JP2015155397A - Biphenol compound, olefin polymerization catalyst using the same, and olefin polymer production method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a transition metal complex having a quadridentate ligand allowing inexpensive production through a simple synthetic route, which forms a polymerization catalyst with high catalytic activity enabling polymerization of a high-molecular mass olefin.

SOLUTION: The biphenol compound is represented by general formula (1). (Q₁ and Q₂ are C1-20 divalent hydrocarbon groups or the like; Q₃ to Q₈ are H, C1-20 hydrocarbon groups or the like; T₁ and T₂ are C6-20 aryloxy groups, amino groups or the like; and m and n are from 0 to 2.)

COPYRIGHT: (C)2015,JPO&INPIT

Description

  The present invention relates to a biphenol compound, a metal complex obtained 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 biphenol compound. The metal complex having such a partial structure is applied to an olefin polymerization catalyst, and the catalyst can produce an olefin polymer having a high molecular weight and is a polymerization catalyst having a high catalytic activity.

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, the complexes with tetradentate ligands reported so far have the advantage of lower production costs compared to metallocene complexes, but may have significantly lower catalytic activity or lower molecular weight of the polymer produced. Therefore, further performance improvement as a catalyst for polyolefin polymerization is demanded.

WO2002036638A2 WO2004069881A1 WO2012006230A1 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.

  The object of the present invention, that is, the problem, in view of the problems of the prior art in the transition metal complex having a tetradentate ligand described above, is high in catalytic activity, can produce a high molecular weight olefin polymer, It is to develop a transition metal complex having a tetradentate ligand that can be synthesized at a low cost by a simple synthetic route compared to a metallocene complex, and for that purpose, a ligand compound capable of forming 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 biphenoxo partial structures derived from novel biphenol compounds that have not been reported as transition metal complexes with tetradentate ligands. In addition, the present inventors have established an electronic environment and found that a biphenol 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 biphenol compound constituting the basic constitution of the present invention is novel as a tetradentate ligand because of its 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 biphenol compound which comprises the basic invention (1st invention) of this invention is a biphenol compound represented by following General formula (1).

(In General Formula (1), Q ₁ and Q ₂ are each independently 4 to 20 carbon atoms substituted with a divalent hydrocarbon group having 1 to 20 carbon atoms and a silyl group having 3 to 18 carbon atoms. And a substituent selected from the group consisting of a divalent hydrocarbon group having 1 to 20 carbon atoms substituted with a halogen atom, Q _{3 to} Q ₈ are each independently Selected from the group consisting of 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, and a silyl group substituted with a hydrocarbon group having 1 to 20 carbon atoms. T ₁ and T ₂ each independently represent 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, or 2 to 10 carbon atoms. Ester group, amino group, substituted amino group having 1 to 12 carbon atoms, substituted imino group having 1 to 12 carbon atoms A pyridyl group optionally having a substituent having 5 to 10 carbon atoms, a pyrrolidyl group optionally having a substituent having 4 to 10 carbon atoms, and a piperidyl group optionally having a substituent having 5 to 10 carbon atoms , A hydrofuryl group optionally having a substituent having 4 to 10 carbon atoms, an imidazolyl group optionally having a substituent having 4 to 10 carbon atoms, and a substituent selected from the group consisting of halogen. n independently represents an arbitrary number selected from 0, 1, and 2.)

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 biphenol compound constituting the basic constitution of the present invention is novel as a tetradentate ligand, and is characterized by the chemical, steric and electronic structure of the ligand, thereby polymerizing α-olefins. A unique catalytic function is revealed.
That is, the biphenol compound has a structure represented by the above general formula (1), and is used as a catalyst component of an olefin polymerization catalyst in the present invention. Forming a catalyst. The biphenol compound represented by the general formula (1) in the present invention has a basic feature of forming a chelate cyclic structure as a biphenoxo ligand during complex formation, and these features make the specificity of the present invention unique. It can be estimated that it will bring.
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. Thus, it is considered that the chain transfer reaction is suppressed during the polymerization of the polyolefin, and the molecular weight of the generated polyolefin is more controlled to the polymer side.

  In addition, as shown in the following general formula (2), the biphenol compound in the present invention is expected to form a metal biphenoxo structure having a five-membered ring or more as shown in the following general formula (2). It is considered that this five-membered or higher chelate exhibits high stability and contributes to improvement in performance as a complex catalyst.

(In the general formula _{(2), Q 1 ~Q 8} , T 1, T 2, m, and n are the same as substituents in biphenol compound represented by the above general formula (1), M is The metal atom selected from the group which consists of a 4-10 group transition metal is shown, X < ₁ >, X < ₂ > is respectively independently a hydrogen atom, a C1-C20 hydrocarbon group, and a C1-C10. And a substituent selected from the group consisting of an alkoxy group, 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.)

  Furthermore, the biphenoxo ligand derived from the two hydroxyl structure of biphenol has an electron donor property to the central metal at the time of complex formation as compared with the diphenoxo ligand reported so far, for example. Thus, it is considered that the chain transfer reaction including β elimination is suppressed during polyolefin polymerization, 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. From the literature, no tetradentate complex having a 2,2′-biphenoxo group derived from a 2,2′-biphenol partial structure has been reported so far.
That is, in the present invention, it is a biphenol compound capable of forming 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 biphenol compound represented by the general formula (1) described in paragraphs 0011 to 0013 is configured as the basic invention (1), and further includes the biphenol compound of the basic invention (1) and a transition metal compound of group 4 to 10 A metal complex obtained by reacting with a complex precursor, that is, a metal complex represented by the general formula (2) described above in paragraphs 0015 to 0017 is configured as the basic invention (2), and each of the inventions below is a It is intended to add ancillary requirements to the basic invention or to show embodiments 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.

