JP5622376B2 - Novel metal complex, method for producing α-olefin polymer using the same, and method for producing α-olefin and propenoic acid derivative ester copolymer - Google Patents

Description

  The present invention relates to an α-olefin polymer, a metal complex useful for the production of an α-olefin and a propenoic acid derivative ester copolymer, a method for producing a novel α-olefin polymer using the same, and the α-olefin and propenoic acid. The present invention relates to a method for producing a derivative ester copolymer.

  A method of copolymerizing ethylene and 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 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).

Nickel catalyst using a ligand having phosphorus and oxygen as coordination atoms, so-called SHOP-based catalyst (Shell Higher Olefin Process-based catalyst) can be used to polymerize ethylene in a polar solvent and have few branches It is known that linear polymers can be obtained. 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 as a catalyst component, biscycloocta Diene 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 Examples of Patent Document 2, an example of copolymerization of ethylene and methyl acrylate is described. However, since an amorphous polymer is by-produced, it is necessary to remove the amorphous polymer by acetone extraction. was there. 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. It has been reported that a copolymer of ethylene and methyl acrylate can be obtained by using 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 techniques for improving the molecular weight of olefin polymers and olefin / acrylate copolymers.

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.

  An object of the present invention is to provide an α-olefin polymer or an α-olefin / propenoic acid derivative ester copolymer (for example, an α-olefin / (meth) acrylic) having few branches and crystallinity in view of the problems of the prior art. Acid ester copolymer), particularly a novel catalyst component for the production of a polymer having a high molecular weight, and an α-olefin polymer or α-olefin / propenoic acid derivative ester copolymer (for example, α-olefin. It is providing the manufacturing method of (meth) acrylic acid ester copolymer).

As a result of intensive research, the present inventors have found that a ligand having an aryl group as a nucleus and two substituents R on phosphorus, arsenic or antimony (denoted as E1 in the present invention) bonded to the aryl group. ^At least one of ⁴ is an aryl group containing one or more hetero atom-containing groups, and has a specific structure in which a metallacycle including M, E ¹ , X ¹ , and Y ¹ forms a 6-membered ring Using a transition metal complex as a catalyst component, it has been found that a polymer having an extremely high molecular weight can be obtained by polymerization of α-olefin or copolymerization of α-olefin and (meth) acrylate. It came to be completed.

That is, according to the first invention of the present invention, a compound represented by the following general formula (B) or (C) is contacted with a transition metal complex (D) containing a transition metal belonging to Group 10 of the periodic table. A metal complex characterized by being obtained by providing is provided.

[In the formula (B) or (C), Z represents hydrogen or a leaving group. m represents the valence of Z. X ¹ represents oxygen. Y ¹ represents carbon. E ¹ represents phosphorus. R ⁴ each independently represents hydrogen or a hydrocarbon group that may contain a C 1-20 hetero atom, and at least one of R ⁴ contains one or more hetero atom-containing groups. It is a hydrocarbon group. R ⁵ each independently represents hydrogen or a hydrocarbon group that may contain a C 1-20 hetero atom. R ¹⁰ , R ¹¹ , R ¹² , and R ¹³ are each independently hydrogen, halogen, a hydrocarbon group that 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 (wherein R ¹ represents hydrogen 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, alkaline earth metal, ammonium, quaternary ammonia. And represents an integer of 0 to 3, and y represents an integer of 0 to 2.) ]

According to the second invention of the present invention, there is provided a method for producing an α-olefin polymer, wherein the α-olefin (a) is polymerized in the presence of the metal complex according to the first invention.
According to a third aspect of the present invention, there is provided the method for producing an α-olefin polymer according to the second aspect , wherein the polymerization is carried out in the presence of a Lewis base.
Furthermore, according to the fourth aspect of the present invention, there is provided the method for producing an α-olefin polymer according to the second aspect , wherein the polymerization is performed in the absence of the organoaluminum compound.

According to a fifth invention of the present invention, α-olefin (a) and propenoic acid derivative ester (b) are copolymerized in the presence of the metal complex according to the first invention. A method for producing an olefin / propenoic acid derivative ester copolymer is provided.
According to a sixth aspect of the present invention, there is provided a process for producing an α-olefin / propenoic acid derivative ester copolymer according to the fifth aspect , wherein the polymerization is carried out in the presence of a Lewis base. The
Furthermore, according to the seventh invention of the present invention, there is provided a process for producing an α-olefin / propenoic acid derivative ester copolymer according to the fifth invention, wherein the polymerization is performed in the absence of an organoaluminum compound. Provided.

  The metal complex of the present invention makes it possible to produce a copolymer of a propenoic acid derivative ester and an α-olefin which are easily available industrially, and the resulting copolymer has a high molecular weight. A high molecular weight can be obtained not only in the copolymer but also in the α-olefin polymer. In general, the molecular weight is one of the dominant factors in the physical properties of the polymer. By increasing the molecular weight, the interaction between the polymer chains is strengthened. Therefore, the polymer and copolymer obtained in the present invention are mechanically It has excellent thermal properties and can be applied as a useful molded product. 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 novel process for producing such α-olefin polymers and α-olefin / propenoic acid derivative ester copolymers, and is extremely useful industrially.

