JP6129598B2 - Diol compound, catalyst for olefin polymerization using the same, and method for producing olefin polymer - Google Patents

Description

  The present invention relates to a diol compound, a metal complex obtained by using the same, a catalyst for α-olefin polymerization using the same, and a method for producing an α-olefin polymer, and more specifically, derived from a specific diol compound. The present invention relates to application of a metal complex having a partial structure to an olefin polymerization catalyst.

Polyethylene resins and polypropylene resins are widely used in various industrial fields as main polymers in polyolefin resins, and since they are outstanding and important industrial materials, further improvements in various performances are always required.
In such a polyolefin resin production process, the catalyst used is a homogeneous catalyst using a heterogeneous solid catalyst such as a Ziegler-Natta catalyst or a Phillips catalyst and a solvent-soluble metal complex such as a metallocene catalyst. Is used exclusively.

  In recent years, inspired by the rapid development of metallocene catalysts, development of complexes different from metallocene complexes, so-called post-metallocene complexes, has been actively promoted. In this group of post metallocene complexes, a transition metal complex having a ligand having a special structure has attracted attention, and many transition metal complexes having a bidentate ligand have been reported.

Recently, a group of complexes having further tetradentate ligands has been studied and developed. For example, a tetradentate complex having two phenoxo ligands and two amine ligands has been reported, Usefulness as a catalyst for olefin polymerization such as ethylene and propylene has been reported (see Patent Document 1 and Non-Patent Document 1).
In addition to this, a tetradentate complex having two phenoxo ligands and two imine ligands (see Patent Document 2 and Non-Patent Document 2), two phenoxo ligands and two ether oxygen ligands. A tetradentate complex (see Patent Documents 3 and 4), a tetradentate complex (see Patent Documents 5 and 6) having two phenoxo ligands and two thioether ligands, two phenoxo ligands and two A tetradentate complex having a phosphine ligand (see Patent Document 7 and Non-patent Document 3), a tetradentate complex having three phenoxo ligands and one amine ligand (see Non-Patent Document 4), and two phenoxo A tetradentate complex having a ligand, one imine ligand and one amide ligand (see Patent Document 8), two phenoxo ligands, one amine ligand and one ether oxygen ligand A tetradentate complex with a 9 and Non-Patent Document 5), a tetradentate complex having three amine ligands and one amide ligand (see Non-Patent Document 6), two imine ligands and two pyridine ligands. A tetradentate complex (see Non-Patent Document 7) or the like having been reported as an olefin polymerization catalyst.

  However, many of the tetradentate complexes reported so far have phenoxo ligands, and the complexes with tetradentate ligands reported so far have the advantage of lower production costs compared to metallocene complexes. However, since the catalytic activity may be extremely low or the molecular weight of the produced polymer may be low, further improvement in performance as a polyolefin polymerization catalyst is required.

WO2002036638A2 WO2004069881A1 WO20120006230A1 WO2011109563A2 WO2011099583A1 WO2011099584A1 WO2006030192A1 WO2011158241A1 WO2001018010A1

S. Segal, A. Yeori, M. Shuster, Y. Rosenberg and M. Kol, Macromolecules, 2008, 41, 1612. Knight, P. D .; Clarke, A. J .; Kimberley, B. S .; Jackson, R. A .; Scott, P. Chem. Commun. 2002, 352-353. R. J. Long, D. J. Jones, V. C. Gibson and A. J. P. White, Organometallics, 2008, 27, 5960. C. Redshaw, MA Rowan, L. Warford, DM Homden, A. Arbaoui, MRJ Elsegood, SH Dale, T. Yamato, CP Casas, S. Matsui and S. Matsuura, Chem.-Eur. J., 2007, 13 , 1090. Tshuva, E. Y .; Goldberg, I .; Kol, M .; Weitman, H .; Goldschmidt, Z. Chem. Commun. 2000, 379-380. WO2001018010A1 S. Bambirra, D. van Leusen, C. G. J. Tazelaar, A. Meetsma and B. Hessen, Organometallics, 2007, 26, 1014. K. Yliheikkil¨a, K. Axenov, M. T. R¨ais¨anen, M. Klinga, M. P. Lankinen, M. Kettunen, M. Leskel¨a and T. Repo, Organometallics, 2007, 26, 980.

  An object of the present invention, ie, a problem is that in view of the problems of the prior art in the above-described transition metal complex having a tetradentate ligand, the catalytic activity is high, a high molecular weight olefin polymer can be produced, and a conventional metallocene is provided. The aim is to develop a transition metal complex having a tetradentate ligand that can be synthesized at a low cost by a synthetic route that is simpler than that of the complex. To that end, a ligand compound that can form such a metal complex, It is an object of the present invention to provide a polyolefin polymerization catalyst and an olefin polymerization method using the same.

  In order to solve the above problems, the present inventors have searched for various ligand compounds that can be used for transition metal complexes having a tetradentate ligand in a metal complex catalyst and can produce a high molecular weight polymer. As a result, we focused on complexes with a dialkoxo partial structure derived from a novel diol compound that have not been reported so far as transition metal complexes having a tetradentate ligand. In addition, the present inventors have established an electronic environment and found that the diol compound having such a specific structure functions as a component of a polymerization catalyst suitable for the above-mentioned purpose, and has led to the creation of the present invention.

  Thus, the diol compound constituting the basic constitution of the present invention is novel as a tetradentate ligand because it has a unique structure, and is characterized by the construction of a chemical and steric and electronic environment of the complex structure, They reveal a catalytic function that allows the desired polymerization of α-olefins.

  And the diol compound which comprises the basic invention (1st invention) of this invention is a diol compound represented by following General formula (1) and (2).

(In General Formulas (1) and (2), Q ₁ and Q ₄ are each independently carbon substituted with a divalent hydrocarbon group having 1 to 20 carbon atoms or a silyl group having 3 to 18 carbon atoms. A substituent selected from the group consisting of a divalent hydrocarbon group having 4 to 20 carbon atoms and a divalent hydrocarbon group having 1 to 20 carbon atoms substituted with a halogen atom is represented by Q ₂ and Q ₃ , respectively. Independently from a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms substituted with a halogen atom, or a silyl group substituted with a hydrocarbon group having 1 to 20 carbon atoms T ₁ and T ₂ each independently represent a substituent selected from the group consisting of: an alkoxy group having 1 to 10 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, an acyl group having 2 to 10 carbon atoms, From an ester group having 2 to 10 carbon atoms, an amino group, a substituted amino group having 1 to 12 carbon atoms or a halogen That shows the selected substituents from the group.)

In addition, here, a theoretical guess why the desired catalytic performance can be exhibited by the complex structure defined in the present invention is presented.
The diol compound constituting the basic constitution of the present invention is novel as a tetradentate ligand, and is characterized by the electronic and steric structure of the ligand, thereby providing a catalytic function in the polymerization of α-olefins. Is manifested.
That is, the diol compound has a structure represented by the above general formula (1) or (2), and is used as a catalyst component of an olefin polymerization catalyst in the present invention, combined with a cocatalyst and the like. An α-olefin polymerization catalyst is formed. The diol compound represented by the general formula (1) or (2) in the present invention is basically characterized in that a chelate cyclic structure is formed as a dialkoxo ligand at the time of complex formation. It can be presumed to bring about the specificity. Specifically, a tetradentate ligand that forms a chelate ring structure contributes to the stabilization of the complex structure, suppresses the formation of structural isomers often observed in tetradentate complexes, and stabilizes the polymerization field. It is considered that the polymerization performance is more preferably controlled.

  In addition, the diol compound in the present invention is expected to form a five-membered ring metal dialkoxo structure as shown in the following general formulas (3) and (4) by complexation. This five-membered ring chelate exhibits high stability and is considered to contribute to the performance improvement as a complex catalyst.

(In the general formulas (3) and (4), Q ₁ , Q ₂ , Q ₃ , Q ₄ , T ₁ and T ₂ are the same as those in the diol compound represented by the general formula (1) or (2). The same as the substituent, M represents a metal atom selected from the group consisting of group 4 to 10 transition metals, and X ₁ and X ₂ each independently represent a hydrogen atom, a carbon number of 1 to 20 Substitution selected from the group consisting of a hydrocarbon group, an alkoxy group having 1 to 10 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, an ester group having 2 to 10 carbon atoms, a substituted amino group having 1 to 12 carbon atoms, or a halogen Group.)

  Furthermore, the dialkoxo ligand derived from the diol structure has an electron donor property to the central metal at the time of complex formation as compared with, for example, the diphenoxo ligands reported so far. In this case, it is considered that the chain transfer reaction including β elimination is suppressed and the molecular weight of the generated polyolefin is controlled to the higher polymer side.

  By the way, as described above, the present invention is significantly different from the conventional invention in terms of the constituent requirements (specific matters of the invention) according to the documents listed above as patent documents and non-patent documents. It is not clear from the literature. That is, in the present invention, it is a diol compound that can form a unique and novel tetradentate ligand, and it is remarkable that a unique chemical, steric and electronic environment has been constructed in the complex structure. It is a characteristic.

  In the above, the background of the creation of the present invention and the basic configuration and features of the invention have been described generally. Here, when overviewing the overall configuration of the present invention, the present invention has the following invention units. It consists of a group.

  The diol compound represented by the general formula (1) or (2) described in paragraphs 0011 to 0013 is configured as the basic invention (1), and further, the diol compound of the basic invention (1) and the group 4 to 10 A metal complex obtained by reacting with a complex precursor which is a transition metal compound, that is, a metal complex represented by the general formula (3) or (4) described above in paragraphs 0015 to 0017 is configured as the basic invention (2). Each of the following inventions adds an additional requirement to the basic invention or indicates an embodiment thereof. All invention units are collectively referred to as an invention group.

And as invention below it, the catalyst component for olefin polymerization containing said metal complex, the following component (A) and (B), and (C) as needed further for olefin polymerization characterized by the above-mentioned It is a catalyst.
Component (A): The above metal complex, Component (B): Compound or ion-exchange layered silicate that reacts with component (A) to form an ion pair, Component (C): Organoaluminum compound

  Furthermore, as another invention, there is an olefin polymerization catalyst in which component (B) is an aluminoxane, an olefin polymerization catalyst in which component (B) is a boron compound, and in the presence of any of the above polymerization catalysts. This is a method for producing an olefin polymer by polymerizing or copolymerizing an olefin.

