JP6207336B2 - Diol compound, catalyst for olefin polymerization, 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.

  The object of the present invention, that is, the problem is that it is possible to produce an olefin polymer having a high molecular weight or high stereoregularity in view of the problems of the prior art in the transition metal complex having a tetradentate ligand described above, and 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.

  The present inventors aim to solve the above-mentioned problems, and can be used for a transition metal complex having a tetradentate ligand in a metal complex catalyst to produce a polymer having a high molecular weight or high stereoregularity. As a result of various search for compounds, a diol having such a specific structure has not been reported so far as a transition metal complex having a tetradentate ligand, and a complex having a dialkoxo partial structure derived from a novel diol compound It has been found that the compound functions as a component of a polymerization catalyst suitable for the above 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).

(In General Formula (1), Q1 to Q3 are each independently a divalent hydrocarbon group having 1 to 20 carbon atoms, a divalent hydrocarbon group having 1 to 20 carbon atoms substituted with a hydroxyl group, or carbon. C2-C20 divalent hydrocarbon group substituted with C1-C10 alkoxy group, C3-C20 divalent hydrocarbon group substituted with C2-C10 ester group, carbon Substitution selected from the group consisting of a divalent hydrocarbon group having 4 to 20 carbon atoms substituted with a silyl group having 3 to 18 carbon atoms, and a divalent hydrocarbon group having 1 to 20 carbon atoms substituted with a halogen atom Indicates a group.
Q4 and Q5 are each independently a hydrogen atom, a halogen 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 an alkoxy group having 1 to 10 carbon atoms. A group consisting of a hydrocarbon group having 2 to 20 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, or a silyl group substituted with a hydrocarbon group having 1 to 20 carbon atoms. The substituent selected from more is shown.
T1 and T2 are each independently 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, an amino group, a substituted amino group having 1 to 12 carbon atoms, or A substituent selected from the group consisting of halogen is shown. )

Here, a theoretical estimation of why the desired catalytic performance can be expressed 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), and is used as a catalyst component of an olefin polymerization catalyst in the present invention. Forming a catalyst. The diol compound represented by the general formula (1) in the present invention is basically characterized in that a chelate cyclic structure is formed as a dialkoxo ligand during complex formation. It can be estimated that it will bring. That is, a tetradentate ligand that forms a chelate cyclic structure contributes to the stabilization of the complex structure, and suppresses the formation of structural isomers often observed in tetradentate complexes and stabilizes the polymerization field, thereby achieving a high steric structure. It is considered that the polymerization performance is more preferably controlled by achieving regularity.
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. I can't get it from the literature. That is, the present invention is characterized by being a diol compound that can form a unique and novel tetradentate ligand.

  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) is constituted as the basic invention (1) as described in paragraph 0011, and is further a diol compound of the basic invention (1) and a group 4-10 transition metal compound. A metal complex obtained by reacting with a complex precursor, that is, a metal complex represented by the following general formula (2) is constituted as a basic invention (2), and each of the following inventions is incidental to the basic invention. It adds a requirement or shows the mode of implementation. All invention units are collectively referred to as an invention group.

(In the general formula (2), Q1, Q2, Q3, Q4, Q5, T1 and T2 are the same as the substituents in the diol compound represented by the general formula (1), and M is 4 to 10). Represents a metal atom selected from the group consisting of group transition metals, X 1 and X 2 are each independently a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a carbon number A substituent selected from the group consisting of 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 halogen is shown.

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.

According to the present invention, an olefin polymer having a high molecular weight or high stereoregularity can be produced and can be synthesized at a low cost by a simple synthetic route as compared with conventional metallocene complexes and can form a metal complex. A diol compound, a catalyst for polyolefin polymerization using the diol compound, and a method for polymerizing olefins using the same can be provided.
In addition, in comparison with the data of each Example described later and each Example and each Comparative Example, the polymer produced according to the present invention has a higher molecular weight or higher stereoregularity than a polymer based on a conventional tetradentate complex. Has been demonstrated. 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 or high stereoregularity, a catalyst for polyolefin polymerization using the metal complex of the present invention, and a method for polymerizing olefins using the same, From an industrial point of view, it 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. Diol Compound (1) Basic Structure The diol compound in the present invention is represented by the following general formula (1).

