dissolved in ethyl acetate (20 mL), and an ethyl acetate solution of hydrochloric acid (4 M, 20 mL) was added at 0 ° C., and the temperature was gradually raised to 25 ° C. The mixture was stirred for 1 hour later. The solvent was removed under reduced pressure, a saturated aqueous sodium bicarbonate solution was added for neutralization, ethyl acetate (50 mL) was added, and the aqueous layer was separated. The organic layer was washed with saturated brine, dried over sodium sulfate, and concentrated under reduced pressure. The concentrated residue was purified by silica gel column chromatography (petroleum ether / ethyl acetate = 10/1) to obtain Compound B-187 (0.100 g, 0.120 mmol, 49% yield).
¹ HNMR (CDCl ₃ , δ, ppm): 8.52 (s, 1H), 8.12-8.02 (m, 3H), 7.52-7.39 (m, 4H), 7.34- 7.16 (m, 10H), 7.09-7.03 (m, 3H), 6.79-6.72 (m, 7H), 6.60-6.54 (m, 3H), 6. 45 (dd, J = 8.4 Hz, 3.2 Hz, 1H), 3.66 (s, 3H); ³¹ PNMR (CDCl ₃ , δ, ppm) -60.1 (s).

  Chemical formulas of the compounds B-168, B-169, B-179, and B-187 synthesized above are shown below.

[Synthesis Example 5]: Synthesis of 2-bis (2,6-dimethoxyphenyl) phosphano-6-pentafluorophenylphenol ligand (B-27DM) (1) 2-bis (2,6-dimethoxyphenyl) phos Synthesis of Fanophenylmethoxymethyl Ether ((B-27DM-5) Phenylmethoxymethyl ether (B-27DM-4, 2.87 g, 20.8 mmol) was dissolved in dehydrated THF (20 mL), and n-butyllithium (8 (3 mL, 20.8 mmol) in n-hexane solution was added dropwise at 0 ° C. The resulting mixture was stirred at 0 ° C. for 30 minutes, then warmed to room temperature and stirred at room temperature for 2 hours. To a THF solution (20.8 mmol, 150 mL) of the compound (B-14-4) obtained in the same manner as in Synthesis Example 7 (2) was added at 0 ° C., and further at room temperature overnight. The reaction solution was quenched with water, and THF was removed under reduced pressure, and the resulting mixture was extracted with dichloromethane, and the organic layer was washed with saturated brine. The mixture was dehydrated and sodium sulfate was filtered off, and the solvent was removed under reduced pressure and concentrated.
The obtained crude product was purified with a silica gel column using dichloromethane as a developing solution, dichloromethane was removed, and 2-bis (2,6-dimethoxyphenyl) phosphanophenylmethoxymethyl ether (B-27DM-5) A white solid was obtained.

(2) Synthesis of 2-bis (2,6-dimethoxyphenyl) phosphano-6-pentafluorophenylphenylmethoxymethyl ether (B-27DM-6) Compound (B-27DM-5, 3.2 g) obtained above , 7.2 mmol) was dissolved in dehydrated THF (50 mL). To this solution, n-butyllithium (2.9 mL, 7.2 mmol) was added dropwise at 0 ° C. The resulting reaction solution was heated while stirring and stirred at room temperature for 2 hours.
The solution was then cooled to −78 ° C. and hexafluorobenzene (4.2 mL, 36 mmol) was added slowly. The solution was warmed to room temperature while stirring and stirred overnight at room temperature. Water was added to quench the reaction and the solvent was removed under reduced pressure. The solid residue was extracted with dichloromethane, and the organic layer was washed with saturated brine.
Next, the organic layer was dehydrated with sodium sulfate, the sodium sulfate was filtered off, and the solvent was removed under reduced pressure and concentrated. The crude product was purified with a silica gel column using a mixed solution of petroleum ether / ethyl acetate (7/1, v / v) as a developing solution, whereby 2-bis (2,6-dimethoxyphenyl) phosphano-6- Pentafluorophenyl phenyl methoxymethyl ether (B-27DM-6) was obtained (1.2 g, 2.0 mmol, 28% yield). The same operation was performed to obtain 6.7 g of compound (B-27DM-6).