  Provided is a diol compound that can be synthesized at a low cost by a simple synthesis route compared to conventional metallocene complexes and can form a metal complex, a useful catalyst for polyolefin polymerization, and a method for polymerizing olefins using the same. The alkoxo ligand complex in which the unique diol compound of the present invention is complexed enables production of a high molecular weight olefin polymer.

In addition, it is proved that the polymer produced by the present invention has a higher molecular weight than the conventional tetradentate complex polymer by comparing the data of each Example described later and each Example and each Comparative Example. Further, as will be apparent from the synthesis route described later, it can be said that the metal complex of the present invention can be synthesized relatively easily by a simple synthesis route as compared with conventional metallocene complexes.
Thereby, it is expected to efficiently produce an olefin polymer having a high molecular weight, and the polyolefin polymerization catalyst by the metal complex of the present invention, and the olefin polymerization method using the same are from an industrial viewpoint. Is very useful.

  Below, the diol compound of this invention, a metal complex, the catalyst for polymerization by it, and the manufacturing method of an olefin polymer using the same are demonstrated in detail for every item.

1. Regarding Diol Compound (1) Basic Configuration The diol compound in the present invention is represented by the following general formula (1) or (2).

(In General Formulas (1) and (2), Q ₁ and Q ₄ are each independently carbon substituted with a divalent hydrocarbon group having 1 to 20 carbon atoms or a silyl group having 3 to 18 carbon atoms. A substituent selected from the group consisting of a divalent hydrocarbon group having 4 to 20 carbon atoms and a divalent hydrocarbon group having 1 to 20 carbon atoms substituted with a halogen atom is represented by Q ₂ and Q ₃ , respectively. Independently from a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms substituted with a halogen atom, or a silyl group substituted with a hydrocarbon group having 1 to 20 carbon atoms T ₁ and T ₂ each independently represent a substituent selected from the group consisting of: an alkoxy group having 1 to 10 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, an acyl group having 2 to 10 carbon atoms, From an ester group having 2 to 10 carbon atoms, an amino group, a substituted amino group having 1 to 12 carbon atoms or a halogen That shows the selected substituents from the group.)

_{(2) Q 1, Q 4} Q 1, Q 4 is a divalent hydrocarbon group having 1 to 20 carbon atoms for, preferably, a divalent hydrocarbon group having 1 to 12 carbon atoms, more preferably, An alkylene group having 1 to 12 carbon atoms, a phenylene group, an alkylene-phenylene-alkylene group, or a biphenylene group;
Preferred specific examples are methylene group, ethylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, 1,4-cyclohexylene group, {methylene- (1,4-cyclohexylene)} group, {Methylene- (1,4-cyclohexylene) -methylene} group, vinylene group, 1-propenylene group, 2-propenylene group, 1-butenylene group, 2-butenylene group, 3-butenylene group, 1-pentenylene group, 2-pentenylene group, 3-pentenylene group, 4-pentenylene group, 1-hexenylene group, 2-hexenylene group, 3-hexenylene group, 4-hexenylene group, 5-hexenylene group, phenylene group, methylenephenylene group, {methylene- (1,4-phenylene) -methylene} group and biphenylene group, more preferably methylene group, Tylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, 4-hexenylene group, {methylene- (1,4-cyclohexylene) -methylene} group, phenylene group, biphenylene group, particularly preferred Are a methylene group, an ethylene group, a trimethylene group, a phenylene group, and a biphenylene group.

Q _{1 and} Q ₄ which are divalent hydrocarbon groups having 4 to 20 carbon atoms substituted with silyl groups having 3 to 18 carbon atoms are preferably the aforementioned divalent hydrocarbon groups having 1 to 20 carbon atoms. Are substituted with a silyl group having 3 to 18 carbon atoms.
Preferred examples are (trimethylsilyl) methylene group, (1-trimethylsilyl) ethylene group, (2-trimethylsilyl) ethylene group, (1-triethylsilyl) ethylene group, (2-triethylsilyl) ethylene group, (1-trimethylsilyl) Trimethylene group, (2-trimethylsilyl) trimethylene group, (3-trimethylsilyl) trimethylene group, (1-trimethylsilyl) tetramethylene group, (2-trimethylsilyl) tetramethylene group, (3-trimethylsilyl) tetramethylene group, (4-trimethylsilyl) ) Tetramethylene group, (1-trimethylsilyl) pentamethylene group, (2-trimethylsilyl) pentamethylene group, (3-trimethylsilyl) pentamethylene group, (4-trimethylsilyl) pentamethylene group, (5-trimethyl) Ryl) pentamethylene group, (1-trimethylsilyl) hexamethylene group, (2-trimethylsilyl) hexamethylene group, (3-trimethylsilyl) hexamethylene group, (4-trimethylsilyl) hexamethylene group, (5-trimethylsilyl) hexamethylene group (6-trimethylsilyl) hexamethylene group, more preferably (trimethylsilyl) methylene group, (1-trimethylsilyl) ethylene group, (2-trimethylsilyl) ethylene group, (1-triethylsilyl) ethylene group, (2- Triethylsilyl) ethylene group, particularly preferably (trimethylsilyl) methylene group, (1-trimethylsilyl) ethylene group, and (2-trimethylsilyl) ethylene group.

Q _{1 and} Q ₄ which are divalent hydrocarbon groups having 1 to 20 carbon atoms substituted with halogen atoms are preferably substituted with halogen atoms for the aforementioned divalent hydrocarbon groups having 1 to 20 carbon atoms. Structure.
Preferred examples are (chloro) methylene group, (1-chloro) ethylene group, (2-chloro) ethylene group, (1-bromo) ethylene group, (2-bromo) ethylene group, (1-chloro) trimethylene group. , (2-chloro) trimethylene group, (3-chloro) trimethylene group, (1-chloro) tetramethylene group, (2-chloro) tetramethylene group, (3-chloro) tetramethylene group, (4-chloro) tetra Methylene group, (1-chloro) pentamethylene group, (2-chloro) pentamethylene group, (3-chloro) pentamethylene group, (4-chloro) pentamethylene group, (5-chloro) pentamethylene group, (1 -Chloro) hexamethylene group, (2-chloro) hexamethylene group, (3-chloro) hexamethylene group, (4-chloro) hexamethylene group, (5-chloro) he Samethylene group and (6-chloro) hexamethylene group, more preferably (chloro) methylene group, (1-chloro) ethylene group, (2-chloro) ethylene group, (1-bromo) ethylene group, (2 -Bromo) ethylene group, particularly preferably (chloro) methylene group, (1-chloro) ethylene group, (2-chloro) ethylene group.

_{(3) Q 2, Q 3} Q 2, Q 3 is a hydrocarbon group having 1 to 20 carbon atoms for is preferably an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group.
Here, examples of the alkyl group and the cycloalkyl group include methyl group, ethyl group, 1-propyl group, isopropyl group, 1-butyl group, isobutyl group, t-butyl group, 1-pentyl group, 1-hexyl group, 1-heptyl group, 1-octyl group, 1-nonyl group, 1-decyl group, tricyclohexylmethyl group, 1,1-dimethyl-2-phenylethyl group, 1-dimethylpropyl group, 1,1,2-trimethyl Propyl group, 1,1-diethylpropyl group, 1-phenyl-2-propyl group, 1,1-dimethylbutyl group, 2-pentyl group, 3-pentyl group, 2-hexyl group, 3-hexyl group, 2- Ethylhexyl, 2-heptyl, 3-heptyl, 4-heptyl, 2-propylheptyl, 2-octyl, 3-nonyl, cyclopropyl, cyclobutyl, cycl Pentyl group, methylcyclopentyl group, cyclohexyl group, methylcyclohexyl group, cycloheptyl group, cyclooctyl group, cyclododecyl group, 1-adamantyl group, 2-adamantyl group, exo-norbornyl group, endo-norbornyl group, 2-bicyclo [ 2.2.2] An octyl group, a nopinyl group, a decahydronaphthyl group, a menthyl group, a neomenthyl group, a neopentyl group, a 5-decyl group, and the like.
Among these, preferred substituents are isopropyl group, isobutyl group, and cyclohexyl group.

Examples of the alkenyl group include a vinyl group, an allyl group, a butenyl group, a cinnamyl group, and a styryl group.
Examples of the aryl group include a phenyl group, a naphthyl group, an anthracenyl group, and a fluorenyl group. Examples of the substituent that can be present in the aromatic ring of these aryl groups include an alkyl group, an aryl group, a fused aryl group, and a phenylcyclohexyl group. Group, phenylbutenyl group, tolyl group, xylyl group, p-ethylphenyl group and the like.
Among these, a preferred substituent is a phenyl group. Among these specific examples, particularly preferred substituents are a methyl group, an ethyl group, and a phenyl group, and particularly preferred is a methyl group.

Q ₂ and Q _{3 which} are hydrocarbon groups having 1 to 20 carbon atoms substituted with a halogen atom are preferably structures in which the above hydrocarbon groups having 1 to 20 carbon atoms are substituted with halogen atoms. .
Specific preferred examples include a trifluoromethyl group or a pentafluorophenyl group.

Q ₂ and Q ₃ which are silyl groups substituted with a hydrocarbon group having 1 to 20 carbon atoms are preferably silyl groups having 3 to 18 carbon atoms, and preferred specific examples thereof are trimethylsilyl group and dimethylphenylsilyl group. , Diphenylmethylphenylsilyl group and triphenylsilyl group.
Among these, a more preferable substituent is a trimethylsilyl group or a dimethylphenylsilyl group, and a trimethylsilyl group is particularly preferable.

_{(4) T} 1, _{T 2} is an alkoxy group having 1 to 10 carbon atoms for T 1, _{T 2} is preferably an alkoxy group having 1 to 4 carbon atoms, preferred examples are methoxy group, an ethoxy group , Isopropoxy group, 1-propoxy group, 1-butoxy group, t-butoxy group and the like.
Among these, a more preferable substituent is a methoxy group, an ethoxy group, or an isopropoxy group, and a methoxy group is particularly preferable.

T ₁ and T ₂ which are aryloxy groups having 6 to 20 carbon atoms are preferably aryloxy groups having 6 to 12 carbon atoms, and preferred examples thereof include phenoxy group, 4-methylphenoxy group and 4-methoxyphenoxy group. 2,6-dimethylphenoxy group, and 2,6-di-t-butylphenoxy group.
Among these, a more preferable substituent is a phenoxy group or a 2,6-dimethylphenoxy group, and a phenoxy group is particularly preferable.