(In General Formula (1), Q1 to Q3 are each independently a divalent hydrocarbon group having 1 to 20 carbon atoms, a divalent hydrocarbon group having 1 to 20 carbon atoms substituted with a hydroxyl group, or carbon. C2-C20 divalent hydrocarbon group substituted with C1-C10 alkoxy group, C3-C20 divalent hydrocarbon group substituted with C2-C10 ester group, carbon Substitution selected from the group consisting of a divalent hydrocarbon group having 4 to 20 carbon atoms substituted with a silyl group having 3 to 18 carbon atoms, and a divalent hydrocarbon group having 1 to 20 carbon atoms substituted with a halogen atom Indicates a group.
Q4 and Q5 are each independently a hydrogen atom, a halogen 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 an alkoxy group having 1 to 10 carbon atoms. A group consisting of a hydrocarbon group having 2 to 20 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, or a silyl group substituted with a hydrocarbon group having 1 to 20 carbon atoms. The substituent selected from more is shown.
T1 and T2 are each independently 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, an amino group, a substituted amino group having 1 to 12 carbon atoms, or A substituent selected from the group consisting of halogen is shown. )

(2) Q1 to Q3 Q1 to Q3, which are divalent hydrocarbon groups having 1 to 20 carbon atoms, are preferably divalent hydrocarbon groups having 1 to 12 carbon atoms, more preferably 1 to 1 carbon atoms. 12 alkylene groups, phenylene groups, alkylene-phenylene-alkylene groups, and biphenylene groups.
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.

Q1-Q3, which is a C1-C20 divalent hydrocarbon group substituted with a hydroxyl group, preferably includes a hydroxyl group-substituted product of the aforementioned C1-C20 divalent hydrocarbon group.
Preferred examples are (1-hydroxy) methylene group, (1-hydroxy) ethylene group, (2-hydroxy) ethylene group, (1-hydroxy) trimethylene group, (2-hydroxy) trimethylene group, (3-hydroxy) Trimethylene group, (1-hydroxy) tetramethylene group, (2-hydroxy) tetramethylene group, (3-hydroxy) tetramethylene group, (4-hydroxy) tetramethylene group, (1-hydroxy) pentamethylene group, (2 -Hydroxy) pentamethylene group, (3-hydroxy) pentamethylene group, (4-hydroxy) pentamethylene group, (5-hydroxy) pentamethylene group, (1-hydroxy) hexamethylene group, (2-hydroxy) hexamethylene group Group, (3-hydroxy) hexamethylene group, (4-hydroxy) hexa Tylene group, (5-hydroxy) hexamethylene group, (6-hydroxy) hexamethylene group, more preferably (1-hydroxy) methylene group, (1-hydroxy) ethylene group, (2-hydroxy) ethylene group , (5-hydroxy) pentamethylene group and (6-hydroxy) hexamethylene group, particularly preferably (1-hydroxy) methylene group, (1-hydroxy) ethylene group and (2-hydroxy) ethylene group. .

Q1 to Q3, which are divalent hydrocarbon groups having 2 to 20 carbon atoms substituted with an alkoxy group having 1 to 10 carbon atoms, are preferably the aforementioned divalent hydrocarbon groups having 1 to 20 carbon atoms, The structure substituted with the C1-C10 alkoxy group is mentioned.
Preferred examples are (1-methoxy) methylene group, (1-methoxy) ethylene group, (2-methoxy) ethylene group, (1-ethoxy) ethylene group, (2-ethoxy) ethylene group, (1-methoxy) Trimethylene group, (2-methoxy) trimethylene group, (3-methoxy) trimethylene group, (1-methoxy) tetramethylene group, (2-methoxy) tetramethylene group, (3-methoxy) tetramethylene group, (4-methoxy) ) Tetramethylene group, (1-methoxy) pentamethylene group, (2-methoxy) pentamethylene group, (3-methoxy) pentamethylene group, (4-methoxy) pentamethylene group, (5-methoxy) pentamethylene group, (1-methoxy) hexamethylene group, (2-methoxy) hexamethylene group, (3-methoxy) hexamethylene group, (4 Methoxy) hexamethylene group, (5-methoxy) hexamethylene group, (6-methoxy) hexamethylene group, more preferably (1-methoxy) methylene group, (1-methoxy) ethylene group, (2-methoxy) ) Ethylene group, (1-ethoxy) ethylene group, (2-ethoxy) ethylene group, particularly preferably (1-methoxy) methylene group, (1-methoxy) ethylene group, (2-methoxy) ethylene group. is there.