(3) Synthesis of 2-bis (2,6-dimethoxyphenyl) phosphano-6-pentafluorophenylphenol hydrochloride (B-27DMHCl) Compound (B-27DM-6, 5.5 g, 9) obtained above 0.0 mmol) was added to a solution of hydrogen chloride in ethyl acetate (4M, 100 mL) at 0 ° C. The resulting mixture was gradually warmed to room temperature and then stirred at room temperature for 1.5 hours. When ethyl acetate was removed under reduced pressure, 2-bis (2,6-dimethoxyphenyl) phosphano-6-pentafluorophenylphenol hydrochloride (B-27DMHCl) was obtained as a white solid.

(4) Synthesis of 2-bis (2,6-dimethoxyphenyl) phosphano-6-pentafluorophenylphenol ligand (B-27DM) Hydrochloride (B-27DMHCl, 5.0 g, 7.7 mmol), hydrogen carbonate A mixture of saturated aqueous sodium (200 mL) and ethyl acetate (100 mL) was stirred at room temperature under an argon atmosphere for 2 hours. The target compound was extracted from the obtained reaction mixture with ethyl acetate, and the organic layer was washed with brine. After dehydration with sodium sulfate, sodium sulfate was filtered off and the solvent was removed under reduced pressure.
The crude product is washed with a mixed solvent of petroleum ether and ethyl acetate, and the desired 2-bis (2,6-dimethoxyphenyl) phosphano-6-pentafluorophenylphenol ligand (B-27DM) is obtained as a white solid. Obtained (2.8 g, 5.0 mmol, 60% yield).
¹ HNMR (CDCl ₃ , δ, ppm): 7.72 (dq, J = 7.6, 1.5 Hz, 1H), 7.25 (br (s), 1H), 7.21 (t, J = 8.3 Hz, 2H), 7.09 (d, J = 6.8 Hz, 1H), 6.87 (dt, J = 7.6, 1.0 Hz, 1H), 6.48 (dd, J = 8 ^{.3,3.0Hz, 4H), 3.36 (s} , 12H); 31 PNMR (CDCl 3, δ, ppm): - 59.1 (s).

[Synthesis Example 6]: (Synthesis of Ligand B-30)
Ligand B-30 was synthesized according to the following scheme.

(I) To a THF solution of compound 1 (5.20 g, 20.0 mmol), a THF solution of isopropylmagnesium chloride (2.0 M, 10.0 mL, 20.0 mmol) was added dropwise at −50 ° C., and 1 at room temperature. Stir for hours. Thereafter, phosphorus trichloride (1.37 g, 10.0 mmol) was added at −78 ° C., and the mixture was stirred until it reached room temperature to obtain a solution containing Compound 3.
(Ii) A THF solution (100 mL) of compound 4 (3.14 g, 10.0 mmol) was cooled to 0 ° C., and a hexane solution of n-butyllithium (2.5 M, 4.00 mL, 10.0 mmol) under an argon atmosphere. ) Was added dropwise and stirred at 0 ° C. for 1 hour and at room temperature for 1 hour to obtain a solution containing Compound 5. The compound 3 solution was added dropwise to the compound 5 solution at −30 ° C., and the mixture was stirred at room temperature overnight. Water was added to stop the reaction, the organic solvent was removed under reduced pressure, and then ethyl acetate was added to separate the water phase. The organic phase was washed with saturated brine, dried over sodium sulfate, and concentrated under reduced pressure. The concentrated residue was purified by silica gel column chromatography using petroleum ether / ethyl acetate (10/1) as a developing solution to obtain Compound 6.
(Iii) Compound 6 (1.34 g, 2.17 mmol) was added at −78 ° C. to ethyl acetate (50 mL) bubbled with hydrogen chloride for 15 minutes, gradually warmed to room temperature, and then stirred for 1.5 hours. did. The solvent was removed under reduced pressure, a saturated aqueous sodium bicarbonate solution was added for neutralization, ethyl acetate (50 mL) was added, and the aqueous phase was separated. The oil phase was washed with saturated brine, dried over sodium sulfate, and concentrated under reduced pressure. The concentrated residue was purified by silica gel column chromatography (petroleum ether / ethyl acetate = 10/1) to obtain Compound B-30 (0.9 g, 0.36 mmol, 72% yield).
¹ HNMR (CDCl ₃ , δ, ppm): 8.37 (s, 1H), 7.92 (d, J = 8.4 Hz, 2H), 7.65 (d, J = 8.0 Hz, 3H), 7.33 (t, J = 7.4 Hz, 2H), 7.22-7.05 (m, 4H), 6.91-6.89 (m, 1H), 6.41-6.35 (m , 5H), 3.51 (s, 12H); ³¹ PNMR (CDCl ₃ , δ, ppm) -60.1 (s).