T ₁ and T ₂ which are acyl groups having 2 to 10 carbon atoms are preferably acyl groups having 2 to 8 carbon atoms, and preferred specific examples are acetyl group, propionyl group, butyryl group, isobutyryl group, valeryl group. , Isovaleryl group, pivaloyl group, and benzoyl group.
Among these, more preferred substituents are an acetyl group, a pivaloyl group, and a benzoyl group, and particularly preferred is a benzoyl group.

T ₁ and T ₂ which are ester groups having 2 to 10 carbon atoms are preferably ester groups having 2 to 8 carbon atoms, and preferred specific examples are methoxycarbonyl group, ethoxycarbonyl group, n-propoxycarbonyl group, Isopropoxycarbonyl group, n-butoxycarbonyl group, t-butoxycarbonyl group, (4-hydroxybutoxy) carbonyl group, (4-glycidylbutoxy) carbonyl group, phenoxycarbonyl group, succinic anhydride group, succinimide group Can be mentioned.
Among these, more preferred substituents include a methoxycarbonyl group, an ethoxycarbonyl group, a (4-hydroxybutoxy) carbonyl group, and a succinic anhydride group, and particularly preferred are a methoxycarbonyl group and a succinic anhydride group. It is a group.

Preferable specific examples of T ₁ and T ₂ which are substituted amino groups having 1 to 12 carbon atoms include monomethylamino group, dimethylamino group, monoethylamino group, diethylamino group, monoisopropylamino group, diisopropylamino group, and monophenylamino. Group, diphenylamino group, bis (trimethylsilyl) amino group, morpholinyl group.
Of these, more preferred substituents are a dimethylamino group and a bis (trimethylsilyl) amino group.

Preferable specific examples of T ₁ and T ₂ which are halogen are fluorine, chlorine and bromine. Of these, a more preferred substituent is chlorine.

(5) Specific example of diol compound As a preferable specific example of the diol compound used for the metal complex of the present invention, the following diol compounds may be mentioned. These are examples, and it is obvious that the present invention is not limited to these.

2. About metal complex (1) About basic composition The metal complex in this invention is a metal complex obtained by making a diol compound and the complex precursor which is a 4-10 group transition metal compound react, Specifically, the following It is a metal complex shown by General formula (3) or (4).

(In the general formulas (3) and (4), Q ₁ , Q ₂ , Q ₃ , Q ₄ , T ₁ and T ₂ are the same as those in the diol compound represented by the general formula (1) or (2). The same as the substituent, M represents a metal atom selected from the group consisting of group 4 to 10 transition metals, and X ₁ and X ₂ each independently represent a hydrogen atom, a carbon number of 1 to 20 Substitution selected from the group consisting of a hydrocarbon group, an alkoxy group having 1 to 10 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, an ester group having 2 to 10 carbon atoms, a substituted amino group having 1 to 12 carbon atoms, or a halogen Group.)

M, which is a metal atom selected from the group consisting of Group 4 to 10 transition metals, is preferably a Group 4 to 6 transition metal, and particularly preferably a Group 4 transition metal.
Preferable specific examples are titanium, zirconium and hafnium, and more preferably zirconium and hafnium.

_{(2) X 1, X 2} X 1, X 2 is a hydrocarbon group having 1 to 20 carbon atoms for is preferably an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group.
Here, examples of the alkyl group and the cycloalkyl group include methyl group, ethyl group, 1-propyl group, isopropyl group, 1-butyl group, t-butyl group, isobutyl group, 1-pentyl group, 1-hexyl group, 1-heptyl group, 1-octyl group, 1-nonyl group, 1-decyl group, tricyclohexylmethyl group, 1,1-dimethyl-2-phenylethyl group, 1-dimethylpropyl group, 1,1,2-trimethyl Propyl group, 1,1-diethylpropyl group, 1-phenyl-2-propyl group, 1,1-dimethylbutyl group, 2-pentyl group, 3-pentyl group, 2-hexyl group, 3-hexyl group, 2- Ethylhexyl, 2-heptyl, 3-heptyl, 4-heptyl, 2-propylheptyl, 2-octyl, 3-nonyl, cyclopropyl, cyclobutyl, cycl Pentyl group, methylcyclopentyl group, cyclohexyl group, methylcyclohexyl group, cycloheptyl group, cyclooctyl group, cyclododecyl group, 1-adamantyl group, 2-adamantyl group, exo-norbornyl group, endo-norbornyl group, 2-bicyclo [ 2.2.2] An octyl group, a nopinyl group, a decahydronaphthyl group, a menthyl group, a neomenthyl group, a neopentyl group, a 5-decyl group, and the like.
Among these, preferred substituents are isopropyl group, isobutyl group, and cyclohexyl group.

Examples of the alkenyl group include a vinyl group, an allyl group, a butenyl group, a cinnamyl group, and a styryl group.
Examples of the aryl group include a phenyl group, a naphthyl group, an anthracenyl group, and a fluorenyl group. Examples of the substituent that can be present in the aromatic ring of these aryl groups include an alkyl group, an aryl group, a fused aryl group, and a phenylcyclohexyl group. Group, phenylbutenyl group, tolyl group, xylyl group, p-ethylphenyl group and the like. Among these, a preferred substituent is a phenyl group.
Among these specific examples, preferred substituents are a methyl group, an allyl group, a benzyl group, and a phenyl group, and particularly preferred are a methyl group and a benzyl group.

X ₁ and X ₂ which are an alkoxy group having 1 to 10 carbon atoms are preferably an alkoxy group having 1 to 4 carbon atoms, and preferred specific examples are a methoxy group, an ethoxy group, an isopropoxy group, and a 1-propoxy group. 1-butoxy group, t-butoxy group and the like.
Among these, a more preferred substituent is a methoxy group, an ethoxy group, or an isopropoxy group, and particularly preferably an isopropoxy group.

X ₁ and X ₂ which are aryloxy groups having 6 to 20 carbon atoms are preferably aryloxy groups having 6 to 12 carbon atoms, and preferred specific examples are phenoxy group, 4-methylphenoxy group and 4-methoxyphenoxy group. 2,6-dimethylphenoxy group, and 2,6-di-t-butylphenoxy group.
Among these, a more preferable substituent is a phenoxy group or a 2,6-dimethylphenoxy group, and a phenoxy group is particularly preferable.

X ₁ and X ₂ which are ester groups having 2 to 10 carbon atoms are preferably ester groups having 2 to 8 carbon atoms, and preferred specific examples thereof are methoxycarbonyl group, ethoxycarbonyl group, n-propoxycarbonyl group, Isopropoxycarbonyl group, n-butoxycarbonyl group, t-butoxycarbonyl group, (4-hydroxybutoxy) carbonyl group, (4-glycidylbutoxy) carbonyl group, phenoxycarbonyl group, succinic anhydride group, succinimide group Can be mentioned.
Among these, more preferable substituents include a methoxycarbonyl group, an ethoxycarbonyl group, a (4-hydroxybutoxy) carbonyl group, and a succinic anhydride group, and a methoxycarbonyl group is particularly preferable.

Preferred examples of X ₁ and X ₂ which are substituted amino groups having 1 to 12 carbon atoms include monomethylamino group, dimethylamino group, monoethylamino group, diethylamino group, monoisopropylamino group, diisopropylamino group, monophenylamino Group, diphenylamino group, bis (trimethylsilyl) amino group, morpholinyl group. Of these, a more preferred substituent is a dimethylamino group.

Preferable specific examples of X ₁ and X ₂ which are halogen are fluorine, chlorine and bromine. Of these, a more preferred substituent is chlorine.

Among the specific examples of the substituents X ₁ and X ₂ , particularly preferable substituents are a methyl group, an ethyl group, a benzyl group, an isopropoxy group, and a chloro group, and particularly preferably a benzyl group and a chloro group. It is.

(3) Specific examples of metal complexes Specific preferred examples of the metal complexes of the present invention include the following zirconium complexes. These are examples, and it is obvious that the present invention is not limited to these.

3. Synthesis of Diol Compound and Synthesis of Metal Complex Obtained by Reaction of Diol (1) Basic Synthesis Route The synthesis of the diol compound in the present invention can be carried out by any diol synthesis route.

That is, specific examples include reduction of ketone, coupling of ketone, oxidation of olefin, and hydroxylation of epoxide. Specific diol synthesis examples are described in detail as ligand synthesis examples in the examples.
The synthesis route of the metal complex obtained by reacting the diol can be arbitrarily determined from the structure of the target compound. Specific examples include a route for reacting the diol compound as a raw material with a complex precursor, and a raw material. A route in which a complex precursor is reacted after deprotonation of a diol compound is mentioned.

(2) Complex Precursor The complex precursor which is a group 4-10 transition metal compound in the present invention is preferably a group 4-6 transition metal complex, and particularly preferably a group 4 transition metal complex. .
Preferred examples are titanium halides such as titanium tetrachloride, titanium trichloride, titanium tetrabromide, titanium tetraiodide, tetrakis (dimethylamido) titanium, dichlorobis (dimethylamido) titanium, trichloro (dimethylamido) titanium, tetrakis Amido titanium such as (diethylamido) titanium, tetra (isopropoxo) titanium, tetra (n-butoxo) titanium, dichloro (diisopropoxo) titanium, trichloro (isopropoxo) titanium, etc., dichlorodimethyltitanium, diisopropoxo (dimethyl) titanium, Alkyl titanium such as trichloro (methyl) titanium and tetrabenzyltitanium, and compounds obtained by changing titanium of each of the above compounds to zirconium and hafnium.
More preferably, titanium tetrachloride, zirconium tetrachloride, hafnium tetrachloride, tetrakis (dimethylamido) titanium, tetrakis (dimethylamido) zirconium, tetrakis (dimethylamido) hafnium, tetraisopropoxytitanium, tetraisopropoxyzirconium, tetra Isopropoxohafnium, tetrabenzylzirconium and tetrabenzylhafnium are preferable, and titanium tetrachloride, zirconium tetrachloride, hafnium tetrachloride, tetrabenzylzirconium and tetrabenzylhafnium are particularly preferable.

(3) Reaction with Complex Precursor The amount of the complex precursor used in the present invention is usually 0.5 to 3 mol, preferably 1 mol to 1 mol of the diol compound represented by the general formula (1) or (2). Is in the range of 0.7 to 1.5 moles.
The complex synthesis reaction may be performed in a reactor used for copolymerization with an α-olefin, or may be performed in a container separate from the reactor. After complex formation, the metal complex may be isolated and extracted and used as a catalyst, or may be used as a catalyst without isolation. Furthermore, it can be carried out in the presence of a carrier described later.