  Compared with conventional metallocene complexes, it can be synthesized at a low cost by a simple synthesis route, and can be used to form a metal complex, a biphenol compound capable of forming a metal complex, a catalyst having a high catalytic activity, and a useful polyolefin polymerization catalyst and an olefin using the same. A polymerization method can be provided, and the high-molecular-weight olefin polymer can be produced by the biphenoxo ligand complex in which the unique biphenol compound of the present invention is complexed.

In addition, by comparison with the data of each Example described later and each Example and each Comparative Example, the polymerization catalyst of the present invention has a high catalytic activity, and the polymer produced according to the present invention is more than the conventional tetradentate complex polymer. Has also been demonstrated to have a high molecular weight. 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.

It is a 13C-NMR chart of the ethylene polymer produced in Example 4 of the present invention. It is a 13C-NMR chart of the propylene polymer produced in Example 12 of the present invention.

  Below, the biphenol 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. About Biphenol Compound (1) Basic Configuration The biphenol compound in the present invention is represented by the following general formula (1).

(In General Formula (1), Q ₁ and Q ₂ are each independently 4 to 20 carbon atoms substituted with a divalent hydrocarbon group having 1 to 20 carbon atoms and a silyl group having 3 to 18 carbon atoms. And a substituent selected from the group consisting of a divalent hydrocarbon group having 1 to 20 carbon atoms substituted with a halogen atom, Q _{3 to} Q ₈ are each independently Selected from the group consisting of 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, and a silyl group substituted with a hydrocarbon group having 1 to 20 carbon atoms. T ₁ and T ₂ each independently represent 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, or 2 to 10 carbon atoms. Ester group, amino group, substituted amino group having 1 to 12 carbon atoms, substituted imino group having 1 to 12 carbon atoms A pyridyl group optionally having a substituent having 5 to 10 carbon atoms, a pyrrolidyl group optionally having a substituent having 4 to 10 carbon atoms, and a piperidyl group optionally having a substituent having 5 to 10 carbon atoms , A hydrofuryl group optionally having a substituent having 4 to 10 carbon atoms, an imidazolyl group optionally having a substituent having 4 to 10 carbon atoms, and a substituent selected from the group consisting of halogen. n independently represents an arbitrary number selected from 0, 1, and 2.)

_{(2) Q 1, Q 2} Q 1, Q 2 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 ₂ 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 ₂ which are divalent hydrocarbon groups having 1 to 20 carbon atoms substituted with halogen atoms are preferably substituted with the 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 3 ~Q 8 Q} 3 ~Q 8 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 _{3 to} Q _{8 which} are a hydrocarbon group having 1 to 20 carbon atoms substituted with a halogen atom are preferably a structure in which the above hydrocarbon group having 1 to 20 carbon atoms is substituted with a halogen atom. .
Specific preferred examples include a trifluoromethyl group or a pentafluorophenyl group.

Q _{3 to} Q ₈ 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, 3,5-di-t-butylphenoxy group and 2,6-di-t-butylphenoxy group.
Among these, more preferred substituents are a phenoxy group, 3,5-di-t-butylphenoxy group or 2,6-dimethylphenoxy group, and particularly preferably a phenoxy group, 3,5-di- t-Butylphenoxy group.

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 diphenylamino group.

Preferred examples of T ₁ and T ₂ which are substituted iminos having 1 to 12 carbon atoms include phenylimino group, pentafluorophenylimino group, 2,6-dimethylphenylimino group, 3,5-di-t-butylphenyl. An imino group is mentioned.
Of these, more preferred substituents are a phenylimino group and a pentafluorophenylimino group.

Preferred specific examples of T ₁ and T ₂ which are pyridyl groups which may have a substituent having 5 to 10 carbon atoms include 2-pyridyl group, 3-pyridyl group, 2- (3-methyl) pyridyl group, 2 -(4-methyl) pyridyl group, 3- (2-methyl) pyridyl group, 3- (4-methyl) pyridyl group, 2- (4-chloromethyl) pyridyl group, 3- (4-chloromethyl) pyridyl group Is mentioned.
Among these, more preferable substituents include a 2-pyridyl group, a 3-pyridyl group, and a 2- (4-methyl) pyridyl group, and a 2-pyridyl group is particularly preferable.

Preferred specific examples of T ₁ and T ₂ which are pyrrolidyl groups which may have a substituent having 4 to 10 carbon atoms include 2-pyrrolidyl group, 3-pyrrolidyl group, 2- (1-methyl) pyrrolidyl group, 2 -(1-butyl) pyrrolidyl group, 2- (1-cyclopentenyl) pyrrolidyl group, 2- (4-methoxycarbonyl) pyrrolidyl group, 2- (5-methoxycarbonyl) pyrrolidyl group, 2- (6-methoxycarbonyl) A pyrrolidyl group is mentioned.
Among these, more preferred substituents include 2-pyrrolidyl group, 3-pyrrolidyl group, 2- (1-methyl) pyrrolidyl group, 2- (6-methoxycarbonyl) pyrrolidyl group, and particularly preferably 2-pyrrolidyl group.

Preferred examples of T ₁ and T ₂ which are piperidyl groups which may have a substituent having 5 to 10 carbon atoms include 2-piperidyl group, 3-piperidyl group, 2- (1,2,3,6- Tetrahydro) piperidyl group, 2- (1-methyl) piperidyl group, 2- (1-ethyl) piperidyl group, 2- (4-methyl) piperidyl group, 2- (5-methyl) piperidyl group, 2- (6- A methyl) piperidyl group.
Among these, more preferred substituents include 2-piperidyl group, 3-piperidyl group, 2- (1,2,3,6-tetrahydro) piperidyl group, and 2- (6-methyl) piperidyl group. Particularly preferred are 2-piperidyl group and 2- (1,2,3,6-tetrahydro) piperidyl group.