The present invention provides a transition metal complex (D) containing a specific compound (B) and / or (C) and a transition metal belonging to Groups 9, 10 and 11 of the periodic table such as nickel, palladium, cobalt, copper or rhodium. And (a) a method for producing an α-olefin polymer and (a) α which is performed in the presence of the catalyst component using the metal complex (A) which is a reaction product obtained by the reaction with This is a method for producing an α-olefin / propenoic acid derivative ester copolymer comprising copolymerizing an olefin and (b) a propenoic acid derivative ester.
Hereinafter, the constituent monomer of the polymer, the metal complex as the catalyst component, the production method and the like 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. Constituent monomer (a) α-olefin of polymer The component (a) in the present invention is an α-olefin represented by the general formula CH ₂ ═CHR ⁷ . Here, R < ⁷ > is hydrogen 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, preferred examples of the component (a) include α-olefins in which R ⁷ is hydrogen 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) Propenic acid derivative ester The component (b) in the present invention is a propenoic acid derivative ester represented by the general formula CH ₂ = C (R ⁸ ) CO ₂ (R ⁹ ). Here, R < ⁸ > is hydrogen 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. Therefore, although R ⁸ is hydrogen or a hydrocarbon group having 1 to 10 carbon atoms, as a preferable component (b), R ⁸ is hydrogen or a propenoic acid derivative ester that is a hydrocarbon group having 1 to 5 carbon atoms. Is mentioned. More preferable component (b) includes a methacrylic ester in which R ⁸ is a methyl group or an acrylate ester in which R ⁸ is hydrogen. Similarly, when the carbon number of R ⁹ exceeds 30, the polymerization activity tends to decrease. Therefore, although the number of carbon atoms of ^{R 9} is 1 to 30, ^{R 9} is preferably 1 to 18 carbon atoms, more preferably from 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 metal complex of the present invention is represented by the following general formula (A).

In the formula, M represents a transition metal belonging to Group 9, 10 or 11 of the periodic table. R ³ represents hydrogen or a hydrocarbon group that may contain a hetero atom having 1 to 20 carbon atoms. 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. Y ¹ represents carbon or silicon. E ¹ represents phosphorus, arsenic or antimony. R ⁴ each independently represents hydrogen or a hydrocarbon group that may contain a C 1-20 hetero atom, and at least one of R ⁴ contains one or more hetero atom-containing groups. It is a hydrocarbon group. R ⁵ each independently represents hydrogen or a hydrocarbon group that may contain a C 1-20 hetero atom. R ¹⁰ , R ¹¹ , R ¹² , and R ¹³ are each independently hydrogen, halogen, a hydrocarbon group that 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 ', Represents PO ₃ M' ₂ , P (O) (OR ² ) ₂ M 'or an epoxy-containing group. Here, R ¹ represents hydrogen 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 from 0 to 3, and y represents an integer from 0 to 2. A plurality of groups appropriately selected from R ⁴ , R ⁵ , R ¹⁰ , R ¹¹ , R ¹² , and R ¹³ are connected to each other and selected from an alicyclic ring, an aromatic ring, or oxygen, nitrogen, and sulfur. Heterocycles containing heteroatoms may be formed. At this time, the number of ring members is 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 hydrogen or a hydrocarbon group that may contain a hetero atom having 1 to 20 carbon atoms. 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 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, L1 has ¹ to 16 carbon atoms, and more preferably 1 to 10 carbon atoms. 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 using a scavenger that removes the ligand from M is essential for the expression of the olefin polymerization ability (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 and cyclic olefins, and particularly preferred L ¹ is pyridine, lutidine (dimethylpyridine), picoline (methylpyridine). , R ¹ CO ₂ R ² (wherein R ¹ and R ² are as defined 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, Y ¹ represents carbon or silicon. Of these, carbon is preferred. In the present invention, E ¹ represents phosphorus, arsenic or antimony. Of these, phosphorus is preferred.

In the present invention, each R ⁴ independently represents hydrogen or a hydrocarbon group that may contain a C 1-20 hetero atom, and at least one of R ⁴ represents a hetero atom containing group. It is a hydrocarbon group containing at least one group. R ⁴ is in the vicinity of the metal M and interacts with M sterically and / or electronically. In order to exert such an effect, R ⁴ is preferably bulky. R ⁴ preferably has 3 to 20 carbon atoms, more preferably 6 to 20 carbon atoms.
In R ⁴ , 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 an oxygen group, an alkoxy group, an aryloxy group, an acyl group, an aroyl group, and a carboxylate group, and a nitrogen-containing group includes an amino group and an amide group. Examples of the sulfur-containing group include a thioalkoxy group and thioaryloxy, examples of the phosphorus-containing substituent include a phosphino group, examples of the silicon-containing group include a trialkylsilyl group, a dialkylarylsilyl group, An alkyldiarylsilyl group is mentioned. 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 thiomethoxy group, thioethoxy group, thio-n-propoxy group, thioisopropoxy group, thio-n-butoxy group, thio-t-butoxy group, thiophenoxy group, p-methylthiophenoxy group, p- A methoxythiophenoxy group etc. can be mentioned. Examples of the phosphorus-containing substituent include dimethylphosphino group, diethylphosphino group, di-n-propylphosphino group, cyclohexylphosphino group and the like.

In R ^4, it is sufficient that at least one R ⁴ has one or more heteroatom-containing groups, and it is particularly preferable that R ⁴ contains two heteroatom-containing groups. As the combination of R ^4, when two R ⁴ has at least two heteroatom-containing groups both, and one of R ⁴ has two or more heteroatom-containing groups There are two cases where the remaining one R ⁴ has one or less heteroatom-containing groups, but two R ⁴ have two or more heteroatom-containing groups. Preferably it is.

In the present invention, each R ⁴ independently represents hydrogen or a hydrocarbon group that may contain a hetero atom having 1 to 20 carbon atoms. More specifically, R ⁴ may contain a hetero atom. Examples thereof include a good branched chain hydrocarbon group, an alicyclic hydrocarbon group which may contain a hetero atom, and an aryl group which may contain a hetero atom. As described above, R ⁴ is preferably bulky. Therefore, among these, an alicyclic hydrocarbon group which may contain a hetero atom, or an aryl group which may contain a hetero atom is preferable, and an aryl group which may contain a hetero atom is preferred. Most preferred. Examples of such an aryl group include a phenyl group, a naphthyl group, and an anthracenyl group.