Q1-Q3, which is a C3-C20 divalent hydrocarbon group substituted with a C2-C10 ester group, is preferably the aforementioned C1-C20 divalent hydrocarbon group, Examples include structures substituted with an ester group having 2 to 10 carbon atoms.
Preferred specific examples are (methoxycarbonyl) methylene group, (1-methoxycarbonyl) ethylene group, (2-methoxycarbonyl) ethylene group, (1-ethoxycarbonyl) ethylene group, (2-ethoxycarbonyl) ethylene group, (1 -Methoxycarbonyl) trimethylene group, (2-methoxycarbonyl) trimethylene group, (3-methoxycarbonyl) trimethylene group, (1-methoxycarbonyl) tetramethylene group, (2-methoxycarbonyl) tetramethylene group, (3-methoxycarbonyl) ) Tetramethylene group, (4-methoxycarbonyl) tetramethylene group, (1-methoxycarbonyl) pentamethylene group, (2-methoxycarbonyl) pentamethylene group, (3-methoxycarbonyl) pentamethylene group, (4-methoxycarbonyl) ) Bae Tamethylene group, (5-methoxycarbonyl) pentamethylene group, (1-methoxycarbonyl) hexamethylene group, (2-methoxycarbonyl) hexamethylene group, (3-methoxycarbonyl) hexamethylene group, (4-methoxycarbonyl) hexa A methylene group, (5-methoxycarbonyl) hexamethylene group, (6-methoxycarbonyl) hexamethylene group, more preferably (methoxycarbonyl) methylene group, (1-methoxycarbonyl) ethylene group, (2-methoxycarbonyl). ) Ethylene group, (1-ethoxycarbonyl) ethylene group, (2-ethoxycarbonyl) ethylene group, particularly preferably (methoxycarbonyl) methylene group, (1-methoxycarbonyl) ethylene group, (2-methoxycarbonyl). Ethylene group .

Q1-Q3, which is a C4-C20 divalent hydrocarbon group substituted with a C3-C18 silyl group, is preferably the aforementioned C1-C20 divalent hydrocarbon group, Examples include structures 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.

Q1-Q3, which is a C1-C20 divalent hydrocarbon group substituted with a halogen atom, preferably has a structure in which the aforementioned C1-C20 divalent hydrocarbon group is substituted with a halogen atom. The body is mentioned.
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) Q4 and Q5 Preferable specific examples of Q4 and Q5 which are halogen atoms are fluorine, chlorine and bromine. Of these, a more preferred substituent is chlorine.

Q4 and Q5 which are hydrocarbon groups having 1 to 20 carbon atoms are preferably an alkyl group, a cycloalkyl group, an alkenyl group and 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.

Q4 and Q5, which are hydrocarbon groups having 1 to 20 carbon atoms substituted with a halogen atom, preferably include 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.

Q4 and Q5 which are hydrocarbon groups having 2 to 20 carbon atoms substituted with an alkoxy group having 1 to 10 carbon atoms are preferably the above-described hydrocarbon groups having 1 to 20 carbon atoms, Examples include structures substituted with alkoxy groups.
Preferable examples are C2-C6 hydrocarbon groups substituted with methoxy group, ethoxy group, isopropoxy group, 1-propoxy group, 1-butoxy group or t-butoxy group. More preferably, it is a C2-C6 hydrocarbon group substituted by a methoxy group or an ethoxy group, and specifically includes 1- (methoxymethyl) ethyl group, 1- (ethoxymethyl) ethyl group, 1- ( Phenoxymethyl) ethyl group, 1- (methoxyethyl) ethyl group, 1- (ethoxyethyl) ethyl group, di (methoxymethyl) methyl group, di (ethoxymethyl) methyl group, di (phenoxymethyl) methyl group . Particularly preferred are 1- (methoxymethyl) ethyl group and 1- (ethoxymethyl) ethyl group.