Preferred specific examples of T ₁ and T ₂ which are hydrofuryl groups which may have a substituent having 4 to 10 carbon atoms include 2-tetrahydrofuryl group, 3-tetrahydrofuryl group, 2- (5-methyl) tetrahydrofuryl. Group, 2- (5-isopropyl) tetrahydrofuryl group, 2- (5-ethyl) tetrahydrofuryl group, 2- (5-methoxy) tetrahydrofuryl group, 2- (5-acetyl) tetrahydrofuryl group, 2- (4 , 5-Benzo) tetrahydrofuryl group.
Among these, more preferred substituents include 2-tetrahydrofuryl group, 3-tetrahydrofuryl group, 2- (5-methyl) tetrahydrofuryl group, 2- (5-isopropyl) tetrahydrofuryl group, 2- (4 , 5-Benzo) tetrahydrofuryl group, particularly preferably 2-tetrahydrofuryl group, 2- (5-methyl) tetrahydrofuryl group, 2- (5-isopropyl) tetrahydrofuryl group.

Preferred examples of T ₁ and T ₂ which are imidazolyl groups optionally having 4 to 10 carbon atoms include 2-imidazolyl group, 2- (1-methyl) imidazolyl group, and 2- (1-benzyl). Examples include imidazolyl group, 2- (1-acetyl) imidazolyl group, 2- (4,5-benzo) imidazolyl group, and 2- (1-methyl-4,5-benzo) imidazolyl group.
Among these, more preferred substituents include 2-imidazolyl group, 2- (1-methyl) imidazolyl group, and 2- (4,5-benzo) imidazolyl group, and particularly preferably 2- (1 -Methyl) imidazolyl group and 2- (4,5-benzo) imidazolyl 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 biphenol compound The following biphenol compound is mentioned as a preferable specific example of the biphenol compound used for the metal complex of this invention. These are examples, and it is obvious that the present invention is not limited to these.

2. About Metal Complex (1) Basic Configuration The metal complex in the present invention is a metal complex obtained by reacting a biphenol compound and a complex precursor which is a group 4-10 transition metal compound. This is a metal complex represented by the general formula (2).

(In the general formula _{(2), Q 1 ~Q 8} , T 1, T 2, m, and n are the same as substituent in the biphenol compound represented by the general formula (1), M, 4 10 represents a metal atom selected from the group consisting of a group 10 transition metal, and X ₁ and X ₂ are each independently a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or an alkoxy having 1 to 10 carbon atoms. And a substituent selected from the group consisting of a group, 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, and a halogen.)

(2) About M 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.

_{(3) 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 isopropoxo group, and a chloro group, and particularly preferably a benzyl group and a chloro group. is there.

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

3. Synthesis of Biphenol Compound and Synthesis of Metal Complex Obtained by Reaction of Biphenol (1) Basic Synthesis Route The synthesis of the biphenol compound in the present invention can be performed by any biphenol synthesis route.

That is, as a specific example, a method of introducing a substituent using 2,2′-biphenol as a raw material can be mentioned. Specific biphenol synthesis examples are described in detail as ligand synthesis examples in the examples.
The synthesis route of the metal complex obtained by reacting biphenol can be arbitrarily determined from the structure of the target compound. Specific examples include a route for reacting a biphenol compound as a raw material with a complex precursor, and a raw material. A route for reacting a complex precursor after deprotonation of a certain biphenol 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 moles, preferably 0.7 moles with respect to 1 mole of the biphenol compound represented by the general formula (1). It is in the range of ~ 1.5 mol.
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 biphenol 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): a metal complex obtained by reacting the biphenol compound represented by the general formula (1) or a metal complex represented by the general formula (2) Component (B): reacting with the component (A) to form an ion pair Compound to be formed or ion-exchange layered silicate Component (C): Organoaluminum compound

(2) About each component a) Component (A)
Component (A) is a metal complex obtained by reacting a biphenol compound represented by general formula (1) or a metal complex represented by general formula (2), and two or more of the same or different 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. A solid dry methylaluminoxane (DMAO) obtained by distilling off the MAO solution is also suitable.
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, tris (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 (Perf Oro binaphthyl) 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 trialkyl-substituted ammonium such as trimethylammonium, triethylammonium, tripropylammonium, tri (t-butyl) ammonium and tri (n-butyl) ammonium, and dialkylammonium such as di (n-propyl) ammonium and dicyclohexylammonium Can be illustrated.
Examples of anilinium include N, N-dialkylanilinium such as N, N-dimethylanilinium, N, N-diethylanilinium, and N, N-dimethyl-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 a 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, t-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 0083 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 3) _{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 3) 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 ₃ ) 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. The smectite group silicate may contain impurities.
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 alone or in combination of two or more.

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 of compounds having a polymerizable double bond include 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. Can do.

(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 Grignard 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, Q value)
(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. The FR (flow rate ratio) was calculated from the ratio of MFR _{10 kg} and MFR (= MFR _{10 kg} / MFR), which was MFR similarly measured at 190 ° C. under a load of 10 kg.