In R ⁴ 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 may be directly bonded to the aromatic skeleton, or a methylene group. It may be bonded to the aromatic skeleton through a spacer such as When the heteroatom-containing group is bonded to the aromatic skeleton via a methylene group, the number of methylene groups is preferably one. The substitution position is preferably ortho to the carbon bonded to E ¹ in the aromatic skeleton in R ⁴ . By doing so, it is possible to take a spatial arrangement so that the hetero atom in R ⁴ interacts with M.

Specific examples of preferable R ⁴ include 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-tri Methoxymethylphenyl group, 4-methyl-2,6-dimethoxymethylphenyl group, 4-t-butyl-2,6-dimethoxymethylphenyl group, 1,3-dimethoxymethyl-2-naphthyl group, 2,6-di Phenoxymethylphenyl 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 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, Examples thereof include 6-di (2-phenoxyethyl) phenyl group and 1,3-di (2-phenoxyethyl) -2-naphthyl group.

In the present invention, each R ⁵ independently represents hydrogen or a hydrocarbon group that may contain a C 1-20 hetero atom. When the carbon number of R ⁵ is 11 or more, the metal complex tends to be deteriorated in stability. Therefore, R ⁵ has 0 to 20 carbon atoms, preferably 0 to 10 carbon atoms, and more preferably 0 to 6 carbon atoms. R ⁵ may be linked to a plurality of groups appropriately selected from R ⁴ , R ¹⁰ , R ¹¹ , R ¹² , and R ¹³ to form an alicyclic ring or an aromatic ring. At this time, the number of ring members is 5 to 8, and it may or may not have a substituent on the ring. Also, the two R ⁵ may be linked to each other. At this time, the total carbon number of the two R ⁵ is preferably 2 to 6.

R ¹⁰ , R ¹¹ , R ¹² , and R ¹³ are as described above. Among these, the bulkiness of R ¹¹ is preferred because it tends to give a high molecular weight polymer. R ¹¹ has 1 to 30 carbon atoms, preferably 3 to 30 carbon atoms.
Specific examples of R ¹¹ include, as a hydrocarbon group, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, a phenyl group, and a 1-naphthyl group. 2-naphthyl group, 1-anthracenyl group, 2-anthracenyl group, 9-anthracenyl group, 4-t-butylphenyl group, 2,4-di-t-butylphenyl group, 9-fluorenyl group, cyclohexyl group, etc. As a hetero atom-containing hydrocarbon group, a trifluoromethyl group, a trimethylsilyl group, a triethylsilyl group, a tri-n-propylsilyl group, a triphenylsilyl group, a 2,6-difluorophenyl group, 2,4,6-trifluoro A phenyl group, a pentafluorophenyl group, a cyclohexylamino group, etc. can be mentioned.
Of these, particularly preferred R ¹¹ includes a t-butyl group, a trimethylsilyl group, a phenyl group, a 9-anthracenyl group, a 4-t-butylphenyl group, and a 2,4-di-t-butylphenyl group.

  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, Et represents an ethyl group, iPr represents an isopropyl group, tBu represents a tertiary butyl group, Cy represents a cyclohexyl 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, M may have 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 Forming Metal Complex The metal complex (A) of the present invention is a transition metal complex containing a compound represented by the following general formula (B) and / or (C) and a transition metal of group 9, 10 or 11 It can be obtained by contacting (D).

In the general formulas (B) and (C), Z is hydrogen or a leaving group. m represents the valence of Z. X ¹ , Y ¹ , E ¹ , R ⁴ , R ⁵ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ are as described above.
Z is hydrogen or a leaving group, and specific examples thereof include hydrogen, R ¹ SO ₂ group (where R ¹ is as described above), CF ₃ SO ₂ group, and the like. .

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 in ^{R 1} is as described above, the four ^{R 1} may be the same or ^{_{different), Li +, Na +,}} K +, Mg 2 +, Ca 2 +, a _Al ^{3 +,} further 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 ⁺ .

About the substance shown by general formula (B)-(C), it is compoundable based on a well-known synthesis method.
The metal complex (A) is contained in the reaction product of the compound represented by the above (B) or (C) and the transition metal complex component (D) containing the metal M of the present invention.
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), a biscyclopentadienyl nickel (2), a complex represented by the general formula: Ni (CH ₂ SiR ¹ ₃ ) ₂ L ¹ ₂ (where R ¹ and L ¹ are And a complex represented by the general formula: NiR ¹ ₂ L ¹ ₂ (where R ¹ and L ¹ are as described in this specification) and the like. can do.

The transition metal complex (D) containing a Group 9, 10 or 11 transition metal is represented by the general formula: MR ¹⁰ _p L ¹ _q (where M is a group 9, 10 or 11 transition). The metals R ¹⁰ 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, those preferably used are bis-1,5-cyclooctadiene nickel (0) and a complex represented by the general formula: (CH ₂ CR ¹ CH ₂ ) ₂ Ni (where R ¹ Is as described in this specification.), A complex represented by the general formula: Ni (CH ₂ SiR ¹ ₃ ) ₂ L ¹ ₂ (where R ¹ and L ¹ are described in the present specification). ), A complex represented by the general formula: NiR ¹ ₂ L ¹ ₂ (where R ¹ and L ¹ are as described herein), Pd (dba) ₂ , Pd ₂ (Dba) ₃ , Pd ₃ (dba) ₄ (where dba represents dibenzylideneacetone), Pd (OCOCH ₃ ) ₂ .
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 (below) 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 (where dba represents dibenzylideneacetone), Pd (OCOCH ₃ ) ₂ .

The reaction product according to 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 to 99: 1 (molar ratio) in an organic solvent such as toluene at 0 to 100 ° C. under reduced pressure to increased pressure for 1 to 86400 seconds. When a toluene solution of Ni (COD) ₂ is used as (D), the production of the reaction product can be confirmed by changing the color of the solution from yellow to, for example, red.