  Q4 and Q5, which are alkoxy groups having 1 to 10 carbon atoms, are preferably alkoxy groups having 1 to 4 carbon atoms. Preferred specific examples are methoxy group, 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.

Q4 and Q5 which are aryloxy groups having 6 to 20 carbon atoms are preferably aryloxy groups having 6 to 12 carbon atoms, and preferred specific examples thereof include phenoxy group, 4-methylphenoxy group, 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.

Q4 and Q5 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 specific examples thereof are trimethylsilyl group, dimethylphenylsilyl group, diphenyl. A methylphenylsilyl group and a triphenylsilyl group;
Among these, a more preferable substituent is a trimethylsilyl group or a dimethylphenylsilyl group, and a trimethylsilyl group is particularly preferable.

(4) T1, T2 T1 and T2 which are alkoxy groups having 1 to 10 carbon atoms are preferably alkoxy groups having 1 to 4 carbon atoms, and preferred specific examples are methoxy group, ethoxy group and 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.

T1 and T2 which are aryloxy groups having 6 to 20 carbon atoms are preferably aryloxy groups having 6 to 12 carbon atoms, and specific examples are phenoxy group, 4-methylphenoxy group, 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.

T1 and T2 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, isopropoxy group. Examples include carbonyl group, n-butoxycarbonyl group, t-butoxycarbonyl group, (4-hydroxybutoxy) carbonyl group, (4-glycidylbutoxy) carbonyl group, phenoxycarbonyl group, succinic anhydride group, and succinimide group. .
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.

Preferred specific examples of T1 and T2 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, Examples thereof include a diphenylamino group, a bis (trimethylsilyl) amino group, and a morpholinyl group.
Of these, more preferred substituents are a dimethylamino group and a bis (trimethylsilyl) amino group.

  Preferable specific examples of T1 and T2 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 of the present invention, 1,3-bis (2-benzyloxy-3 ′, 5,5′-trit-butyl-3-biphenylyl) -1,3 -Dihydroxypropane, 1,3-bis (2-methoxy-3 ', 5,5'-tri-t-butyl-3-biphenylyl) -1,3-dihydroxypropane, 1,3-bis (2-methoxy-3) , 5-di-t-butyl-phenyl) -1,3-dihydroxypropane, 1,4-bis (2-benzyloxy-3 ′, 5,5′-tri-t-butyl-3-biphenylyl) -1,4- Dihydroxybutane, 1,4-bis (2-methoxy-3 ′, 5,5′-tri-t-butyl-3-biphenylyl) -1,4-dihydroxybutane, 1,4-bis (2-methoxy-3, 5-di-t-butyl-phenyl) -1, -Dihydroxybutane, 1,5-bis (2-benzyloxy-3 ', 5,5'-tri-butyl-3-biphenylyl) -1,5-dihydroxypentane, 1,5-bis (2-methoxy-3) ', 5,5'-tri-t-butyl-3-biphenylyl) -1,5-dihydroxypentane, 1,5-bis (2-methoxy-3,5-di-t-butyl-phenyl) -1,5- Dihydroxypentane is mentioned. These are examples and it is obvious that the present invention is not limited thereto.

2. Metal Complex (1) Basic Structure The metal complex in the present invention is a metal complex obtained by reacting a diol compound with a complex precursor which is a group 4-10 transition metal compound, or specifically the following general formula: It is a metal complex shown by (2).

  In the general formula (2), Q1 to Q3 are each independently a divalent hydrocarbon group having 1 to 20 carbon atoms, a divalent hydrocarbon group having 1 to 20 carbon atoms substituted with a hydroxyl group, and the number of carbon atoms. A divalent hydrocarbon group having 2 to 20 carbon atoms substituted with an alkoxy group having 1 to 10 carbon atoms, a divalent hydrocarbon group having 3 to 20 carbon atoms substituted with an ester group having 2 to 10 carbon atoms, and the number of carbon atoms A substituent selected from the group consisting of a C 4-20 divalent hydrocarbon group substituted with a 3-18 silyl group and a C 1-20 divalent hydrocarbon group substituted with a halogen atom Indicates.