(4) NMR
[Sample preparation]
About 250 mg of a sample formed into a film having a thickness of about 100 μm was weighed into a sample tube having an outer diameter of 10 mm, and 1.84 ml of ortho-dichlorobenzene and 0.46 ml of deuterated bromobenzene were added. After replacing the upper part of the sample tube with nitrogen, the sample tube was covered and heated and dissolved in a high-temperature bath at 130 ° C. until the sample became uniform.
[13C-NMR measurement]
The measurement was performed under the condition of NOE by gated proton decoupling using an AVANCEIII400 NMR measuring apparatus manufactured by Bruker BioSpin Corporation equipped with a cryoprobe. The flip angle of the excitation pulse was 90 °, the pulse interval was 16.3 seconds, the measurement temperature was 120 ° C., the number of integrations was 500 times or more, and the spectrum observation width was 24, 0.38.5 Hz. Assignment of 13C-NMR spectrum was performed with reference to various documents.

  The synthesis route of the biphenol compounds 1 to 9 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.

[Synthesis Example 1] Synthesis of biphenol compound 1 (synthesis of intermediate compound 1A)

  To a solution of sodium hydride (17.2 g, 428 mmol) in tetrahydrofuran (150 mL) was added a solution of 2,2′-biphenol (20.0 g, 107 mmol) in tetrahydrofuran (150 mL) at 0 ° C., and the mixture was stirred at 10 ° C. for 1 hour. . To this reaction solution, chloromethyl methyl ether (35.2 g, 428 mmol) was added at 0 ° C., and the mixture was stirred at 10 ° C. for 12 hours. After the reaction, ice water (150 mL) was added, and the reaction solution was extracted with ethyl acetate (100 mL × 3 times) and dried over sodium sulfate. After filtration and concentration, purification by column chromatography (pentane / ethyl acetate = 15/1) gave Compound 1A as a colorless oil. The yield was 51% with a yield of 15.0 g.

(Synthesis of Intermediate Compound 1B)

  To a solution of Compound 1A (8.0 g, 29.6 mmol) in tetrahydrofuran (100 mL), normal butyl lithium (35.3 mL, 88.7 mmol, 2.5 M hexane solution) was added dropwise at 0 ° C., and the mixture was stirred at 10 ° C. for 2 hours. did. To this reaction solution, 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (22.0 g, 118 mmol) was added at −78 ° C., and the mixture was stirred at 10 ° C. for 12 hours. After the reaction, ice water (150 mL) was added, and the reaction solution was extracted with ethyl acetate (100 mL × 3 times). After drying over sodium sulfate, filtration and concentration, purification by column chromatography (pentane / ethyl acetate = 10/1) gave Compound 1B as a white solid. The yield was 5.3 g and the yield was 34%.

(Synthesis of Intermediate Compound 1C)

  To a solution of compound 1B (5.3 g, 10.1 mmol), 2-bromopyridine (6.4 g, 40.4 mmol), sodium carbonate (2.2 g, 20.2 mmol) in dimethyl ether (80 mL) / water (10 mL), Tetrakis (triphenylphosphine) palladium (0.58 g, 0.51 mmol) was added at 10 ° C. and refluxed for 12 hours. After cooling to room temperature, the reaction solution was extracted with ethyl acetate (100 mL × 3 times). After washing with water (100 mL × 3 times), drying over sodium sulfate, filtration, concentration, and purification by column chromatography (ethyl acetate) gave Compound 1C as a white solid. Yield 2.2g.

(Synthesis of biphenol compound 1)

To a solution of compound 1C (2.0 g, 4.67 mmol) in ethyl acetate (100 mL) was added hydrochloric acid ethyl acetate solution (100 mL) at 0 ° C., and the mixture was stirred at 10 ° C. for 20 min. After concentration, ethyl acetate (100 mL) was added, and the mixture was washed with a saturated aqueous sodium hydrogencarbonate solution until pH 8 was reached. After drying with sodium sulfate, filtration, concentration, and washing with pentane, a light green solid biphenol compound 1 was obtained. The yield was 1.6 g and the yield was 95%.
1H NMR (CDCl ₃ , ppm): 14.93 (s, 2 H), 8.44 (d, J = 4.0 Hz, 2 H), 8.00 (d, J = 8.4 Hz, 2 H), 7.86 (m, 4 H) , 7.43 (d, J = 7.2 Hz, 2 H), 7.23 (m, 2 H), 7.02 (t, J = 7.6 Hz, 2 H).

[Synthesis Example 2] Synthesis of biphenol compound 2 (synthesis of intermediate compound 2A)

  Compound 1B (5.0 g, 9.50 mmol), 2-bromo-6-isopropylpyridine (3.0 g, 19.0 mmol), sodium carbonate (7.5 g, 19.0 mmol) in dimethyl ether (100 mL) / water (20 mL) ) Tetrakis (triphenylphosphine) palladium (1.0 g, 0.95 mmol) was added to the solution at 10 ° C. and refluxed for 12 hours. After adding ice water (100 mL), the reaction solution was extracted with ethyl acetate (100 mL × 3 times). After washing with saturated brine, drying over sodium sulfate, filtration, concentration, and purification by column chromatography (pentane / ethyl acetate = 10/1) gave Compound 2A as a yellow oil. The yield was 4.0 g and the yield was 83%.