  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. The metal complex (A) is produced. This substitution reaction preferably proceeds quantitatively, but may not proceed completely in some cases. After completion of the reaction, in addition to the metal complex (A), other components derived from (B), (C), and (D) coexist, but when performing the polymerization reaction or copolymerization reaction of the present invention, these other components These components may or may not be removed. Generally, it is preferable to remove these other components because high activity can be obtained.

Incidentally, when performing the reaction, it may coexist L ¹ of the present invention. When nickel or palladium is used as M of the present invention, the stability of the purified metal 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 propenoic acid derivative ester, and the obtained metal complex (A) is used. You may use for superposition | polymerization of (alpha) -olefin, the copolymerization of (alpha) -olefin and a propenoic acid derivative ester, and you may perform reaction in 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 propenoic acid derivative ester. In this case, these monomers may exist or may not exist. Moreover, about the component shown by general formula (B)-(D), 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, Et represents an ethyl group, iPr represents an isopropyl group, Ph represents a phenyl group, Cy represents a cyclohexyl group, and tBu represents a tertiary butyl 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 a reaction between the general formula (B) or (C) and 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. In the reactor used for polymerization of α-olefin and copolymerization of α-olefin and propenoic acid derivative ester (for example, (meth) acrylic acid ester) in the presence or absence of these monomers. You may carry out, and you may carry out in a container different from this reactor.

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 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 and the like, 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 sauconite, 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 said additive, the polymerization inhibitor which prohibits radical polymerization of (b) component, and the additive which has the effect | action which stabilizes a production | generation 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 of 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 copolymerization properties of propenoic acid derivative esters (eg, acrylate esters) can be improved. The amount of the Lewis base is 0.0001 to 1000 equivalents, preferably 0.1 to 100 equivalents, more preferably 0.3 equivalents with respect 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. In addition, the same Lewis base as L ^{1 of} 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 100 MPa, preferably 0.3 MPa to 90 MPa, and the polymerization time is 0.1 minutes to 10 minutes. The time can be selected from the range of 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 employed depending on the purpose. For example, in the case of batch polymerization, it is possible to take a technique in which a predetermined amount of monomer is supplied to a 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 composition of the copolymer, a method of controlling the copolymer by supplying a plurality of monomers to the 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 the bulky substituent 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, compatibilizer, 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) Melting point (Tm), crystallization temperature (Tc):
It calculated | required by the following DSC measurements.
Using a PerkinElmer PYRIS Diamond DSC differential scanning calorimeter, the sample (about 5 mg) was melted at 210 ° C. for 5 minutes, cooled to −20 ° C. at a rate of 10 ° C./min, and then at −20 ° C. for 5 minutes. After being held, the melting curve was obtained by raising the temperature to 210 ° C. at a rate of 10 ° C./min. 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), 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-SP 260VS 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 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 ethylene polymer, K = 4.77E-4, α = 0.70.

2. Ligand, Complex (Synthesis Example 1): Synthesis of Ligand B-39 (1) Synthesis of Intermediate 2 Intermediate 2 was synthesized according to the following scheme.

50 g (0.36 mol) of 2,6-dimethoxybenzene 1 was dissolved in anhydrous THF (500 ml). To this, an n-butyllithium n-hexane solution (166 ml, 0.42 mol) was gradually added at 0 ° C. in a nitrogen atmosphere. A solution of iodine (96.5 g, 0.38 mol) dissolved in anhydrous THF (200 ml) was added dropwise to the obtained solution at 0 ° C. over 40 minutes. The resulting solution was stirred overnight at room temperature. After completion, 80 ml of methanol was added dropwise, and the resulting mixture was concentrated under reduced pressure, water (200 ml) was added, and the mixture was extracted 3 times with ethyl acetate (250 ml). The organic layer was collected, washed with Na ₂ S ₂ O ₃ and brine, and then dried over sodium sulfate. After drying, the inorganic salt was filtered off, concentrated under reduced pressure, and the residue was washed 4 times with methanol (50 ml) and dried, yielding intermediate 2 as a yellow solid. Yield: 63 g (yield: 66%).

(2) Synthesis of Intermediate 4 Intermediate 4 was synthesized according to the following scheme.

7.5 g (28.3 mmol) of Intermediate 2 was dissolved in anhydrous THF. To this, a THF solution of isopropylmagnesium chloride (14.3 ml, concentration: 2M, solvent: anhydrous THF) was gradually added at −50 ° C. under a nitrogen atmosphere, and the resulting mixture was stirred at room temperature for 1 hour.
The mixture was then cooled to −78 ° C. and phosphorus trichloride (1.95 g, 14.1 mmol) was added slowly. Thereafter, the mixture was stirred overnight at room temperature, and the resulting reaction product containing Intermediate 4 was used in the next reaction without further purification.

(3) Synthesis of Intermediate 6 Intermediate 6 was synthesized according to the following scheme.

Compound 5 (3 g, 14.4 mmol) was dissolved in anhydrous THF (40 ml), and a solution of sec-butyllithium (11 ml, 14.4 mol) was gradually added at −78 ° C. under a nitrogen atmosphere, and the resulting mixture was obtained. Was stirred at −78 ° C. for 2 hours.
Then, the THF solution of Intermediate 4 obtained above was added dropwise to the solution at −30 ° C., and the resulting mixture was stirred at room temperature for 1 hour. Sulfur (1.84 g, 57.6 mmol) was added to the obtained reaction mixture, and the mixture was stirred at room temperature overnight. After completion, water was added to the reaction mixture (THF was removed under reduced pressure), extraction was performed with ethyl acetate, and the organic layer was dried over sodium sulfate. The inorganic salt was filtered off and the organic layer was concentrated under reduced pressure. The obtained residue was purified with a column using petroleum ether / ethyl acetate as a solvent to obtain the intended intermediate 6.