  Q4 and Q5 are each independently a hydrogen atom, a halogen 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 an alkoxy group having 1 to 10 carbon atoms. A group consisting of a hydrocarbon group having 2 to 20 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, or a silyl group substituted with a hydrocarbon group having 1 to 20 carbon atoms. The substituent selected from more is shown.

  T1 and T2 are each independently 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, an amino group, a substituted amino group having 1 to 12 carbon atoms, or A substituent selected from the group consisting of halogen is shown.

  M represents a metal atom selected from the group consisting of 4 to 10 group transition metals, and X1 and X2 each independently represent a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a carbon atom having 1 to 10 carbon atoms. And a substituent selected from the group consisting of an alkoxy 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. )

Here, Q1-Q5, T1, and T2 are the same as the substituents in the diol compound represented by the general formula (1).
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) X1 and X2 X1 and X2 which are hydrocarbon groups having 1 to 20 carbon atoms are preferably an alkyl group, a cycloalkyl group, an alkenyl group and 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 benzyl 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, and a fused aryl group. , Phenylcyclohexyl 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.

X1 and X2, which are alkoxy groups having 1 to 10 carbon atoms, are preferably alkoxy groups having 1 to 4 carbon atoms, and preferred specific examples are methoxy group, ethoxy group, isopropoxy group, 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.

X1 and X2 which are aryloxy groups having 6 to 20 carbon atoms are preferably aryloxy groups having 6 to 12 carbon atoms, and specific examples are phenoxy group, 4-methylphenoxy group, 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.

X1 and X2 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, isopropoxy group. Examples include carbonyl group, n-butoxycarbonyl group, t-butoxycarbonyl group, (4-hydroxybutoxy) carbonyl group, (4-glycidylbutoxy) carbonyl group, phenoxycarbonyl group, succinic anhydride group, and succinimide group. .
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 specific examples of X1 and X2 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, Examples thereof include a diphenylamino group, a bis (trimethylsilyl) amino group, and a morpholinyl group. Of these, a more preferred substituent is a dimethylamino group.

  Preferable specific examples of X1 and X2 which are halogen are fluorine, chlorine and bromine. Of these, a more preferred substituent is chlorine.

  Among the specific examples of the substituents X1 and X2, 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.

(3) 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 Diol Compound and Metal Complex Obtained by Reaction of Diol (1) Basic Synthetic Route The synthesis of the diol compound in the present invention can be carried out by any diol synthetic 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 include titanium halides such as titanium tetrachloride, titanium trichloride, titanium tetrabromide, titanium tetraiodide, tetrakis (dimethylamide) titanium, dichlorobis (dimethylamide) titanium, trichloro (dimethylamide) titanium, tetrakis (Diethylamide) Amido titanium such as titanium, tetra (isopropoxo) titanium, tetra (n-butoxo) titanium, dichloro (diisopropoxo) titanium, trichloro (isopropoxo) titanium and other alkoxo titanium, dichlorodimethyl titanium, 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, tetraisopropoxy titanium, 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 0.7 mol, relative to 1 mol of the diol 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 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): a metal complex obtained by reacting the diol 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)
The component (A) is a metal complex obtained by reacting the diol compound represented by the general formula (1) or a metal complex represented by the 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 an Al—O—Al bond 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 (3) can be used, but trialkylaluminum is preferably used.
(R1) _t Al (X3) _(3-t) ... General formula (3)
(In General Formula (3), R1 represents a hydrocarbon group such as an alkyl group, alkenyl group, aryl group, aralkyl group or the like having 1 to 18, preferably 1 to 12 carbon atoms, and X3 represents a hydrogen atom or a halogen atom. And 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, 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 (4).
^{[L1-H] + [B} (R2) (R3) (X4) (X5)] - ··· formula (4)
In the general formula (4), 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 (4), 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 are connected to each other by a bridging group. The substituent of the substituted aromatic hydrocarbon group is preferably an alkyl group typified by a methyl group, an ethyl group, a propyl group, an isopropyl group or the like, or a halogen such as fluorine, chlorine, bromine or iodine. 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 general formula (4) include tributylammonium tetra (pentafluorophenyl) borate, tributylammonium tetra (2,6-ditrifluoromethylphenyl) borate, tributylammonium tetra (3,5- Ditrifluoromethylphenyl) borate, tributylammonium tetra (2,6-difluorophenyl) borate, tributylammonium tetra (perfluoronaphthyl) borate, dimethylanilinium tetra (pentafluorophenyl) borate, dimethylanilinium tetra (2,6- Ditrifluoromethylphenyl) borate, dimethylanilinium tetra (3,5-ditrifluoromethylphenyl) borate, dimethylanilinium tetra (2,6-difluoropheny) ) 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, triethyla Monium tetra (perfluoronaphthyl) borate, tripropylammonium tetra (pentafluorophenyl) borate, tripropylammonium tetra (2,6-ditrifluoromethylphenyl) borate, tripropylammonium tetra (perfluoronaphthyl) borate, tripropylammonium Examples thereof include tetra (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 following General formula (5).
^{[L2] + [B (R2} ) (R3) (X4) (X5)] - ··· formula (5)
In the general formula (5), L2 is carbocation, methyl cation, ethyl cation, propyl cation, isopropyl cation, butyl cation, isobutyl cation, tert-butyl cation, pentyl cation, tropinium cation, benzyl cation, trityl cation, sodium. Examples include cations and protons. R2, R3, X4 and X5 are the same as defined in the general formula (4).