(Synthesis of biphenol compound 2)

To a solution of Compound 2A (4.0 g, 7.80 mmol) in ethyl acetate (40 mL) was added ethyl acetate hydrochloride solution (60 mL) at 0 ° C., and the mixture was stirred at 10 ° C. for 40 minutes.
After adding ice water (50 mL), the mixture was concentrated, ethyl acetate (100 mL) was added, and the mixture was washed with a saturated aqueous sodium hydrogencarbonate solution until pH 8 was reached. After separating and washing with saturated brine, the mixture was dried over sodium sulfate. Filtration and concentration were followed by washing with ethyl acetate (10 mL) to obtain a yellow solid biphenol compound 2. The yield was 2.8 g and the yield was 84%.
1H NMR (CDCl ₃ , ppm): 15.04 (br, 2 H), 7.86 (d, J = 6.4 Hz, 2 H), 7.79 (m, 4 H), 7.44 (d, J = 6.4 Hz, 2 H) , 7.11 (d, J = 7.2 Hz, 2 H), 7.02 (d, J = 7.6 Hz, 2 H), 3.10 (m, 2 H), 1.32 (s, 6 H), 1.31 (s, 6 H) .

[Synthesis Example 3] Synthesis of biphenol compound 3 (synthesis of intermediate compound 3A)

  To a solution of compound 1A (15.0 g, 54.7 mmol) in tetrahydrofuran (150 mL), normal butyl lithium (48.0 mL, 121 mmol, 2.5 M hexane solution) was added dropwise at 0 ° C., and the mixture was stirred at 10 ° C. for 2 hours. To this reaction solution, dimethylformamide (16.0 g, 219 mmol) was added at 0 ° C., and the mixture was stirred at 10 ° C. for 12 hours. After the reaction, ice water (150 mL) was added, and the reaction solution was extracted with ethyl acetate (100 mL × 3 times). After washing with water (50 mL × 3 times), it was dried over sodium sulfate. After filtration and concentration, purification by column chromatography (pentane / ethyl acetate = 10/1) gave solid compound 3A. The yield was 3.6 g and the yield was 30%.

(Synthesis of Intermediate Compound 3B)

  To a solution of compound 3A (0.50 g, 1.51 mmol) in ethyl acetate (30 mL) was added ethyl acetate hydrochloride solution (10 mL) at 10 ° C., and the mixture was stirred at 10 ° C. for 30 min. After concentration, ethyl acetate (50 mL) was added, washed with water (3 × 50 mL), and dried over sodium sulfate. After filtration and concentration, the residue was purified by column chromatography (pentane / ethyl acetate = 5/1) to obtain a solid compound 3B. The yield was 94% with a yield of 0.34 g.

(Synthesis of biphenol compound 3)

To a solution of compound 3B (1.70 g, 7.02 mmol) in ethanol (200 mL) was added aniline (3.72 g, 35.1 mmol) at 10 ° C., and the mixture was stirred at 10 ° C. for 12 hours. The pale yellow precipitate was collected and washed with ethanol to obtain a yellow solid biphenol compound 3. The yield was 2.30 g and the yield was 92%.
1H NMR (CDCl ₃ , ppm): 13.94 (s, 2 H), 8.73 (s, 2 H), 7.53 (d, J = 7.2 Hz, 2 H), 7.47 (m, 2 H), 7.42 (m, 4 H), 7.30 (m, 6 H), 7.08 (t, J = 7.2 Hz, 2 H).

[Synthesis Example 4] Synthesis of biphenol compound 4 (synthesis of intermediate compound 4A)

To a solution of 2-bromopyridine (0.32 g, 2.0 mmol) in diethyl ether (10 mL), normal butyl lithium (0.88 mL, 2.2 mmol, 2.5 M hexane solution) was added dropwise at −78 ° C., and −78 ° C. Stir for 1 hour at ° C. To this reaction solution, intermediate 3A (0.
(30 g, 0.91 mmol) in tetrahydrofuran (2 mL) was added at −78 ° C., and the mixture was stirred at room temperature for 16 hours. After the reaction, ice water (20 mL) was added, and the reaction solution was extracted with ethyl acetate (20 mL × 3 times). After washing with saturated saline (50 mL × 3 times), it was dried over sodium sulfate. After filtration and concentration, purification by column chromatography (pentane / ethyl acetate = 1/1) gave oily compound 4A. The yield was 0.3 g and the yield was 67%.

(Synthesis of biphenol compound 4)

Acetic anhydride (100 mL) was added to a solution of compound 4A (10.0 g, 20.5 mmol) in pyridine (100 mL) at room temperature, and the mixture was stirred at 80 ° C. for 1.5 hours. After the reaction, the reaction mixture was concentrated under reduced pressure, and dissolved by adding ethanol (150 mL). To this solution, triethylamine (20.7 g, 205 mmol) and Pd / C (8.7 g, 4.1 mmol, 5 wt%) were added at room temperature, and then the atmosphere in the flask was replaced with hydrogen. Stir for hours. After the reaction, the filtrate was collected by filtration. The ethyl acetate (50 mL × 3) extract from the solid removed by filtration was concentrated under reduced pressure along with the filtrate. This was again dissolved in ethyl acetate (20 mL), and hydrochloric acid (20 mL, 10 M) was slowly added dropwise thereto at room temperature, and disappearance of the raw material was confirmed by LCMS. The reaction solution was neutralized with saturated aqueous sodium hydrogen carbonate solution to pH 9, and extracted with ethyl acetate (100 mL × 3 times). After washing with saturated brine (150 mL), it was dried over sodium sulfate. After filtration and concentration, purification by column chromatography (pentane / ethyl acetate = 1/1) gave Compound 4 as a white solid. The yield was 3.7 g and the yield was 49%.
1H NMR (CDCl ₃ , ppm): 11.3 (br, 2 H), 8.43 (d, J = 4.0 Hz, 2 H), 7.65 (m, 2 H), 7.31 (m, 2 H), 7.25 (m, 2 H), 7.21 (d, J = 7.2 Hz, 2 H), 7.14 (m, 2 H), 6.94 (m, 2 H), 4.24 (s, 4 H).