4). Olefin Polymerization Catalyst The metal complex obtained by reacting the diol of the present invention forms an olefin polymerization catalyst component, and the catalyst component can be used as an olefin polymerization catalyst. For example, it is preferably used as an olefin polymerization catalyst described below, which contains the metal complex as component (A).

(1) Components of Olefin Polymerization Catalyst The olefin polymerization catalyst of the present invention includes the following (A), (B) and optionally (C) component.
Component (A): Metal complex obtained by reacting the diol compound represented by formula (1) or (2) or metal complex represented by formula (3) or (4) Component (B): Component (A ) Or an ion-exchange layered silicate component (C): an organoaluminum compound

(2) About each component a) Component (A)
Component (A) is a metal complex obtained by reacting a diol compound represented by the general formula (1) or (2) or a metal complex represented by the general formula (3) or (4). More than one species may be used.

B) Component (B)
The component (B) is a compound or ion-exchange layered silicate that reacts with the component (A) to form an ion pair.

An organic aluminum oxy compound is mentioned as one of the components (B). The organoaluminum oxy compound has Al—O—Al bonds in the molecule, and the number of bonds is usually in the range of 1 to 100, preferably 1 to 50. Such an organoaluminum oxy compound is usually a product obtained by reacting an organoaluminum compound with water.
The reaction between organoaluminum and water is usually carried out in an inert hydrocarbon (solvent). As the inert hydrocarbon, aliphatic hydrocarbons such as pentane, hexane, heptane, cyclohexane, methylcyclohexane, benzene, toluene and xylene, alicyclic hydrocarbons and aromatic hydrocarbons can be used. Preference is given to using aromatic hydrocarbons.

As the organoaluminum compound used for the preparation of the organoaluminum oxy compound, any of the compounds represented by the following general formula can be used, but trialkylaluminum is preferably used.
(R ₁ ) _t Al (X ₃ ) _(3-t)
(In the general formula, R ₁ represents a hydrocarbon group such as an alkyl group, alkenyl group, aryl group or aralkyl group having 1 to 18 carbon atoms, preferably 1 to 12 carbon atoms, and X ₃ represents a hydrogen atom or a halogen atom. T represents an integer of 1 ≦ t ≦ 3.)
The alkyl group of the trialkylaluminum may be any of methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, pentyl group, hexyl group, octyl group, decyl group, dodecyl group, etc. An isobutyl group is preferable, and a methyl group is particularly preferable. Two or more of the above organoaluminum compounds can be mixed and used.

The reaction ratio (water / Al molar ratio) between water and the organoaluminum compound is preferably 0.25 / 1 to 1.2 / 1, particularly preferably 0.5 / 1 to 1/1, and the reaction temperature is Usually, it is -70-100 degreeC, Preferably it exists in the range of -20-20 degreeC. The reaction time is usually selected in the range of 5 minutes to 24 hours, preferably 10 minutes to 5 hours. As water required for the reaction, not only mere water but also crystal water contained in copper sulfate hydrate, aluminum sulfate hydrate and the like and components capable of generating water in the reaction system can be used.
Of the organoaluminum oxy compounds described above, those obtained by reacting alkylaluminum with water are usually called aluminoxanes, particularly methylaluminoxane (including those substantially consisting of methylaluminoxane (MAO)). Is suitable as an organoaluminum oxy compound.
Of course, as the organoaluminum oxy compound, two or more of the above organoaluminum oxy compounds can be used in combination, and a solution in which the organoaluminum oxy compound is dissolved or dispersed in the above-described inert hydrocarbon solvent. You may use.

  Other specific examples of the component (B) include borane compounds and borate compounds. More specifically, the borane compound is represented by triphenylborane, tri (o-tolyl) borane, tri (p-tolyl) borane, tri (m-tolyl) borane, tri (o-fluorophenyl) borane, tris ( p-fluorophenyl) borane, tris (m-fluorophenyl) borane, tris (2,5-difluorophenyl) borane, tris (3,5-difluorophenyl) borane, tris (4-trifluoromethylphenyl) borane, tris (3,5-ditrifluoromethylphenyl) borane, tris (2,6-ditrifluoromethylphenyl) borane, tris (pentafluorophenyl) borane, tris (perfluoronaphthyl) borane, tris (perfluorobiphenyl) borane, tris (Perfluoroanthryl) borane, Tris (Perful Robinafuchiru) such as borane and the like.

  Among these, tris (3,5-ditrifluoromethylphenyl) borane, tris (2,6-ditrifluoromethylphenyl) borane, tris (pentafluorophenyl) borane, tris (perfluoronaphthyl) borane, tris (perfluoro) Biphenyl) borane, tris (perfluoroanthryl) borane, and tris (perfluorobinaphthyl) borane are more preferred, and tris (2,6-ditrifluoromethylphenyl) borane, tris (pentafluorophenyl) borane, tris ( Perfluoronaphthyl) borane and tris (perfluorobiphenyl) borane are exemplified as preferred compounds.

When the borate compound is specifically represented, the first example is a compound represented by the following general formula.
[L1-H] ⁺ [B (R2) (R3) (X4) (X5)] ⁻
In the general formula, L1 is a neutral Lewis base, H is a hydrogen atom, and [L1-H] represents a Bronsted acid such as ammonium, anilinium, or phosphonium.
Examples of ammonium include trialkylammonium such as trimethylammonium, triethylammonium, tripropylammonium, tributylammonium, and tri (n-butyl) ammonium, and dialkylammonium such as di (n-propyl) ammonium and dicyclohexylammonium.
Examples of anilinium include N, N-dialkylanilinium such as N, N-dimethylanilinium, N, N-diethylanilinium, N, N-2,4,6-pentamethylanilinium.
Furthermore, examples of the phosphonium include triarylphosphonium such as triphenylphosphonium, tributylphosphonium, tri (methylphenyl) phosphonium, tri (dimethylphenyl) phosphonium, and trialkylphosphonium.

  In the general formula, R2 and R3 are the same or different aromatic or substituted aromatic hydrocarbon groups containing 6 to 20, preferably 6 to 16, carbon atoms, and may be connected to each other by a bridging group. As the substituent of the substituted aromatic hydrocarbon group, an alkyl group represented by a methyl group, an ethyl group, a propyl group, an isopropyl group, or a halogen such as fluorine, chlorine, bromine, or iodine is preferable. Further, X4 and X5 are a hydride group, a halide group, a hydrocarbon group containing 1 to 20 carbon atoms, a substituted hydrocarbon group containing 1 to 20 carbon atoms in which one or more hydrogen atoms are substituted by halogen atoms. It is.

  Specific examples of the compound represented by the above general formula include tributylammonium tetra (pentafluorophenyl) borate, tributylammonium tetra (2,6-ditrifluoromethylphenyl) borate, tributylammonium tetra (3,5-ditrifluoromethyl). Phenyl) borate, tributylammonium tetra (2,6-difluorophenyl) borate, tributylammonium tetra (perfluoronaphthyl) borate, dimethylanilinium tetra (pentafluorophenyl) borate, dimethylanilinium tetra (2,6-ditrifluoromethyl) Phenyl) borate, dimethylanilinium tetra (3,5-ditrifluoromethylphenyl) borate, dimethylanilinium tetra (2,6-difluorophenyl) borate , Dimethylanilinium tetra (perfluoronaphthyl) borate, triphenylphosphonium tetra (pentafluorophenyl) borate, triphenylphosphonium tetra (2,6-ditrifluoromethylphenyl) borate, triphenylphosphonium tetra (3,5- Ditrifluoromethylphenyl) borate, triphenylphosphonium tetra (2,6-difluorophenyl) borate, triphenylphosphonium tetra (perfluoronaphthyl) borate, trimethylammonium tetra (2,6-ditrifluoromethylphenyl) borate, triethylammonium tetra (Pentafluorophenyl) borate, triethylammonium tetra (2,6-ditrifluoromethylphenyl) borate, triethylammoni Mutetra (perfluoronaphthyl) borate, tripropylammonium tetra (pentafluorophenyl) borate, tripropylammonium tetra (2,6-ditrifluoromethylphenyl) borate, tripropylammonium tetra (perfluoronaphthyl) borate, tripropylammonium tetra Examples thereof include (pentafluorophenyl) borate and dicyclohexylammonium tetraphenylborate.

  Among these, tributylammonium tetra (pentafluorophenyl) borate, tributylammonium tetra (2,6-ditrifluoromethylphenyl) borate, tributylammonium tetra (3,5-ditrifluoromethylphenyl) borate, tributylammonium tetra (perfluoro) Naphthyl) borate, dimethylanilinium tetra (pentafluorophenyl) borate, dimethylaniliniumtetra (2,6-ditrifluoromethylphenyl) borate, dimethylaniliniumtetra (3,5-ditrifluoromethylphenyl) borate, dimethylanilinium Tetra (perfluoronaphthyl) borate is preferred.

Moreover, the 2nd example of a borate compound is represented by the following general formula.
[L2] ⁺ [B (R2) (R3) (X4) (X5)] ⁻
In the general formula, L2 is carbo cation, methyl cation, ethyl cation, propyl cation, isopropyl cation, butyl cation, isobutyl cation, tert-butyl cation, pentyl cation, tropinium cation, benzyl cation, trityl cation, sodium cation, proton. Etc. R2, R3, X4 and X5 are the same as defined in the general formula in paragraph 0072 above.