  The chemical formula of Compound B-30 synthesized above is shown below.

[Synthesis Example 7]: (Synthesis of Ligand B-125)
Ligand B-125 was synthesized according to the following scheme.

(I) To a THF solution (20 mL) of compound 1 (2.64 g, 10.0 mmol), a THF solution of isopropyl magnesium chloride (2.00 M, 5.00 mL, 10.0 mmol) was added dropwise at −30 ° C., Stir at room temperature for 1 hour. Thereafter, phosphorus trichloride (0.67 mL, 5.0 mmol) was added at −78 ° C., and the mixture was stirred at room temperature for 2 hours. After removing the solvent and excess phosphorus trichloride under reduced pressure, THF (15 mL) was added to obtain a solution containing compound 2.
(Ii) Compound 3 (4.3 g, 20 mmol), carbazole (5.01 g, 30 mmol), copper (I) iodide (0.19 g, 1.0 mmol), tripotassium phosphate (12.75 g, 60.0 mmol) ) And 1,2-cyclohexanediamine (0.23 g, 2.0 mmol) were refluxed in dioxane (50 mL) at 110 ° C. for 24 hours. The reaction solution was suspended in dichloromethane (120 mL) and washed with water (250 mL). The aqueous phase was extracted twice with dichloromethane (100 mL) and the organic phase was dried over sodium sulfate. The crude product was purified by flash chromatography (petroleum ether / ethyl acetate = 10/1) to give compound 4.
(Iii) A THF solution (25 mL) of compound 4 (1.5 g, 5.0 mmol) is cooled to 0 ° C., and a hexane solution of n-butyllithium (2.0 M, 5.00 mL, 10.0 mmol) is added dropwise. And stirred at room temperature for 2 hours. The solution of compound 2 was added dropwise thereto at −78 ° C. and stirred at room temperature for 16 hours. Water (10 mL) was added to stop the reaction, the organic solvent was removed under reduced pressure, ethyl acetate (20 mL) was added, and the aqueous phase was separated. The organic phase was washed with saturated brine, dried over sodium sulfate, and concentrated under reduced pressure. The concentrated residue was purified by preparative thin layer chromatography (petroleum ether / ethyl acetate = 5/1) to obtain Compound 5.
(Iv) Compound 5 (6.7 g, 10.1 mmol) was added to an ethyl acetate solution (1.00 M, 200 mL) of hydrochloric acid at 0 ° C., and the mixture was warmed to room temperature and stirred for 1.5 hours. The solvent was removed under reduced pressure, neutralized with a saturated aqueous sodium bicarbonate solution, ethyl acetate (80 mL) was added, and the aqueous phase was separated. The organic phase was washed with saturated brine, dried over sodium sulfate, and concentrated under reduced pressure. Recrystallization (petroleum ether / ethyl acetate = 10/1) gave Compound B-125 (4.2 g, 7.5 mmol, 74% yield).
¹ HNMR (CDCl ₃ , δ, ppm): 8.02 (d, J = 7.6 Hz, 2H), 7.60-7.55 (m, 1H), 7.27-7.11 (m, 7H) ), 7.05 (d, J = 8.0 Hz, 2H), 6.86 (dt, J = 7.8 Hz, 1.2 Hz, 1H), 6.75 (s, 1H), 6.40 (dd , J = 8.4 Hz, 2.8 Hz, 4H), 3.47 (s, 12H); ³¹ PNMR (CDCl ₃ , δ, ppm) -60.1 (s).

  The chemical formula of Compound B-125 synthesized above is shown below.

[Example 1]
Copolymerization of Ethylene / Acrylate with Ligand B-168 (1) Formation of Complex The following operations were all performed in a high purity argon atmosphere. Hereinafter, bis-1,5-cyclooctadiene nickel (0) is referred to as Ni (COD) ₂ .
First, B-168 (35 mg) obtained in Synthesis Example 1 was weighed out into a 4 ml vial with a screw cap.
Next, Ni (COD) ₂ (28 mg) was weighed into a 20 ml vial and dissolved in toluene (10 ml) to prepare a 10 mM Ni (COD) ₂ toluene solution. The resulting solution was yellow and transparent. The Ni (COD) ₂ toluene solution (5.0 ml) obtained here was added to a vial having B-168, sealed with a screw cap, and then shaken for 30 seconds to obtain a solution. Thereafter, the color of the solution gradually changed from dark yellow to red, and no precipitation was observed. After standing at room temperature for 3 hours, 0.5 ml of the resulting solution was dispensed into a 2 ml vial, diluted with toluene (1.5 ml), and the reaction product of B-168 and Ni (COD) ₂ A 2.5 mM solution was obtained. Here, the concentration of the reaction product was calculated on the assumption that B-168 and Ni (COD) ₂ reacted 1: 1 to form a nickel complex.