[Synthesis Example 5] Synthesis of biphenol compound 5 (synthesis of intermediate compound 5B)

  A solution of lithium hydride (1.57 g, 39.1 mmol, 60% mineral oil) in dimethylformamide (80 mL) was added to diphenylamine (4.85 g, 28.7 mmol) at room temperature and stirred for 1 hour. To this reaction solution, a solution of compound 5A (6.00 g, 13.1 mmol) in dimethylformamide (20 mL) was added and stirred at room temperature for 16 hours. After the reaction, ice water (40 mL) was added, and the reaction solution was extracted with ethyl acetate (100 mL × 3 times) and dried over sodium sulfate. After filtration and concentration, the residue was purified by column chromatography (pentane / ethyl acetate = 5/1) to obtain a solid compound 5B. The yield was 6.7 g and the yield was 81%.

(Synthesis of biphenol compound 5)

To a solution of compound 5B (4.70 g, 7.39 mmol) in ethyl acetate (10 mL) was added hydrochloric acid / ethyl acetate solution (80 mL, 1.0 M) at room temperature, and the mixture was stirred for 2 hours. The reaction solution was washed with a saturated aqueous sodium hydrogen carbonate solution until pH 8 was extracted, extracted with ethyl acetate (100 mL × 3 times), and dried over sodium sulfate. After filtration and concentration, purification by column chromatography (pentane / ethyl acetate = 5/1) gave solid compound 5. The yield was 2.4 g and the yield was 42%.
1H NMR (CDCl ₃ , ppm): 8.22 (s, 2 H), 7.27 (m, 10 H), 7.20 (d, J = 8.4 Hz, 2 H), 7.14 (dd, J = 0.8, 8.4 Hz, 2 H), 7.02 (m, 4 H), 6.96 (m, 2 H), 5.05 (m, 4 H).

[Synthesis Example 6] Synthesis of biphenol compound 6 (synthesis of intermediate compound 6B)

  Diisopropylamine (10.5 g, 104 mmol) and potassium carbonate (14.4 g, 104 mmol) were added to a dimethylformamide (100 mL) solution of compound 6A (6.0 g, 13.0 mmol), and the mixture was refluxed for 24 hours. After cooling to room temperature, ice water (200 mL) was added, and the reaction mixture was extracted with ethyl acetate (200 mL × 3 times) and dried over sodium sulfate. After filtration and concentration, the residue was purified by column chromatography (pentane / ethyl acetate = 5/1) to obtain a solid compound 6B. The yield was 3.8 g and the yield was 58%.

(Synthesis of biphenol compound 6)

To a solution of compound 6B (2.30 g, 4.60 mmol) in ethyl acetate (60 mL) was added hydrochloric acid / ethyl acetate solution (69 mL, 1.0 M) at room temperature, and the mixture was stirred for 5 hours. The reaction solution was washed with a saturated aqueous sodium hydrogencarbonate solution until pH 8 was extracted, extracted with ethyl acetate (100 mL × 3 times), washed with saturated brine (100 mL × 3 times), and dried over sodium sulfate. After filtration and concentration, the solid compound 6 was obtained by washing with pentane. The yield was 1.7 g and the yield was 89%.
1H NMR (CDCl ₃ , ppm): 11.89 (br, 2 H), 7.26 (d, J = 6.0 Hz, 2 H), 6.97 (d, J = 6.0 Hz, 2 H), 6.82 (t, J = 7.2 Hz, 2 H), 3.90 (s, 4 H), 3.20 (m, 2 H), 1.12 (d, J = 9.2 Hz, 24 H).

[Synthesis Example 7] Synthesis of biphenol compound 7 (synthesis of intermediate compound 7C)

To a solution of compound 7B (9.0 g, 17.1 mmol) in tetrahydrofuran (200 mL) was added sodium hydroxide (4.1 g, 103 mmol) and hydrogen peroxide (10.5 g, 103 mmol, 30 wt%) at room temperature. Stir for hours.
After the reaction, ice water (200 mL) was added, and hydrochloric acid (1M) was added until the pH reached 5. The reaction solution was extracted with ethyl acetate (200 mL × 3 times), washed with a saturated aqueous sodium thiosulfate solution (200 mL × 3 times), washed with saturated brine (100 mL × 3 times), and dried over sodium sulfate. Filtration and concentration gave Compound 7C as a white solid. The yield was 95% with a yield of 5.0 g.

(Synthesis of Intermediate Compound 7D)

  Compound 7C (5.0 g, 16.3 mmol), phenylboronic acid (8.0 g, 65.2 mmol), copper acetate II (3.9 g, 32.6 mmol), triethylamine (34 mL), MS4A (34 g) in dichloromethane ( 300 mL) solution was stirred for 48 hours under oxygen atmosphere. After filtration and concentration, purification by column chromatography (pentane / ethyl acetate = 10/1) gave Compound 7D as a white solid. The yield was 3.8 g and the yield was 50%.

(Synthesis of biphenol compound 7)

To a solution of compound 7D (3.80 g, 8.30 mmol) in ethyl acetate (50 mL) was added hydrochloric acid / ethyl acetate solution (120 mL, 1.0 M) at 0 ° C., and the mixture was stirred at room temperature for 5 hours. Ice water (200 mL) was added to the reaction mixture, and the mixture was extracted with ethyl acetate (100 mL × 3 times), washed with saturated aqueous sodium bicarbonate until pH 8, washed with saturated brine (100 mL × 3 times), sulfuric acid Dry with sodium. After filtration and concentration, purification by column chromatography (pentane / ethyl acetate = 5/1) gave Compound 7 as a white solid. The yield was 2.4 g and the yield was 80%.
1H NMR (CDCl ₃ , ppm): 11.89 (br, 2 H), 7.37 (dd, J = 3.8, 4.4 Hz, 4 H), 7.14 (m, 4 H), 7.09 (dd, J = 1.2, 8.8 Hz , 4 H), 6.97 (m, 4 H), 6.18 (s, 2 H).