Specific examples of the compound include trityl tetraphenyl borate, trityl tetra (o-tolyl) borate, trityl tetra (p-tolyl) borate, trityl tetra (m-tolyl) borate, trityl tetra (o-fluorophenyl) borate, Trityltetra (p-fluorophenyl) borate, trityltetra (m-fluorophenyl) borate, trityltetra (3,5-difluorophenyl) borate, trityltetra (pentafluorophenyl) borate, trityltetra (2,6-ditrifluoro) Methylphenyl) borate, trityltetra (3,5-ditrifluoromethylphenyl) borate, trityltetra (perfluoronaphthyl) borate, tropiniumtetraphenylborate, tropiniumtetra (o-tolyl) Rate, tropinium tetra (p-tolyl) borate, tropinium tetra (m-tolyl) borate, tropinium tetra (o-fluorophenyl) borate, tropinium tetra (p-fluorophenyl) borate, tropinium tetra (m- Fluorophenyl) borate, tropinium tetra (3,5-difluorophenyl) borate, tropinium tetra (pentafluorophenyl) borate, tropinium tetra (2,6-ditrifluoromethylphenyl) borate, tropinium tetra (3,5 - ditrifluoromethylphenyl) borate, tropicity tetra (perfluoro-naphthyl) _{borate, NaBPh 4, NaB (o-} CH 3 -Ph) 4, NaB (p-CH 3 -Ph) 4, NaB (m-CH 3 - Ph) ₄ , Na _{B (o-F-Ph)} 4, NaB (p-F-Ph) 4, NaB (m-F-Ph) 4, NaB (3,5-F 2 -Ph) 4, NaB (C 6 F 5) _{4, NaB (2,6- (CF 3} ) 2 -Ph) 4, NaB (3,5- (CF 3) 2 -Ph) 4, NaB (C 10 F 7) 4, HBPh 4 · 2 diethyl ether, _{HB (3,5-F 2 -Ph)} 4 · 2 diethyl _{ether, HB (C 6 F 5)} 4 · 2 diethyl _{ether, HB (2,6- (CF 3)} 2 -Ph) 4 · 2 diethyl ether, HB (3,5- (CF ₃ ) ₂ -Ph) ₄ · 2 diethyl ether and HB (C ₁₀ H ₇ ) ₄ · 2 diethyl ether can be exemplified.

Among these, trityltetra (pentafluorophenyl) borate, trityltetra (2,6-ditrifluoromethylphenyl) borate, trityltetra (3,5-ditrifluoromethylphenyl) borate, trityltetra (perfluoronaphthyl) borate, Tropinium tetra (pentafluorophenyl) borate, tropinium tetra (2,6-ditrifluoromethylphenyl) borate, tropinium tetra (3,5-ditrifluoromethylphenyl) borate, tropinium tetra (perfluoronaphthyl) borate, _{NaB (C 6 F 5) 4} , NaB (2,6- (CF 3) 2 -Ph) 4, NaB (3,5- (CF 3) 2 -Ph) 4, NaB (C 10 F 7) 4, _{HB (C 6 F 5) 4} · 2 diethyl ether _{, HB (2,6- (CF 3)} 2 -Ph) 4 · 2 diethyl _{ether, HB (3,5- (CF 3)} 2 -Ph) 4 · 2 diethyl _{ether, HB (C 10 H 7)} 4 · 2 diethyl ether is preferred.

More preferably, among these, trityltetra (pentafluorophenyl) borate, trityltetra (2,6-ditrifluoromethylphenyl) borate, tropiniumtetra (pentafluorophenyl) borate, tropiniumtetra (2,6-ditrifluoro) Methylphenyl) borate, NaB (C ₆ F ₅ ) ₄ , NaB (2,6- (CF ₃ ) ₂ -Ph) ₄ , HB (C ₆ F ₅ ) ₄ · 2 diethyl ether, HB (2,6- ( _{CF 3) 2 -Ph) 4 ·} 2 diethyl _{ether, HB (3,5- (CF 3)} 2 -Ph) 4 · 2 diethyl _{ether, HB (C 10 H 7) 4} · 2 diethyl ether.

Furthermore, an ion exchange layered silicate is mentioned as a specific example of a component (B). An ion-exchange layered silicate (hereinafter, sometimes simply referred to as “silicate”) has a crystal structure in which surfaces formed by ionic bonds and the like are stacked in parallel with each other and have a binding force. Refers to a silicate compound in which the ions to be exchanged are exchangeable. Various known silicates are known, and are specifically described in Shiramizu Haruo "Clay Mineralogy" Asakura Shoten (1995).
In the present invention, those preferably used as the component (B) belong to the smectite group, and specific examples include montmorillonite, sauconite, beidellite, nontronite, saponite, hectorite, and stevensite. Among these, montmorillonite is preferable from the viewpoint of increasing the polymerization activity and molecular weight of the copolymer portion.

Most silicates are naturally produced mainly as a main component of clay minerals, and therefore often contain impurities (such as quartz and cristobalite) other than ion-exchanged layered silicates. Hybrids may be contained in the smectite silicate.
The silicate may be subjected to acid treatment and / or salt treatment. In the treatment, the corresponding acid and base may be mixed to produce a salt in the reaction system.

As the component (B), a mixture of the organoaluminum oxy compound and a borane compound, a borate compound, or an ion-exchange layered silicate can be used. Furthermore, each may be used independently and 2 or more types may be used.

C) Component (C)
An example of the organoaluminum compound used as the component (C) is represented by the following general formula.
Al (R4) _a X _(3-a)
In the general formula, R4 represents a hydrocarbon group having 1 to 20 carbon atoms, X represents hydrogen, halogen, an alkoxy group, or a siloxy group, and a represents a number greater than 0 and 3 or less.
Specific examples of the organoaluminum compound represented by the general formula include trialkylaluminum such as trimethylaluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum, halogen or alkoxy such as diethylaluminum monochloride, diethylaluminum monomethoxide An alkyl aluminum is mentioned.

  Of these, triisobutylaluminum is preferred. Two or more of the above organoaluminum compounds may be used in combination. Further, the above aluminum compound may be modified with alcohol, phenol or the like. Examples of these modifiers include methanol, ethanol, 1-propanol, isopropanol, butanol, phenol, 2,6-dimethylphenol, 2,6-di-t-butylphenol, and preferable specific examples include 2,6. -Dimethylphenol, 2,6-di-t-butylphenol.

(3) Catalyst preparation method In the preparation method of the catalyst for olefin polymerization according to the present invention, the method of contacting the components (A) and (B) and, if necessary, (C) is not particularly limited. The following methods can be exemplified.

(I) Method of adding component (C) after contacting component (A) and component (B) (ii) After contacting component (A) and component (C), component (B) (Iii) Method of adding component (A) after contacting component (B) and component (C) (iv) Contacting each component (A), (B), (C) simultaneously How to make.
Furthermore, different types of components may be used as a mixture in each component, or the components may be contacted in different orders. This contact may be performed not only at the time of catalyst preparation but also at the time of prepolymerization with olefin or at the time of polymerization of olefin.
Alternatively, the component (B) and the component (C) may be contacted, and then the mixture of the component (A) and the component (C) may be added, and the components may be divided and brought into contact with each component.
The contact of each of the components (A), (B), and (C) is preferably performed in an inert hydrocarbon solvent such as pentane, hexane, heptane, toluene, and xylene in an inert gas such as nitrogen. The contact can be performed at a temperature between −20 ° C. and the boiling point of the solvent, and is preferably performed at a temperature between room temperature and the boiling point of the solvent.

5. Polymerization Method (1) Monomer The above-mentioned catalyst for olefin polymerization can be used for homopolymerization of α-olefins or copolymerization of two or more types of α-olefins.
The α-olefins include those having 2 to 30 carbon atoms, preferably 2 to 8 carbon atoms, specifically, ethylene, propylene, 1-butene, 1-hexene, 1-octene, 4-methyl-1 -Examples include pentene. More preferably, ethylene and propylene are mentioned.
α-olefins can also be copolymerized with two or more α-olefins. The copolymerization may be any of alternating copolymerization, random copolymerization, and block copolymerization. Of course, it is also possible to use a small amount of a comonomer other than α-olefin. In this case, styrenes such as styrene, 4-methylstyrene, 4-dimethylaminostyrene, 1,4-butadiene, 1,5-hexadiene, Examples include compounds having polymerizable double bonds such as dienes such as 1,4-hexadiene and 1,7-octadiene, cyclic compounds such as norbornene and cyclopentene, and oxygen-containing compounds such as hexenol, hexenoic acid and methyl octenoate. be able to.

(2) Polymerization method In the present invention, the polymerization reaction can be carried out in the presence of the aforementioned supported catalyst, preferably by slurry polymerization or gas phase polymerization. In the case of slurry polymerization, with substantially no oxygen, water, etc., aliphatic hydrocarbons such as isobutane, hexane and heptane, aromatic hydrocarbons such as benzene, toluene and xylene, and alicyclic rings such as cyclohexane and methylcyclohexane Ethylene or the like is polymerized in the presence or absence of an inert hydrocarbon solvent selected from group hydrocarbons. Needless to say, liquid monomers such as liquid ethylene and liquid propylene can also be used as the solvent.
In the case of gas phase polymerization, ethylene or the like is polymerized in a reactor in which a gas stream of ethylene or comonomer is introduced, circulated or circulated. In the present invention, more preferred polymerization is gas phase polymerization.

  The polymerization conditions are such that the temperature is 0 to 250 ° C., preferably 20 to 110 ° C., more preferably 60 to 100 ° C., and the pressure is normal pressure to 10 MPa, preferably normal pressure to 4 MPa, more preferably 0.5 to 2 MPa. The polymerization time is usually 5 minutes to 10 hours, preferably 5 minutes to 5 hours.

Even if a component for removing water, a so-called scavenger, is added to the polymerization system, it can be carried out without any trouble. Such scavengers include organoaluminum compounds such as trimethylaluminum, triethylaluminum and triisobutylaluminum, the organoaluminum oxy compounds, modified organoaluminum compounds containing branched alkyl, organozinc compounds such as diethyl zinc and dibutyl zinc, diethyl Organic magnesium compounds such as magnesium, dibutylmagnesium and ethylbutylmagnesium, and grinier compounds such as ethylmagnesium chloride and butylmagnesium chloride are used.
Of these, triethylaluminum, triisobutylaluminum, and ethylbutylmagnesium are preferable, and triethylaluminum is particularly preferable.

  The present invention can also be applied to a multistage polymerization system having two or more stages having different polymerization conditions without any trouble.

  In the following, the present invention will be specifically described by way of examples to demonstrate the rationality and significance of the configuration of the present invention and the superiority over the prior art.