(4) Synthesis of Ligand B-39 Ligand B-39 was synthesized according to the following scheme.

Intermediate 6 (9 g) was dissolved in ethyl acetate (150 ml) and hydrogen chloride gas was bubbled at −40 ° C. for 15 minutes. The temperature was gradually raised to room temperature, and the mixture was further stirred at room temperature for 30 minutes. The reaction mixture was concentrated under reduced pressure to give Intermediate 7 as a white solid (6.2 g).
Raney nickel catalyst was suspended in THF (20 ml), a solution of intermediate 7 (4.2 g, 7 mmol) in THF (180 ml) was added, and the mixture was stirred at room temperature for 16 hours. The solid was then filtered off and the filtrate was concentrated under reduced pressure. The obtained solid was recrystallized with a mixed solvent of ethyl acetate and petroleum ether to obtain the target ligand B-39 as a white solid. Yield 2.8g.
¹ H-NMR (CDCl ₃ , δ ppm): 7.17 (2H, t), 6.97 (1H, d), 6.60 (1H, d), 6.59 (1H, t), 6.55 (1H, t), 6.43 (4H, dd), 6.33 (1H, d), 3.92 (2H, d), 3.55 (12H, s), 1.35 (9H, s) ;
³¹ P-NMR (CDCl ₃ , δ ppm): −48.2 (s)

Synthesis Example 2 Synthesis of Ligand B-43 (1) Synthesis of Intermediate 2 Intermediate 2 was synthesized according to the following scheme. Here, MOM represents a methoxymethyl group (the same applies hereinafter).

Orthocresol 1 (50 g, 463 mmol) was stirred at 0 ° C. in a THF (600 ml) solution of sodium hydride (2.91 g, 1.5 eq, dispersed in mineral oil at a concentration of 60%) prepared separately. It was dripped. The temperature was gradually raised to room temperature, and the reaction was allowed to proceed for 1 hour at room temperature.
Then, chloromethoxymethane (52.7 ml, 770 mmol) was added dropwise at 0 ° C., the temperature was raised to room temperature, and the mixture was stirred at room temperature overnight. Water was added to the obtained reaction mixture, THF was removed under reduced pressure, and extraction operation was performed using water and ethyl acetate. The organic layer was washed with 10% aqueous NaOH solution, then with saturated brine, and dried over sodium sulfate. The inorganic salt was filtered off and concentrated under reduced pressure. The resulting oil was purified by distillation under reduced pressure to obtain 50 g of the intended intermediate 2.

(2) Synthesis of Intermediate 3 Intermediate 3 was synthesized according to the following scheme.

5 g (32.9 mmol) of Intermediate 2 was dissolved in THF (80 ml), and n-butyllithium (2.5 M, 13.2 ml, 32.9 mmol) was added dropwise thereto at 0 ° C. under a nitrogen atmosphere. Stir at that temperature for 2 hours.
Next, a THF solution of B (OMe) ₃ (5.6 ml, 1.5 eq.) Was gradually added to this reaction mixture at −78 ° C., and the mixture was warmed to room temperature and stirred overnight at room temperature. 20 mL of 1N hydrochloric acid was added to the obtained reaction mixture, and extraction operation was performed using water and diethyl ether. The organic layer was washed with saturated brine and dried over sodium sulfate. The inorganic salt was filtered off and concentrated under reduced pressure. The resulting crude product was recrystallized using petroleum ether to obtain Intermediate 3.

(3) Synthesis of Intermediate 4 Intermediate 4 was synthesized according to the following scheme.

  Intermediate 3 (12.88 g, 47.8 mmol), 1-bromo-3,5-di-tert-butylbenzene (103 g, 1.1 eq.), Tetrakis (triphenylphosphine) palladium (2.76 g,. 05 eq.), Sodium carbonate (6.10 g, 1.2 eq.), Distilled water (8 ml), ethanol (8 ml) and toluene (150 ml) were stirred at 100 ° C. for 16 hours. After cooling to room temperature, extraction operation was performed using water and ethyl acetate. The organic layer was washed with saturated brine and dried over sodium sulfate. The inorganic salt was filtered off and concentrated under reduced pressure. The resulting oil was purified by a column using petroleum ether / ethyl acetate (80/1) as a solvent to obtain 16 g of a crude product. 50 ml of methanol was added to the obtained crude product, and the precipitated solid was collected by filtration. The obtained solid was dried under reduced pressure for 1 hour to obtain Intermediate 4 (14.5 g) as a colorless solid.

(4) Synthesis of Intermediate 5 Intermediate 5 was synthesized according to the following scheme.

2.43 g (7.1 mmol) of Intermediate 4 was dissolved in THF (40 ml), and sec-butyllithium was added dropwise thereto at −78 ° C., followed by stirring at that temperature for 2 hours. Subsequently, 2 g (7.1 mmol) of P (o-OMePh) ₂ Cl was added dropwise at −30 ° C., the temperature was gradually raised to room temperature, and the mixture was stirred at room temperature overnight. Sulfur (0.91 g, 27.4 mmol) was added to the obtained reaction mixture, and the mixture was stirred at room temperature overnight. Water was added to the obtained reaction mixture, THF was removed under reduced pressure, and extraction operation was performed using water and ethyl acetate. The organic layer was washed with saturated brine and dried over sodium sulfate. The inorganic salt was filtered off and concentrated under reduced pressure. The resulting solid was purified with a column using petroleum ether / ethyl acetate (5/1) as a solvent to obtain 1.6 g of the intended intermediate 5.

(5) Synthesis of Intermediate 6 Intermediate 6 was synthesized according to the following scheme.

  Intermediate 5 (1.6 g) was dissolved in ethyl acetate and hydrogen chloride gas was bubbled at −78 ° C. for 15 minutes. The temperature was gradually raised to room temperature, and the mixture was further stirred at room temperature for 1 hour. The reaction mixture was concentrated under reduced pressure to obtain Intermediate 6.