[Synthesis Example 8] Synthesis of biphenol compound 8 (synthesis of intermediate compound 8B)

  To a solution of compound 8A (0.15 g, 0.35 mmol) in acetone (10 mL), phenol (0.083 g, 0.88 mmol) and potassium carbonate (0.20 g, 1.40 mmol) were added and refluxed for 12 hours. After cooling to room temperature, filtration and concentration, ethyl acetate (50 mL) was added, washed with aqueous sodium hydroxide solution (20 mL × 3 times, 3M), washed with saturated brine (20 mL × 3 times), and sodium sulfate. Dried. Filtration and concentration gave an oily compound 8B. The yield was 95% with a yield of 0.15 g.

(Synthesis of biphenol compound 8)

To an ethyl acetate solution (60 mL) of compound 8B (2.00 g, 4.12 mmol) was added hydrochloric acid / ethyl acetate solution (60 mL, 1.0 M) at 0 ° C., and the mixture was stirred at room temperature for 6 hours. Ice water (50 mL) was added to the reaction mixture, and the mixture was extracted with ethyl acetate (50 mL × 3 times), washed with saturated aqueous sodium bicarbonate until pH 8, washed with saturated brine (50 mL × 3 times), sulfuric acid Dry with sodium. After filtration and concentration, the residue was purified by column chromatography (pentane / ethyl acetate = 10/1) to obtain Compound 8 as a yellow oil. The yield was 68% with a yield of 1.1 g.
1H NMR (DMSO-d6, ppm): 8.74 (s, 2 H), 7.36 (d, J = 8.4 Hz, 2 H), 7.31 (dd, J = 7.2, 8.4 Hz, 4 H), 7.16 (d, J = 7.6 Hz, 2 H), 7.03 (d, J = 8.0 Hz, 4 H), 6.95 (m, 4 H), 5.14 (s, 4 H).

[Synthesis Example 9] Synthesis of biphenol compound 9 (synthesis of intermediate compound 9B)

To a solution of compound 9A (10.0 g, 37.0 mmol) in 1,4-dioxane (200 mL), (PinB) ₂ (11.3 g, 44.6 mmol), potassium acetate (5.4 g, 55.5 mmol), Pd (Dppf) Cl ₂ (1.3 g, 1.85 mmol) was added and refluxed for 16 hours. After cooling to room temperature, the mixture was filtered, concentrated, and extracted with ethyl acetate (3 × 100 mL). The extract was washed with saturated saline (50 mL × 3 times) and dried over sodium sulfate. After filtration and concentration, the residue was purified by column chromatography (pentane / ethyl acetate = 20/1) to obtain a white solid compound 9B. The yield was 6.7 g and the yield was 57%.

(Synthesis of Intermediate Compound 9C)

To a solution of compound 9B (0.5 g, 1.58 mmol) in ethanol (20 mL) was added sodium hydroxide (0.13 g, 3.2 mmol), H ₂ NOH · HCl (0.17 g, 2.4 mmol), and 24 Reflux for hours. After cooling to room temperature, ice water (50 mL) was added to the reaction solution, extracted with ethyl acetate (50 mL × 3 times), washed with saturated brine (50 mL × 3 times), and dried over sodium sulfate. Filtration and concentration gave compound 9C as a pale yellow oil. The yield was 0.28 g and the yield was 90%.

(Synthesis of Intermediate Compound 9E)

  Compound 9C (4.48 g, 21.7 mmol) and potassium carbonate (4.80 g, 34.8 mmol) were added to a solution of compound 9D (4.00 g, 8.70 mmol) in acetone (50 mL), and the mixture was refluxed for 24 hours. After cooling to room temperature, filtration, concentration, and purification by column chromatography (pentane / ethyl acetate = 5/1) gave Compound 9E as a colorless oil. The yield was 4.0 g and the yield was 66%.

(Synthesis of biphenol compound 9)

To a solution of compound 9E (4.50 g, 6.30 mmol) in ethyl acetate (20 mL) was added hydrochloric acid / ethyl acetate solution (90 mL, 1.0 M) at 0 ° C., and the mixture was stirred at room temperature for 4 hours. Ice water (200 mL) was added to the reaction mixture, and the mixture was extracted with ethyl acetate (200 mL × 3 times), washed with saturated aqueous sodium hydrogen carbonate solution until pH 8, washed with saturated brine (80 mL × 3 times), sulfuric acid Dry with sodium. After filtration and concentration, purification by column chromatography (pentane / ethyl acetate = 10/1) gave Compound 9 as a white solid. The yield was 1.6 g and the yield was 45%.
1H NMR (DMSO-d6, ppm): 8.69 (s, 2 H), 7.40 (br, 2 H), 7.15 (br, 2 H), 6.97 (m, 4 H), 6.83 (s, 4 H), 5.13 (m, 4 H), 1.27 (s, 36 H).

[Example 1]
An equimolar amount of tetrabenzylzirconium and biphenol compound 1 were weighed into 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 After washing with ethanol, it was recovered by drying under reduced pressure at 80 ° C. for 3 hours.