1. Evaluation method (1) Molecular weight and molecular weight distribution (Mw, Mn)
(Measurement conditions) Model used: 150C manufactured by Waters Inc. Detector: MIRAN1A / IR detector manufactured by FOXBORO (measurement wavelength: 3.42 μm) Measurement temperature: 140 ° C. Solvent: Orthodichlorobenzene (ODCB) Column: AD806M manufactured by Showa Denko KK / S (3) Flow rate: 1.0 mL / min Injection volume: 0.2 mL
(Preparation of sample) A sample was prepared by preparing a 1 mg / mL solution using ODCB (containing 0.5 mg / mL BHT (2,6-di-t-butyl-4-methylphenol)) at 140 ° C. It took about 1 hour to dissolve.
(Calculation of molecular weight) The standard polystyrene method was used, and the conversion from the retention capacity to the molecular weight was performed using a calibration curve prepared in advance with standard polystyrene. Standard polystyrenes used are brands manufactured by Tosoh Corporation, and are F380, F288, F128, F80, F40, F20, F10, F4, F1, A5000, A2500, and A1000. A calibration curve was prepared by injecting 0.2 mL of a solution dissolved in ODCB (containing 0.5 mg / mL BHT) so that each would be 0.5 mg / mL. The calibration curve used was a cubic equation obtained by approximation by the least square method. The following numerical values were used for the viscosity formula [η] = K × M ^α used for conversion to molecular weight.
PS: K = 1.38 × 10 ⁻⁴ , α = 0.7
PE: K = 3.92 × 10 ⁻⁴ , α = 0.733
PP: K = 1.03 × 10 ⁻⁴ , α = 0.78

(2) Melting point (Tm)
Using a DSC6200 differential scanning calorimeter manufactured by Seiko Instruments Inc., the sheet-like sample piece was packed in a 5 mg aluminum pan, heated from room temperature to 200 ° C. at a heating rate of 100 ° C./min, and held for 5 minutes. Thereafter, the temperature was lowered to 20 ° C. at 10 ° C./min for crystallization, and then the temperature was raised to 200 ° C. at 10 ° C./min to obtain a melting curve.
The peak top temperature of the main endothermic peak in the final temperature increase step performed to obtain the melting curve was defined as the melting point Tm, and the peak area of the peak was defined as ΔHm.
(3) MFR and FR
The MFR was measured at 190 ° C. and a 2.16 kg load according to JIS K6760. MFR _{10 kg} was similarly measured under the conditions of 190 ° C. and 10 kg load.

[Synthesis Example 1] Synthesis of Diol Compound 1 A synthesis route of Diol compounds 1 to 3 in the present invention is shown below. Unless otherwise specified in the following synthesis examples, the operation was performed in a purified nitrogen atmosphere, and the solvent used was dehydrated and deoxygenated.

２−ブロモ−６−フルオロフェノール（２３．０ｇ，１２０ｍｍｏｌ）、フェニルホウ酸（２９．３ｇ，２４０ｍｍｏｌ）、酢酸銅ＩＩ（２１．８ｇ，１２０ｍｍｏｌ）、トリエチルアミン（６０．６ｇ，６００ｍｍｏｌ）、モレキュラシーブス４Ａ（１０．０ｇ）に塩化メチレン（２００ｍＬ）を加え、１５℃で４８時間撹拌した。反応後、ろ過により回収した濾液と、ろ過により分取された固体を酢酸エチル（１５０ｍＬ×３回）で抽出した溶液を混合し、減圧下で濃縮した。
カラムクロマトグラフィー（ペンタン）で精製することにより、無色オイル状の化合物５を得た。収量６．４ｇで収率２０％であった。 (Synthesis of Intermediate Compound 5)

2-bromo-6-fluorophenol (23.0 g, 120 mmol), phenylboric acid (29.3 g, 240 mmol), copper acetate II (21.8 g, 120 mmol), triethylamine (60.6 g, 600 mmol), molecular sieves 4A ( Methylene chloride (200 mL) was added to 10.0 g) and stirred at 15 ° C. for 48 hours. After the reaction, the filtrate collected by filtration and a solution obtained by extracting the solid separated by filtration with ethyl acetate (150 mL × 3 times) were mixed and concentrated under reduced pressure.
By purification by column chromatography (pentane), a colorless oily compound 5 was obtained. The yield was 6.4 g and the yield was 20%.

化合物５（６．４ｇ，２３．９ｍｍｏｌ）のトルエン（６０ｍＬ）溶液に、オルソトリルホスフィン（２．９１ｇ，９．５６ｍｍｏｌ）、トリス（ジベンジリデンアセトン）ジパラジウム（４．３８ｇ，４．７８ｍｍｏｌ）、ビニルトリブチルスズ（８．３０ｇ，２６．２ｍｍｏｌ）を１５℃でそれぞれ加えた後、１１０℃で１６時間撹拌した。反応後、１５℃に冷却し、１規定の塩酸（２００ｍＬ）を加えてクエンチした。反応液を酢酸エチル（１５０ｍＬ×３回）で抽出し、硫酸ナトリウムで乾燥した。濃縮後、カラムクロマトグラフィー（ペンタン）で精製することにより、無色オイル状の化合物６を得た。収量１０．０ｇであった。 (Synthesis of Intermediate Compound 6)

To a toluene (60 mL) solution of compound 5 (6.4 g, 23.9 mmol), orthotolylphosphine (2.91 g, 9.56 mmol), tris (dibenzylideneacetone) dipalladium (4.38 g, 4.78 mmol), Vinyltributyltin (8.30 g, 26.2 mmol) was added at 15 ° C., and the mixture was stirred at 110 ° C. for 16 hours. After the reaction, the mixture was cooled to 15 ° C. and quenched by adding 1N hydrochloric acid (200 mL). The reaction solution was extracted with ethyl acetate (150 mL × 3 times) and dried over sodium sulfate. After concentration, purification by column chromatography (pentane) gave colorless oily compound 6. The yield was 10.0 g.

(１，３−ビス(２，４，６−トリメチルフェニル)−２−イミダゾリジニリデン)ジクロロ(フェニルメチレン)(トリシクロヘキシルホスフィン)ルテニウム（０．７３５ｇ，１．１７ｍｍｏｌ）の塩化メチレン（５０ｍＬ）溶液を、化合物６（１０．０ｇ）に１５℃で加え、１２時間還流した。反応後、室温まで冷却した後、減圧下で濃縮し、カラムクロマトグラフィー（ペンタン／酢酸エチル＝２０／１）で精製することにより、白色固体の化合物７を得た。収量３．０ｇで収率６４％であった。 (Synthesis of Intermediate Compound 7)

(1,3-bis (2,4,6-trimethylphenyl) -2-imidazolidinylidene) dichloro (phenylmethylene) (tricyclohexylphosphine) ruthenium (0.735 g, 1.17 mmol) in methylene chloride (50 mL) Was added to compound 6 (10.0 g) at 15 ° C. and refluxed for 12 hours. After the reaction, the mixture was cooled to room temperature, concentrated under reduced pressure, and purified by column chromatography (pentane / ethyl acetate = 20/1) to obtain a white solid compound 7. The yield was 64% with a yield of 3.0 g.

化合物７（３．０ｇ，７．５０ｍｍｏｌ）のターシャリーブタノール（６０ｍＬ）及びテトラヒドロフラン（２０ｍＬ）、水（６ｍＬ）混合溶液に、４−メチルモルホリンＮ−オキシド（１．９３ｇ，１６．５ｍｍｏｌ）及び四酸化オスミウム（０．０１９０ｇ，０．０７５ｍｍｏｌ）を１５℃で加え、室温で１６時間撹拌した。この反応液に、飽和亜硫酸水素ナトリウム水溶液（１００ｍＬ）を加え、室温で３０分間撹拌した。反応液を酢酸エチル（１００ｍＬ×３回）で抽出し、飽和食塩水で洗浄した後、硫酸ナトリウムで乾燥した。濃縮後、カラムクロマトグラフィー（ペンタン／酢酸エチル＝５／１）で精製することにより、白色固体の化合物１を得た。収量２．７ｇで収率８３％であった。
¹H NMR (CDCl₃, ppm): 7.31 (m, 4 H), 7.09 (dd, J = 7.6 Hz, 2 H), 7.02 (dd, J = 3.2, 10.8 Hz, 2 H), 6.94 (m, 6 H), 6.83 (d, J = 8.0 Hz, 2 H), 4.66 (s, 2 H), 2.96 (s, 2 H). (Synthesis of Compound 1)

To a mixed solution of compound 7 (3.0 g, 7.50 mmol) in tertiary butanol (60 mL) and tetrahydrofuran (20 mL), water (6 mL), 4-methylmorpholine N-oxide (1.93 g, 16.5 mmol) and tetra Osmium oxide (0.0190 g, 0.075 mmol) was added at 15 ° C., and the mixture was stirred at room temperature for 16 hours. A saturated aqueous sodium hydrogen sulfite solution (100 mL) was added to the reaction solution, and the mixture was stirred at room temperature for 30 minutes. The reaction mixture was extracted with ethyl acetate (100 mL × 3 times), washed with saturated brine, and dried over sodium sulfate. After concentration, purification by column chromatography (pentane / ethyl acetate = 5/1) gave Compound 1 as a white solid. The yield was 2.7 g and the yield was 83%.
¹ H NMR (CDCl ₃ , ppm): 7.31 (m, 4 H), 7.09 (dd, J = 7.6 Hz, 2 H), 7.02 (dd, J = 3.2, 10.8 Hz, 2 H), 6.94 (m, 6 H), 6.83 (d, J = 8.0 Hz, 2 H), 4.66 (s, 2 H), 2.96 (s, 2 H).

２−ブロモ−４−ターシャリーブチル−６−（３’，５’−ジターシャリーブチルフェニル）フェノール（１５．０ｇ，３５．９ｍｍｏｌ）、フェニルホウ酸（８．７５ｇ，７１．８ｍｍｏｌ）、酢酸銅ＩＩ（６．５３ｇ，３５．９ｍｍｏｌ）、トリエチルアミン（２５．０ｍＬ，１７９ｍｍｏｌ）、モレキュラシーブス４Ａ（１０ｇ）に塩化メチレン（２００ｍＬ）を加え、１５℃で４８時間撹拌した。反応後、氷水（２０ｍＬ）を加え、減圧で濃縮した。酢酸エチル（１００ｍＬ×３回）で抽出し、硫酸ナトリウムで乾燥した後、カラムクロマトグラフィー（ペンタン／酢酸エチル＝１００／１）で精製することにより、白色固体の化合物９を得た。収量６．３ｇで収率３６％であった。 [Synthesis Example 2] Synthesis of Diol Compound 2 (Synthesis of Intermediate Compound 9)

2-bromo-4-tertiarybutyl-6- (3 ′, 5′-ditertiarybutylphenyl) phenol (15.0 g, 35.9 mmol), phenylboric acid (8.75 g, 71.8 mmol), copper acetate II (6.53 g, 35.9 mmol), triethylamine (25.0 mL, 179 mmol), molecular sieves 4A (10 g) were added with methylene chloride (200 mL), and the mixture was stirred at 15 ° C. for 48 hours. After the reaction, ice water (20 mL) was added and the mixture was concentrated under reduced pressure. Extraction with ethyl acetate (100 mL × 3 times), drying over sodium sulfate, and purification by column chromatography (pentane / ethyl acetate = 100/1) gave Compound 9 as a white solid. The yield was 6.3 g and the yield was 36%.