(2) Copolymerization of ethylene / acrylic acid ester A predetermined amount of acrylic acid ester as dry monomer (1 L) and a comonomer was introduced into an induction stirring autoclave having an internal volume of 2 L. The temperature of the autoclave was raised to a predetermined temperature while stirring, and then ethylene was supplied to the autoclave so that the temperature and pressure were adjusted to predetermined conditions. After completion of the adjustment, a predetermined amount of the reaction product obtained in (1) was supplied to start copolymerization. After polymerization for a predetermined time, ethanol was added to stop the reaction. After removing the unreacted gas, the autoclave was opened, filtration, solvent washing, and heat drying were performed to obtain a copolymer.
The types and amounts of comonomers used for copolymerization are listed in Table 2. The comonomer was used after being purified at room temperature in a high-purity argon atmosphere using a column packed with Aldrich Inhibitor Remover manufactured by Aldrich. Table 2 also shows the amount of toluene used in the polymerization, the polymerization temperature, and the autoclave internal pressure during the polymerization.
In Table 2, tBA represents tbutyl acrylate. Moreover, active Vp represents the copolymer yield (kg) per 1 hour of polymerization time per 1 mol of complexes used for polymerization. Vp was calculated on the assumption that B-168 and Ni (COD) ₂ reacted one-on-one to form a nickel complex. The GPC and DSC measurement results for the obtained polymer are also shown in Table 2.

[Example 2]
Copolymerization of ethylene / acrylic acid ester using ligand B-169 (1) Formation of complex A complex was prepared in the same manner as in Example 1 except that B-169 (30 mg) obtained in Synthesis Example 2 was used as the ligand. Was formed.

(2) Copolymerization of ethylene / acrylic acid ester Copolymerization of ethylene / acrylic acid ester was carried out in the same manner as in Example 1 except that the compound obtained in (1) above was used as a complex. The results are shown in Table 2.

[Example 3]
Copolymerization of ethylene / acrylic acid ester using ligand B-179 (1) Complex formation The complex was prepared in the same manner as in Example 1 except that B-179 (33 mg) obtained in Synthesis Example 3 was used as the ligand. Formation was performed.

(2) Copolymerization of ethylene / acrylic acid ester Copolymerization of ethylene / acrylic acid ester was carried out in the same manner as in Example 1 except that the compound obtained in (1) above was used as a complex. The results are shown in Table 2.

[Example 4]
Copolymerization of ethylene acrylate with ligand B-187 (1) Complex formation The complex was prepared in the same manner as in Example 1 except that B-187 (33 mg) obtained in Synthesis Example 4 was used as the ligand. Formation was performed.

(2) Copolymerization of ethylene / acrylic acid ester Copolymerization of ethylene / acrylic acid ester was carried out in the same manner as in Example 1 except that the compound obtained in (1) above was used as a complex. The results are shown in Table 2.

[Comparative Example 1]
Copolymerization of ethylene / acrylic acid ester using B-27DM (1) Formation of complex Formation of complex in the same manner as in Example 1 except that B-27DM (28 mg) obtained in Synthesis Example 5 was used as the ligand. Went.

(2) Copolymerization of ethylene / acrylic acid ester Copolymerization of ethylene / acrylic acid ester was carried out in the same manner as in Example 1 except that the compound obtained in (1) above was used as a complex. The results are shown in Table 3.

[Comparative Example 2]
Copolymerization of ethylene / acrylic acid ester using B-30 (1) Formation of complex In the same manner as in Example 1 except that B-30 (24 mg) obtained in Synthesis Example 6 was used as the ligand, Formation was performed.

(2) Copolymerization of ethylene / acrylic acid ester Copolymerization of ethylene / acrylic acid ester was carried out in the same manner as in Example 1 except that the compound obtained in (1) above was used as a complex. The results are shown in Table 3.

[Comparative Example 3]
Copolymerization of ethylene / acrylic acid ester using B-125 (1) Formation of complex In the same manner as in Example 1, except that B-125 (24 mg) obtained in Synthesis Example 7 was used as a ligand. Formation was performed.