(6) Synthesis of Ligand B-43 Ligand B-43 was synthesized according to the following scheme.

Raney nickel catalyst (1.5 g, 17.5 mmol) was suspended in THF (10 ml), a solution of intermediate 6 (0.8 g, 1.4 mmol) in THF (20 ml) was added, and the mixture was stirred at room temperature for 48 hours. The solid was then filtered off and the filtrate was concentrated under reduced pressure. The obtained solid was recrystallized with a mixed solvent of ethyl acetate and petroleum ether to obtain the target ligand B-43 as a white solid.
¹ H-NMR (CDCl ₃ , δ ppm): 7.35 (1H, s), 7.28-7.18 (6H, m), 6.99 (2H, t), 6.86 (2H, t) 6.80-6.77 (2H, m), 6.74 (1H, t), 5.79 (1H, s), 3.66 (6H, s), 3.46 (2H, s), 1.29 (18H, s);
³¹ P-NMR (CDCl ₃ , δ ppm): −33.6 (s)

Synthesis Example 3 Synthesis of Ligand B-34 (1) Synthesis of Intermediate 3 Intermediate 3 was synthesized according to the following scheme.

  Intermediate 2 (0.57 g, 4.1 mmol), 1-bromo-3,5-di-tert-butylbenzene (1.0 g, 3.7 mmol), tetrakis (triphenylphosphine) palladium (0.21 g, 0 .05 eq.), Sodium carbonate (0.59 g, 1.5 eq.), Distilled water (1 ml), ethanol (2 ml), and toluene (20 ml) were stirred at 100 ° C. for 16 hours. After cooling to room temperature, extraction operation was performed using water and ethyl acetate. The organic layer was washed with saturated brine and dried over sodium sulfate. The inorganic salt was filtered off and concentrated under reduced pressure. The resulting oil was purified by a column using petroleum ether / ethyl acetate (80/1) as a solvent to obtain 1 g of a crude product 3.

(2) Synthesis of Intermediate 4 Intermediate 4 was synthesized according to the following scheme.

While stirring Intermediate 3 (26 g, 92 mmol) in a solution of sodium hydride (2.91 g, 1.5 eq, dispersed in mineral oil at a concentration of 60%) prepared separately in THF (600 ml) at 0 ° C. It was dripped. The temperature was gradually raised to room temperature, and the reaction was allowed to proceed for 1 hour at room temperature.
Then, chloromethoxymethane (52.7 ml, 770 mmol) was added dropwise at 0 ° C., the temperature was raised to room temperature, and the mixture was stirred at room temperature overnight. Water was added to the obtained reaction mixture, THF was removed under reduced pressure, and extraction operation was performed using water and ethyl acetate. The organic layer was washed with 10% NaOH aqueous solution and then with saturated brine and dried over sodium sulfate. The inorganic salt was filtered off and concentrated under reduced pressure to obtain 26 g of the intended intermediate 4.

(3) Synthesis of Intermediate 6 Intermediate 6 was synthesized according to the following scheme.

  2.15 g (6.6 mmol) of Intermediate 4 was dissolved in THF (40 ml), and tert-butyllithium (4.1 mL, 6.6 mmol) was added dropwise thereto at −78 ° C., and the temperature was gradually raised to room temperature. And stirred at room temperature for 3 hours. Subsequently, 1.87 g (6.6 mmol) of compound 5 (THF solution 20 mL) was added dropwise at 0 ° C., the temperature was gradually raised to room temperature, and the mixture was stirred at room temperature overnight. Sulfur (0.91 g, 27.4 mmol) was added to the obtained reaction mixture, and the mixture was stirred at room temperature for 4 hours. Water was added to the obtained reaction mixture, THF was removed under reduced pressure, and extraction operation was performed using water and ethyl acetate. The organic layer was washed with saturated brine and dried over sodium sulfate. The inorganic salt was filtered off and concentrated under reduced pressure. The resulting solid was purified by a column using petroleum ether / ethyl acetate (20/1) as a solvent, and 1.2 g (32%) of the intended intermediate 6 was obtained. )Obtained.

(4) Synthesis of Ligand B-34 Ligand B-34 was synthesized according to the following scheme.

Intermediate 6 (1.2 g) was dissolved in 25 mL of ethyl acetate and hydrogen chloride gas was bubbled at −78 ° C. for 15 minutes. The temperature was gradually raised to room temperature, and the mixture was further stirred at room temperature for 1 hour. The reaction mixture was concentrated under reduced pressure to give ligand B-34.
¹ H-NMR (CDCl ₃ , δ ppm): 7.44-7.35 (6H, m), 6.94-6.91 (6H, m), 6.87-6.85 (2H, m), 6.44 (1H, d), 3.78 (6H, s), 1.38 (18H, s);
³¹ P-NMR (CDCl ₃ , δ ppm): −47.3 (s)

Synthesis Example 4 Synthesis of Ligand B-7 (1) Synthesis of Intermediate 2 Intermediate 2 was synthesized according to the following scheme.

2,4-di-t-butylphenol (10 g, 48.5 mmol) was dissolved in THF (100 ml). This solution was added dropwise to a separately prepared TFH (200 ml) solution of sodium hydride (2.91 g, 1.5 eq, dispersed in mineral oil at a concentration of 60%) at 0 ° C. with stirring. The temperature was gradually raised to room temperature, and the reaction was allowed to proceed at room temperature for 2 hours.
Next, chloromethoxymethane (7.76 g) was added dropwise at 0 ° C., the temperature was raised to room temperature, and the mixture was reacted at room temperature for 3 hours. The cloudy white solution was extracted with water and ethyl acetate. The organic layer was washed with aqueous KOH (1M, 150 ml), then water (150 ml) and dried over sodium sulfate. The inorganic salt was filtered off and concentrated under reduced pressure to obtain a pale yellow oil. The obtained oil was purified by a column using petroleum ether / ethyl acetate (40/1) as a solvent to obtain 10.5 g of the intended intermediate 2.