化合物９（３．０ｇ，６．０４ｍｍｏｌ）のトルエン（４０ｍＬ）溶液に、トリス（オルソトリル）ホスフィン（０．７４ｇ，２．４４ｍｍｏｌ）、トリス（ジベンジリデンアセトン）ジパラジウム（１．１２ｇ，１．２２ｍｍｏｌ）、ビニルトリブチルスズ（２．１２ｇ，６．６８ｍｍｏｌ）を１５℃でそれぞれ加えた後、１１０℃で１６時間撹拌した。反応後、１５℃に冷却し、１規定の塩酸（２００ｍＬ）を加えてクエンチした。反応液を酢酸エチル（１００ｍＬ×３回）で抽出し、硫酸ナトリウムで乾燥した。ろ過、濃縮後、カラムクロマトグラフィー（ペンタン）で精製することにより、無色オイル状の化合物１０を得た。収量３．５ｇであった。 (Synthesis of Intermediate Compound 10)

To a toluene (40 mL) solution of compound 9 (3.0 g, 6.04 mmol), tris (orthotolyl) phosphine (0.74 g, 2.44 mmol), tris (dibenzylideneacetone) dipalladium (1.12 g, 1.22 mmol) ) And vinyltributyltin (2.12 g, 6.68 mmol) were added at 15 ° C., and the mixture was stirred at 110 ° C. for 16 hours. After the reaction, the mixture was cooled to 15 ° C. and quenched by adding 1N hydrochloric acid (200 mL). The reaction solution was extracted with ethyl acetate (100 mL × 3 times) and dried over sodium sulfate. After filtration and concentration, colorless oily compound 10 was obtained by purification by column chromatography (pentane). The yield was 3.5 g.

(１，３−ビス(２，４，６−トリメチルフェニル)−２−イミダゾリジニリデン)ジクロロ(フェニルメチレン)(トリシクロヘキシルホスフィン)ルテニウム（０．５０ｇ，０．７９５ｍｍｏｌ）の塩化メチレン（２０ｍＬ）溶液を、化合物１０（７．０ｇ）に１５℃で加え、４８時間還流した。反応後、室温まで冷却した後、減圧下で濃縮し、カラムクロマトグラフィー（ペンタン）で精製することにより、白色固体の化合物１１を得た。収量３．５ｇで収率５０％であった。 (Synthesis of Intermediate Compound 11)

(1,3-bis (2,4,6-trimethylphenyl) -2-imidazolidinylidene) dichloro (phenylmethylene) (tricyclohexylphosphine) ruthenium (0.50 g, 0.795 mmol) in methylene chloride (20 mL) Was added to compound 10 (7.0 g) at 15 ° C. and refluxed for 48 hours. After the reaction, the reaction mixture was cooled to room temperature, concentrated under reduced pressure, and purified by column chromatography (pentane) to obtain Compound 11 as a white solid. The yield was 3.5 g and the yield was 50%.

ビス（ジヒドロキニニル）フタラジン（０．０４ｇ，０．０５０８ｍｍｏｌ）、フェリシアン化カリウム（２５．４ｇ，７６．０ｍｍｏｌ）、オスミウム（ＶＩ）酸カリウム二水和物（０．３９０ｇ，１．０６ｍｍｏｌ）、炭酸カリウム（１０．４ｇ，７６．０ｍｍｏｌ）のターシャリーブタノール（２６ｍＬ）及び水（２６ｍＬ）混合溶液に、メタンスルホンアミド（２．３９ｇ，２５．２ｍｍｏｌ）及び、化合物１１（４．０ｇ，５．０８ｍｍｏｌ）のテトラヒドロフラン（８０ｍＬ）溶液を加え、３０℃で２４時間撹拌した。この反応液に、飽和亜硫酸水素ナトリウム水溶液（１００ｍＬ）を加え、室温で１時間撹拌した。反応液を酢酸エチル（１００ｍＬ×３回）で抽出し、飽和食塩水で洗浄した後、硫酸ナトリウムで乾燥した。ろ過、濃縮後、カラムクロマトグラフィー（ペンタン／酢酸エチル＝５／１）で精製することにより、白色固体の化合物２を得た。収量３．３ｇで収率８０％であった。
¹H NMR (CDCl₃, ppm): 7.47 (d, J = 2.4 Hz, 2 H), 7.33 (d, J = 2.4 Hz, 2 H), 7.14 (t, J = 1.6 Hz, 2 H), 7.00 (d, J = 1.6 Hz, 4 H), 6.94 (dd, J = 7.6, 8.4 Hz, 4 H), 6.72 (m, 2 H), 6.46 (d, J = 7.6 Hz, 4 H), 5.19 (s, 2 H), 3.26 (br, 2 H), 1.35 (s, 18 H), 1.19 (s, 36 H). (Synthesis of Compound 2)

Bis (dihydroquininyl) phthalazine (0.04 g, 0.0508 mmol), potassium ferricyanide (25.4 g, 76.0 mmol), potassium osmium (VI) dihydrate (0.390 g, 1.06 mmol), potassium carbonate ( 10.4 g, 76.0 mmol) in a mixed solution of tertiary butanol (26 mL) and water (26 mL), methanesulfonamide (2.39 g, 25.2 mmol) and compound 11 (4.0 g, 5.08 mmol) Tetrahydrofuran (80 mL) solution was added and stirred at 30 ° C. for 24 hours. A saturated aqueous sodium hydrogen sulfite solution (100 mL) was added to the reaction solution, and the mixture was stirred at room temperature for 1 hour. The reaction mixture was extracted with ethyl acetate (100 mL × 3 times), washed with saturated brine, and dried over sodium sulfate. After filtration and concentration, purification by column chromatography (pentane / ethyl acetate = 5/1) gave Compound 2 as a white solid. The yield was 3.3 g and the yield was 80%.
¹ H NMR (CDCl ₃ , ppm): 7.47 (d, J = 2.4 Hz, 2 H), 7.33 (d, J = 2.4 Hz, 2 H), 7.14 (t, J = 1.6 Hz, 2 H), 7.00 (d, J = 1.6 Hz, 4 H), 6.94 (dd, J = 7.6, 8.4 Hz, 4 H), 6.72 (m, 2 H), 6.46 (d, J = 7.6 Hz, 4 H), 5.19 ( s, 2 H), 3.26 (br, 2 H), 1.35 (s, 18 H), 1.19 (s, 36 H).

２−ブロモ−４−ターシャリーブチル−６−（３’，５’−ジターシャリーブチルフェニル）フェノール（５．００ｇ，１２．０ｍｍｏｌ）のアセトン（５０ｍＬ）溶液に、炭酸カリウム（５．００ｇ，３６．０ｍｍｏｌ）及びイソプロピルアイオダイド（６．１２ｇ，３６．０ｍｍｏｌ）を加え、１２時間還流した。
反応後、ろ過により回収した濾液と、ろ過により分取された固体を酢酸エチル（２０ｍＬ×３回）で抽出した溶液を混合し、減圧下で濃縮した。カラムクロマトグラフィー（ペンタン）で精製することにより、白色固体の化合物１２を得た。収量３．５ｇで収率６５％であった。 [Synthesis Example 3] Synthesis of Diol Compound 3 (Synthesis of Intermediate Compound 12)

To a solution of 2-bromo-4-tertiarybutyl-6- (3 ′, 5′-ditertiarybutylphenyl) phenol (5.00 g, 12.0 mmol) in acetone (50 mL) was added potassium carbonate (5.00 g, 36 0.0 mmol) and isopropyl iodide (6.12 g, 36.0 mmol) were added and refluxed for 12 hours.
After the reaction, the filtrate collected by filtration and a solution obtained by extracting the solid separated by filtration with ethyl acetate (20 mL × 3 times) were mixed and concentrated under reduced pressure. Compound 12 was obtained as a white solid by purification by column chromatography (pentane). The yield was 3.5 g and the yield was 65%.

化合物１２（８．２ｇ，１８．３ｍｍｏｌ）のトルエン（１００ｍＬ）溶液に、トリス（オルソトリル）ホスフィン（２．２２ｇ，７．３１ｍｍｏｌ）、トリス（ジベンジリデンアセトン）ジパラジウム（３．３４ｇ，３．６５ｍｍｏｌ）、ビニルトリブチルスズ（６．３６ｇ，２０．１ｍｍｏｌ）を１５℃でそれぞれ加えた後、１１０℃で３６時間撹拌した。反応後、１５℃に冷却し、１規定の塩酸（３００ｍＬ）を加えてクエンチした。反応液を酢酸エチル（２００ｍＬ×３回）で抽出し、硫酸ナトリウムで乾燥した。ろ過、濃縮後、カラムクロマトグラフィー（ペンタン）で精製することにより、無色オイル状の化合物を得た（収量１２．０ｇ）。更に、分取ＨＰＬＣにより精製することにより、白色固体の化合物１３を得た。収量４．０ｇで収率５７％であった。 (Synthesis of Intermediate Compound 13)

To a toluene (100 mL) solution of Compound 12 (8.2 g, 18.3 mmol), tris (orthotolyl) phosphine (2.22 g, 7.31 mmol), tris (dibenzylideneacetone) dipalladium (3.34 g, 3.65 mmol). ) And vinyltributyltin (6.36 g, 20.1 mmol) were added at 15 ° C., respectively, followed by stirring at 110 ° C. for 36 hours. After the reaction, the mixture was cooled to 15 ° C. and quenched by adding 1N hydrochloric acid (300 mL). The reaction solution was extracted with ethyl acetate (200 mL × 3 times) and dried over sodium sulfate. After filtration and concentration, purification by column chromatography (pentane) gave a colorless oily compound (yield 12.0 g). Furthermore, the compound 13 of white solid was obtained by refine | purifying by preparative HPLC. The yield was 4.0 g and the yield was 57%.