(2) Copolymerization of ethylene / acrylic acid ester and homopolymerization of ethylene The ethylene / acrylic acid ester copolymerization was carried out in the same manner as in Example 1 except that the compound obtained in (1) above was used as the complex. went. The results are shown in Table 3.

According to Tables 2 and 3, in the metal complex represented by the general formula (A) of the present invention, R ⁴ and R ⁵ in the general formula (A) contain two or more heteroatom-containing groups, and at least one of them A polymer having a high activity and a relatively high molecular weight by containing an electron-withdrawing substituent with respect to an aryl group having two or more kinds of heteroatom-containing groups and R ¹¹ being a mother nucleus. It can be seen that is obtained. For example, Example 1 using a nickel complex of a reaction product of ligand B-168 and Ni (COD) ₂ and comparison using a nickel complex of a reaction product of ligand B-27DM and Ni (COD) ₂ In comparison with Example 1, compared to Comparative Example 1 in which R ⁴ and R ⁵ are the same and R ¹¹ is unsubstituted in ligand B-27DM (R ¹¹ is a hydrogen group), Example 1 shows that ligand B -168 (R ¹¹ is CF ₃ group) R ⁴ and R ⁵ contain two or more hetero atom-containing groups, at least one of them contains two or more hetero atom-containing groups, and R ¹¹ It can be seen that a polymer having high activity and high Mw is obtained by having an electron-withdrawing substituent with respect to the aryl group which is a mother nucleus.

  The polymerization catalyst comprising the metal complex of the present invention is a catalyst having nickel as a metal center in place of rare and expensive palladium, and by using the polymerization catalyst comprising the metal complex of the present invention, it is highly active and industrial. Easily, α-olefin polymers and copolymers of (meth) acrylic acid esters and α-olefins can be produced, and the polymers and copolymers obtained in the present invention are mechanically Since it has excellent thermal properties and can be applied as a useful molded article, it is extremely useful in industry.

Claims (4)

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

[Wherein, M represents nickel or palladium . R ³ represents a hydrogen atom or a hydrocarbon group that may contain a C 1-20 hetero atom. L ¹ represents a ligand coordinated to M. 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 are each independently a hydrocarbon group optionally containing a hetero atom having 1 to 40 carbon atoms, and R ⁴ and R ⁵ are selected from the group consisting of an alkoxy group and an aryloxy group. 2 or more selected oxygen atom-containing groups are contained, and both R ⁴ and R ⁵ are substituted with the oxygen atom-containing group at the 2-position and the 6-position, and at least one of R ⁴ and R ⁵ is at the 2-position and 6-position. Represents an aromatic hydrocarbon group substituted with an oxygen atom-containing group at a different position . R ¹⁰ , R ¹² and R ¹³ are each independently a hydrogen atom, a halogen atom, a hydrocarbon group which may contain a C 1-30 hetero atom, OR ² , CO ₂ R ² , CO ₂ M ', C (O) N (R ¹ ) ₂ , C (O) R ² , SR ² , SO ₂ R ² , SOR 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 ) ₂ M ′ or an epoxy-containing group, R ¹¹ is a halogen atom, a hydrocarbon group containing one or more hetero atoms having 1 to 30 carbon atoms, CO ₂ R ² , CO ₂ M ′, C (O) N (R ¹ ) ₂ , SO ₂ R ² , SOR ² , CN, NO ₂ , SO ₃ M ′, PO ₃ M ′ ₂ or P (O) (OR ² ) ₂ M ′ (wherein R ¹ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, R ² represents a hydrocarbon group having 1 to 20 carbon atoms, M 'represents an alkali metal, of ammonium, quaternary ammonium or phosphonium, x represents an integer of 0 to 3, y is 0-2 Represents an integer.) In addition, a plurality of groups appropriately selected from R ⁴ , R ⁵ , R ¹⁰ , R ¹² or R ¹³ are connected to each other and contain an alicyclic ring, an aromatic ring, or a heteroatom selected from oxygen, nitrogen or sulfur The number of ring members may be 5 to 8, and it may or may not have a substituent on the ring. ] 2. The metal complex according to claim 1 , wherein R ¹¹ in the general formula (A) is an electron-attracting substituent with respect to the aryl group which is a mother nucleus. In the general formula (A), R ¹¹ is a fluorine atom, perfluoro methyl group, metal complex according to claim 1 or 2, characterized in that a perfluorophenyl radical or CN. An α-olefin / (meth) acrylic acid ester copolymer is produced by copolymerizing an α-olefin and a (meth) acrylic acid ester in the presence of the metal complex according to claim 1. A method for producing a polymer.