(2) Synthesis of Intermediate 4 Intermediate 4 was synthesized according to the following scheme.

0.75 g (3.0 mmol) of Intermediate 2 was dissolved in THF (30 ml), and n-butyllithium (2.5 M, 1.2 ml, 3.0 mmol) was added dropwise at 0 ° C. under an argon atmosphere. did. The temperature was gradually raised to room temperature, and the reaction was carried out at room temperature for 3 hours.
Next, a solution of bis (2-methoxyphenyl) chlorophosphine (700 mg, 2.50 mmol) dissolved in 15 ml of THF was added dropwise to the reaction mixture at 0 ° C. The temperature was gradually raised to room temperature, and the mixture was stirred at room temperature overnight. After completion of the stirring, deaerated saturated ammonium chloride aqueous solution (10 ml) was added, the organic layer was separated, extracted with diethyl ether, washed with brine (10 ml), dried over sodium sulfate, and intermediate 4 was obtained. Obtained.
The same operation was repeated to finally obtain 8 g of intermediate 4.

(3) Synthesis of Intermediate B-7_HCl Intermediate B-7_HCl was synthesized according to the following scheme.

  Intermediate 4 (8 g) obtained in Synthesis Example 4 (2) was dissolved in diethyl ether (500 ml), and hydrogen chloride gas was bubbled at −78 ° C. for 25 minutes. Then, it heated up to room temperature and stirred overnight at room temperature. After completion of stirring, the solvent was distilled off to obtain B-7_HCl.

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

Of the intermediate B-7_HCl obtained in Synthesis Example 4 (3), 7.3 g was dissolved in diethyl ether (500 ml), and ammonia gas was bubbled at −78 ° C. for 30 minutes.
Next, the temperature was gradually raised to room temperature, and the mixture was stirred at room temperature overnight. After completion of the stirring, the solvent was distilled off to obtain crude B-7. The crude B-7 obtained here was dispersed in diethyl ether (10 ml), and then 100 ml of n-hexane was added to perform suspension washing. After removing the solid components, the solvent was removed under reduced pressure to obtain the target ligand B-7. Yield: 5.2g.
¹ H-NMR (MeOD, δ ppm): 7.38-6.69 (m, 10H), 3.70 (s, 6H), 1.43 (s, 9H), 1.10 (s, 9H);
³¹ P-NMR (MeOD, δ ppm): −48.2 (s).

(Synthesis Example 4)
Synthesis of nickel complex 1:
1.237 g (4.0 mmol) of acyltriphenylphosphoranylmetallene and 1.10 g (4.0 mmol) of bis-1,5-cyclooctadiene nickel (0) (hereinafter referred to as Ni (COD) ₂ ), 40 ml of toluene was added at room temperature to obtain a yellow suspension. To this suspension, 0.86 g (8.0 mmol) of 2,6-lutidine was added using a syringe. The resulting mixture was stirred at room temperature, then heated to 60 ° C. with stirring, and reacted at 60 ° C. for 3.5 hours to obtain a dark brown solution. The resulting solution was filtered with a cannula, and the resulting dark yellow filtrate was concentrated under reduced pressure to ¼ of the original volume. To this concentrated solution, n-hexane (about 3 ml) was added dropwise until the liquid became cloudy.
Next, the turbid liquid was heated to 65 ° C. to obtain a transparent solution. The obtained transparent solution was slowly cooled to room temperature over 2 to 3 hours, and yellow fine crystals were precipitated at around room temperature. The resulting crystals were kept overnight in the mother liquor. Thereafter, the supernatant was filtered off with a cannula, the remaining solid was washed twice with 3 ml of n-hexane, and finally the solid was dried at 6 × 10 ⁻³ mbar under reduced pressure for 1 hour to obtain 1.17 g of yellow crystals. Obtained (yield: 60.4%).
¹ H-NMR (C ₆ D ₆ , δ ppm): 7.67 (m, 5H), 7.37 (d, 2H), 7.2-7.0 (m, 4H), 6.77 (m, 4H), 6.56 (d, 1H), 6.50 (t, 1H), 6.15 (d, 1H), 4.20 (s, 1H), 3.49 (s, 6H), 2. 06 (s, 3H);
³¹ P-NMR (C ₆ D ₆ , δ ppm): 21.78 (s).

[Examples 1 to 10]
Ethylene homopolymerization and ethylene / acrylic acid ester copolymerization using ligand B-39 obtained in Synthesis Example 1
(1) Formation of complex All the following operations were performed in a high-purity argon atmosphere. Hereinafter, bis-1,5-cyclooctadiene nickel (0) is referred to as Ni (COD) ₂ .
First, B-39 (23.4 mg) obtained in Synthesis Example 1 was weighed 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-39, 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-39 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-14 and Ni (COD) ₂ reacted one-to-one to form a nickel complex.

(2) Ethylene homopolymerization and ethylene / acrylic acid ester copolymerization To a stirring blade having an internal volume of about 10 ml and an autoclave with an inner cylinder were charged dry toluene (4.2 ml) and a predetermined amount of acrylic acid ester as a conomonomer. When ethylene homopolymerization was performed, the acrylic ester was not charged. 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, carbon monoxide was blown. After removing the unreacted gas, the inner cylinder was taken out, and the solvent and unreacted comonomer were removed under reduced pressure, followed by drying until a constant weight was obtained.
The types and amounts of comonomers used for copolymerization are listed in Table 1. The comonomer was used after purification at room temperature in a high-purity argon atmosphere using a column packed with Aldrich Inhibitor Remover manufactured by Aldrich.
Table 1 also shows the amount of toluene used for the polymerization, the polymerization temperature, and the autoclave internal pressure during the polymerization. In Table 1, 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-14 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 1.