(１，３−ビス(２，４，６−トリメチルフェニル)−２−イミダゾリジニリデン)ジクロロ(フェニルメチレン)(トリシクロヘキシルホスフィン)ルテニウム（０．３１ｇ，０．５０ｍｍｏｌ）の塩化メチレン（１０ｍＬ）溶液を、化合物１３（４．０ｇ）に１５℃で加え、４８時間還流した。反応後、室温まで冷却した後、減圧下で濃縮し、カラムクロマトグラフィー（ペンタン）で精製することにより、白色固体の化合物１４を得た。収量２．０ｇで収率５０％であった。 (Synthesis of Intermediate Compound 14)

(1,3-bis (2,4,6-trimethylphenyl) -2-imidazolidinylidene) dichloro (phenylmethylene) (tricyclohexylphosphine) ruthenium (0.31 g, 0.50 mmol) in methylene chloride (10 mL) To compound 13 (4.0 g) at 15 ° C. and refluxed for 48 hours. After the reaction, the reaction mixture was cooled to room temperature, concentrated under reduced pressure, and purified by column chromatography (pentane) to obtain Compound 14 as a white solid. The yield was 2.0 g and the yield was 50%.

ビス（ジヒドロキニニル）フタラジン（０．００９０ｇ，０．０１１５ｍｍｏｌ）、フェリシアン化カリウム（６．３３ｇ，１９．０ｍｍｏｌ）、オスミウム（ＶＩ）酸カリウム二水和物（０．０９６５ｇ，０．２６２ｍｍｏｌ）、炭酸カリウム（２．６２ｇ，１９．０ｍｍｏｌ）のターシャリーブタノール（６．８ｍＬ）及び水（６．８ｍＬ）混合溶液に、メタンスルホンアミド（０．００６０ｇ，６．３３ｍｍｏｌ）及び、化合物１４（１．０ｇ，１．２７ｍｍｏｌ）のテトラヒドロフラン（４０ｍＬ）溶液を加え、２５℃で２４時間撹拌した。この反応液に、飽和亜硫酸水素ナトリウム水溶液（１００ｍＬ）を加え、室温で１時間撹拌した。反応液を酢酸エチル（１００ｍＬ×３回）で抽出し、飽和食塩水で洗浄した後、硫酸ナトリウムで乾燥した。ろ過、濃縮後、カラムクロマトグラフィー（ペンタン／酢酸エチル＝５／１）で精製することにより、白色固体の化合物３を得た。収量０．８ｇで収率８０％であった。
¹H NMR (CDCl₃, ppm): 7.38 (s, 2 H), 7.30 (s, 4 H), 7.15 (s, 2 H), 7.11 (s, 2 H), 5.55 (m, 2 H), 4.60 (d, J = 4.8 Hz, 2 H), 3.70 (m, 2 H), 1.35 (s, 36 H), 1.18 (s, 18 H), 1.10 (d, J = 6.0 Hz, 6 H), 0.92 (d, J = 6.0 Hz, 6 H). (Synthesis of Compound 3)

Bis (dihydroquininyl) phthalazine (0.0090 g, 0.0115 mmol), potassium ferricyanide (6.33 g, 19.0 mmol), potassium osmium (VI) dihydrate (0.0965 g, 0.262 mmol), potassium carbonate ( To a mixed solution of 2.62 g, 19.0 mmol) of tertiary butanol (6.8 mL) and water (6.8 mL), methanesulfonamide (0.0060 g, 6.33 mmol) and compound 14 (1.0 g, 1 .27 mmol) in tetrahydrofuran (40 mL) was added, and the mixture was stirred at 25 ° C. for 24 hours. A saturated aqueous sodium hydrogen sulfite solution (100 mL) was added to the reaction solution, and the mixture was stirred at room temperature for 1 hour. The reaction mixture was extracted with ethyl acetate (100 mL × 3 times), washed with saturated brine, and dried over sodium sulfate. After filtration and concentration, purification by column chromatography (pentane / ethyl acetate = 5/1) gave Compound 3 as a white solid. The yield was 80 g with a yield of 0.8 g.
¹ H NMR (CDCl ₃ , ppm): 7.38 (s, 2 H), 7.30 (s, 4 H), 7.15 (s, 2 H), 7.11 (s, 2 H), 5.55 (m, 2 H), 4.60 (d, J = 4.8 Hz, 2 H), 3.70 (m, 2 H), 1.35 (s, 36 H), 1.18 (s, 18 H), 1.10 (d, J = 6.0 Hz, 6 H), 0.92 (d, J = 6.0 Hz, 6 H).

[Example 1]
An equimolar amount of tetrabenzylzirconium and the diol compound 1 were weighed in a 30 mL flask sufficiently purged with nitrogen, and dehydrated toluene (10 mL) was added thereto, followed by mixing and stirring at room temperature for 5 minutes to prepare a complex solution. Next, the inside of the stainless steel autoclave with an induction stirrer with an internal volume of 1.5 L was replaced with purified nitrogen, and purified toluene and MAO (2000 equivalents / Zr) were introduced into the autoclave under a purified nitrogen atmosphere (total amount 700 mL). After maintaining a predetermined polymerization temperature and an ethylene pressure of 2.0 MPa, the previously prepared complex solution was injected to initiate polymerization. During the reaction, the temperature was kept constant, and ethylene was continuously supplied so that the pressure was maintained.
After the polymerization was completed by press-fitting ethanol (10 mL), the ethylene was purged, the autoclave was cooled to room temperature, the obtained polymer was reprecipitated with ethanol (1 L), and the solid substance obtained by filtration was filtered. After washing with ethanol, it was recovered by drying under reduced pressure at 80 ° C. for 3 hours.

[Example 2, Example 3, Comparative Example 1]
Compound 2 is used in Example 2, Compound 3 is used in Example 3, and publicly known literature (paragraph 0 is used in Comparative Example 1).
N, N′-bis (3-tert-butyl-5-methoxy-2-hydroxyphenylmethyl) -N, N′-dimethylethylenediamine (Compound 4) synthesized with reference to Non-Patent Document 1) listed above in 007 A polymer was produced according to Example 1 except that was used. Table 1 summarizes the polymerization conditions and the physical property evaluation results of the obtained polymer.

[Consideration by comparison of results of Examples and Comparative Examples]
Example 1 showed a low MFR value such that the produced polyethylene did not show fluidity in a high-temperature molten state, whereas the polymer obtained in Comparative Example 1 was too fluid. This polymer fluidity is well known to have a close relationship with its molecular weight, indicating that the polyethylene obtained in this example has a high molecular weight. Further, in Examples 2 and 3, a higher Mw is obtained as compared with Comparative Example 1.
As described above, by using the metal complex of the present invention, a polymer having a higher molecular weight than that of the comparative example could be obtained. As a result, the rationality and significance of the configuration requirements in the present invention and the superiority of the present invention over the prior art are clarified.

According to the present invention, an olefin polymer having a molecular weight higher than that of a conventional metal complex can be economically produced by a metal complex that can be easily synthesized, a catalyst including the metal complex, and an olefin polymerization method. It is very useful in the industry.

Claims (8)

A diol compound represented by the following general formula (1) or (2) is selected from a halogenated zirconium, a halogenated hafnium, an amidozirconium, an amidohafnium, an alkoxozirconium, an alkoxohafnium, an alkylzirconium or an alkylhafnium. A metal complex comprising a transition metal compound .

(In General Formulas (1) and (2), Q ₁ and Q ₄ are each independently carbon substituted with a divalent hydrocarbon group having 1 to 24 carbon atoms or a silyl group having 3 to 18 carbon atoms. A substituent selected from the group consisting of a divalent hydrocarbon group having 4 to 20 carbon atoms and a divalent hydrocarbon group having 1 to 20 carbon atoms substituted with a halogen atom is represented by Q ₂ and Q ₃ , respectively. Independently from a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms substituted with a halogen atom, or a silyl group substituted with a hydrocarbon group having 1 to 20 carbon atoms T ₁ and T ₂ each independently represent a substituent selected from the group consisting of: an alkoxy group having 1 to 10 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, an acyl group having 2 to 10 carbon atoms, A substituent selected from the group consisting of an amino group or a substituted amino group having 1 to 12 carbon atoms is shown.) The metal complex according to claim 1, which is represented by the following general formula (3) or (4).

(In the general formulas (3) and (4), Q ₁ , Q ₂ , Q ₃ , Q ₄ , T ₁ and T ₂ are the same as those in the diol compound represented by the general formula (1) or (2). are the same as substituent, M represents zirconium or _hafnium, X 1, _{X 2} are each independently a hydrocarbon group having a carbon number of 1-20, an alkoxy group having 1 to 10 carbon atoms, carbon number 1 A substituent selected from the group consisting of ˜12 substituted amino groups or halogens.) The catalyst component for olefin polymerization containing the metal complex of Claim 1 or 2. A transition metal selected from a diol compound represented by the general formula (1) or (2) and zirconium halide, hafnium halide, amidozirconium, amidohafnium, alkoxozirconium, alkoxohafnium, alkylzirconium or alkylhafnium. The manufacturing method of the metal complex characterized by making a compound react.

(In General Formulas (1) and (2), Q ₁ and Q ₄ are each independently carbon substituted with a divalent hydrocarbon group having 1 to 24 carbon atoms or a silyl group having 3 to 18 carbon atoms. A substituent selected from the group consisting of a divalent hydrocarbon group having 4 to 20 carbon atoms and a divalent hydrocarbon group having 1 to 20 carbon atoms substituted with a halogen atom is represented by Q ₂ and Q ₃ , respectively. Independently from a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms substituted with a halogen atom, or a silyl group substituted with a hydrocarbon group having 1 to 20 carbon atoms T ₁ and T ₂ each independently represent a substituent selected from the group consisting of: an alkoxy group having 1 to 10 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, an acyl group having 2 to 10 carbon atoms, A substituent selected from the group consisting of an amino group or a substituted amino group having 1 to 12 carbon atoms is shown.) An olefin polymerization catalyst comprising the following components (A) and (B), and (C) as necessary.
Component (A): Metal complex according to claim 1 or 2 Component (B): Compound or ion-exchange layered silicate that reacts with component (A) to form an ion pair Component (C): Organoaluminum compound 6. The olefin polymerization catalyst according to claim 5, wherein the component (B) is an aluminoxane. The olefin polymerization catalyst according to claim 5, wherein the component (B) is a boron compound. A method for producing an olefin polymer, comprising polymerizing or copolymerizing an olefin in the presence of the polymerization catalyst according to any one of claims 5 to 7.