[Examples 2 to 11, Comparative Example 1 (ethylene polymerization)]
In Examples 2 to 11 and Comparative Example 1, a polymer was produced under the polymerization conditions shown in Table 1 according to the operation of Example 1. In Comparative Example 1, N, N′-bis (3-tert-butyl-5-methoxy-2-hydroxyphenylmethyl) -N, which was synthesized with reference to a known document (Non-patent Document 1 described above in paragraph 0007), was used. N′-dimethylethylenediamine (Compound 10) was used. The physical property evaluation results of the obtained polymer are shown in Table 1, and the 13C NMR chart of the polymer obtained in Example 4 is shown in FIG. In addition, in the polymer manufactured by Example 4, only the linear saturated terminal (2.1 carbon / 1000 carbon) and the vinyl group (2.0 carbon / 1000 carbon) were detected at the terminal.

[Example 12 (propylene polymerization)]
100 μmol of tetrabenzylzirconium and biphenol compound 4 were weighed in a 30 mL flask sufficiently purged with nitrogen, and dehydrated toluene (10 mL) was added thereto, and then mixed and stirred at room temperature for 5 minutes to prepare a complex solution. Next, the inside of a stainless steel autoclave with an induction stirrer with an internal volume of 1.5 L was replaced with purified nitrogen, and purified toluene and DMAO (10 mmol) toluene solution were introduced into the autoclave under a purified nitrogen atmosphere (total amount 700 mL). After maintaining the polymerization temperature at 70 ° C. and the propylene pressure at 1.0 MPa, the previously prepared complex solution was injected to initiate the polymerization. During the reaction, the temperature was kept constant and propylene was continuously supplied so that the pressure was maintained.
After the polymerization was completed by press-fitting ethanol (10 mL), the propylene was purged, the autoclave was cooled to room temperature, the obtained polymer was reprecipitated with ethanol (1 L), and the solid obtained by filtration After washing with ethanol, it was recovered by drying under reduced pressure at 80 ° C. for 3 hours. Yield 9.6 g, Mw 63,000, Mw / Mn 9.5, melting point 154.7 ° C., mm 72.8%. A 13C NMR chart of the resulting polymer is shown in FIG.

[Consideration by comparison of results of Examples and Comparative Examples]
In Examples 1 to 11, high molecular weight polyethylene having a molecular weight of 300,000 or more could be produced, whereas in Comparative Example 1, the molecular weight remained at 10,000 or less. The catalytic activities of Examples 1 to 11 are also generally good.
Further, not only ethylene but also propylene can be polymerized. In Example 12, it was shown that polypropylene having a molecular weight of 60,000 or more could be produced, and the catalytic activity was generally good.
As described above, by using the metal complex of the present invention that can be synthesized relatively easily, a polymer having a higher molecular weight than that of the comparative example can be obtained, and the catalytic activity is generally good. 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 (12)

A biphenol compound represented by the following general formula (1).

(In General Formula (1), Q ₁ and Q ₂ are each independently 4 to 20 carbon atoms substituted with a divalent hydrocarbon group having 1 to 20 carbon atoms and a silyl group having 3 to 18 carbon atoms. And a substituent selected from the group consisting of a divalent hydrocarbon group having 1 to 20 carbon atoms substituted with a halogen atom, Q _{3 to} Q ₈ are each independently Selected from the group consisting of 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, and a silyl group substituted with a hydrocarbon group having 1 to 20 carbon atoms. T ₁ and T ₂ each independently represent 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, or 2 to 10 carbon atoms. Ester group, amino group, substituted amino group having 1 to 12 carbon atoms, substituted imino group having 1 to 12 carbon atoms It may have a pyridyl group optionally having 5 to 10 carbon atoms, a pyrrolidyl group optionally having 4 to 10 carbon atoms, or a substituent having 5 to 10 carbon atoms. A good piperidyl group, a hydrofuryl group optionally having a substituent having 4 to 10 carbon atoms, an imidazolyl group optionally having a substituent having 4 to 10 carbon atoms, and a substituent selected from the group consisting of halogens M and n are each independently an arbitrary number selected from 0, 1, and 2.) In general formula (1), m and n are 0, The biphenol compound of Claim 1 characterized by the above-mentioned. In general formula (1), m and n are 1, The biphenol compound of Claim 1 characterized by the above-mentioned. A metal complex obtained by reacting the biphenol compound according to any one of claims 1 to 3 with a complex precursor which is a group 4-10 transition metal compound. The metal complex according to claim 4, which is represented by the following general formula (2).

(In the general formula _{(2), Q 1 ~Q 8} , T 1, T 2, m, and n are the same as substituent in the biphenol compound represented by the general formula (1), M, 4 10 represents a metal atom selected from the group consisting of a group 10 transition metal, and X ₁ and X ₂ are each independently a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or an alkoxy having 1 to 10 carbon atoms. And a substituent selected from the group consisting of a group, 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, and a halogen.) The metal complex according to claim 5, wherein m and n in the general formula (2) are 0. The metal complex according to claim 5, wherein m and n in the general formula (2) are 1. The catalyst component for olefin polymerization containing the metal complex of any one of Claims 4-7. An olefin polymerization catalyst comprising the following components (A) and (B), and (C) as necessary.
Component (A): Metal complex according to any one of claims 4 to 7 Component (B): Compound or ion-exchange layered silicate that reacts with component (A) to form an ion pair Component (C) : Organoaluminum compound The olefin polymerization catalyst according to claim 9, wherein the component (B) is an aluminoxane. Component (B) is a boron compound, The catalyst for olefin polymerization of Claim 9 characterized by the above-mentioned. The manufacturing method of an olefin polymer characterized by superposing | polymerizing or copolymerizing an olefin in presence of the polymerization catalyst of any one of Claims 9-11.

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