[Examples 11 to 15]
Ethylene homopolymerization and ethylene / acrylic acid ester copolymerization using ligand B-39 obtained in Synthesis Example 1
(1) Formation of complex It implemented like Example 1-10.

(2) Ethylene homopolymerization and ethylene / acrylic acid ester copolymerization Ethylene homopolymerization and ethylene / acrylic were conducted in the same manner as in Examples 1 to 10 except that 2,6-lutidine was added to the autoclave as an additive. The acid ester was copolymerized.
The results are shown in Table 1.

[Examples 16 to 19]
Homopolymerization of ethylene and copolymerization of ethylene / acrylic acid ester using ligand B-43 obtained in Synthesis Example 2:
(1) Formation of complex A complex was formed in the same manner as in Examples 1 to 10, except that B-43 (27.0 mg) obtained in Synthesis Example 2 was used as the ligand.

(2) Homopolymerization of ethylene and copolymerization of ethylene / acrylic acid ester Except for using the compound obtained in (1) above as a complex, the homopolymerization of ethylene and ethylene / acrylic acid ester were conducted in the same manner as in Examples 1-10. Acrylic ester copolymerization was performed.
The results are shown in Table 2. The items described in Table 2 are the same as in Table 1.

[Examples 20 and 21]
Homopolymerization of ethylene and copolymerization of ethylene / acrylic acid ester using ligand B-43 obtained in Synthesis Example 2:
(1) Formation of complex It implemented like Example 16-19.

(2) Ethylene homopolymerization and ethylene / acrylic acid ester copolymerization Ethylene homopolymerization and ethylene / acrylic were carried out in the same manner as in Examples 16 to 19 except that 2,6-lutidine was added as an additive to the autoclave. The acid ester was copolymerized.
The results are shown in Table 2.

[Comparative Examples 1 and 2]
Homopolymerization of ethylene using B-34 and copolymerization of ethylene acrylate:
(1) Formation of complex A complex was formed in the same manner as in Examples 1 to 10 except that B-34 (26.3 mg) obtained in Synthesis Example 3 was used as a ligand.

(2) Ethylene homopolymerization and ethylene / acrylic acid ester copolymerization Ethylene homopolymerization and ethylene / acrylic acid ester copolymerization were carried out in the same manner as in Examples 1 to 10, except that a 2-liter autoclave was used. Went.
The results are shown in Table 3. The items described in Table 3 are the same as in Table 1.

[Comparative Examples 3 to 23]
Homopolymerization of ethylene using B-7 and copolymerization of ethylene acrylate:
(1) Formation of complex A complex was formed in the same manner as in Examples 1 to 10, except that B-7 (22.5 mg) obtained in Synthesis Example 4 was used as the ligand.

(2) Homopolymerization of ethylene and copolymerization of ethylene / acrylic acid ester Except for using the compound obtained in (1) above as a complex, the homopolymerization of ethylene and ethylene / acrylic acid ester were conducted in the same manner as in Examples 1-10. Acrylic ester copolymerization was performed.
The results are shown in Table 4. The items described in Table 4 are the same as in Table 1.

[Comparative Examples 24-35]
Homopolymerization of ethylene using nickel complex 1 and copolymerization of ethylene acrylate:
Polymerization was carried out in the same manner as in Examples 1 to 10 except that the nickel complex 1 obtained in Synthesis Example 5 was used instead of the contact product of the ligand and the transition metal complex component (D).
The results are shown in Table 5. The items described in Table 5 are the same as in Table 1.

  The polymerization catalyst used in the present invention uses a nickel-centered catalyst instead of rare and expensive palladium, and the polymer or copolymer obtained in the present invention has mechanical and thermal properties. Since it can be applied as an excellent and useful molded article, it is extremely useful in industry.

Claims (7)

Following general formula (B) or metal compound represented by the (C), characterized by comprising obtained by contacting the transition metal complex (D) containing a transition metal belonging to group 10 of the periodic table Complex.

[In the formula (B) or (C), Z represents hydrogen or a leaving group. m represents the valence of Z. X ¹ represents oxygen. Y ¹ represents carbon. E ¹ represents phosphorus. R ⁴ each independently represents hydrogen or a hydrocarbon group that may contain a C 1-20 hetero atom, and at least one of R ⁴ contains one or more hetero atom-containing groups. It is a hydrocarbon group. R ⁵ each independently represents hydrogen or a hydrocarbon group that may contain a C 1-20 hetero atom. R ¹⁰ , R ¹¹ , R ¹² , and R ¹³ are each independently hydrogen, halogen, a hydrocarbon group that 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 (wherein R ¹ represents hydrogen 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, alkaline earth metal, ammonium, quaternary ammonia. And represents an integer of 0 to 3, and y represents an integer of 0 to 2.) ]   The manufacturing method of the alpha olefin polymer characterized by superposing | polymerizing alpha olefin (a) in presence of the metal complex of Claim 1. The method for producing an α-olefin polymer according to claim 2 , wherein the polymerization is carried out in the presence of a Lewis base. The method for producing an α-olefin polymer according to claim 2 , wherein the polymerization is carried out in the absence of an organoaluminum compound.   Production of an α-olefin / propenoic acid derivative ester copolymer comprising copolymerizing an α-olefin (a) and a propenoic acid derivative ester (b) in the presence of the metal complex according to claim 1. Method. The method for producing an α-olefin / propenoic acid derivative ester copolymer according to claim 5 , wherein the polymerization is carried out in the presence of a Lewis base. The method for producing an α-olefin / propenoic acid derivative ester copolymer according to claim 5 , wherein the polymerization is carried out in the absence of an organoaluminum compound.