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. 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 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) General formula (6)
In General Formula (6), 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 (6) include trialkylaluminum such as trimethylaluminum, triethylaluminum, tripropylaluminum and triisobutylaluminum, halogen such as diethylaluminum monochloride and diethylaluminum monomethoxide. Or the alkoxy-containing alkylaluminum 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, 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 Can be mentioned.

(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, Q value)
(Measurement conditions) Model used: Waters 150C Detector: FOXBORO MI
RAN1A / IR detector (measurement wavelength: 3.42 μm) Measurement temperature: 140 ° C. Solvent: Orthodichlorobenzene (ODCB) Column: AD806M / S (three) manufactured by Showa Denko KK Flow rate: 1.0 mL / min Injection amount: 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.

  A synthesis route of the diol compounds 1 to 5 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 Diol Compounds 1 and 2 (Synthesis of Intermediate Compound 1A)

To a solution of N, O-dimethylhydroxylamine hydrochloride (2.9 g, 30.0 mmol) in methylene chloride (10 mL) was added trimethylaluminum toluene solution (2.0 M, 15.0 mL, 30.0 mmol) at 0 ° C., Stir for 30 minutes. To the reaction solution, valerolactone (2.0 g, 20.0 mmol) was added dropwise, stirred at 0 ° C. for 30 minutes, and further stirred at room temperature for 16 hours. The reaction mixture was cooled to 0 ° C., hydrochloric acid (0.1 N, 5 mL) was added, and the mixture was stirred at room temperature for 1 hr. After adding magnesium sulfate (4.0 g, 33.3 mmol), the mixture was stirred for 10 minutes, and the filtrate was collected by filtration. The solid obtained by filtration was extracted by adding methylene chloride (50 mL), mixed with the previous filtrate, and concentrated to obtain an oily product 1A. The yield was 1.2 g and the yield was 37%.
1H NMR (DMSO-d6, ppm): 4.35 (t, J = 5.2 Hz, 1 H), 3.65 (s, 3 H), 3.40 (dd, J = 11.6, 6.4 Hz, 2 H), 3.08 (s, 3 H), 2.37 (dd, J = 7.6, 7.2 Hz, 2 H), 1.54 (m, 2 H), 1.43 (m, 2 H).

(Synthesis of Intermediate Compound 1B)

Oxalyl chloride (1.18 g, 9.3 mmol) was slowly added to a solution of dimethyl sulfoxide (1.45 g, 18.6 mmol) in methylene chloride (10 mL) at −78 ° C. and stirred for 5 minutes. To this reaction solution, a methylene chloride solution (2 mL) of compound 1A (1.0 g, 6.2 mmol) was slowly added dropwise at −78 ° C. and stirred at the same temperature for 1 hour. Triethylamine (3.1 g, 31.0 mmol) was added to the reaction solution, and the mixture was stirred at room temperature for 16 hours. The reaction solution was poured into diethyl ether (10 mL), and the filtrate was collected by filtration. After concentration, purification by column chromatography (pentane / ethyl acetate = 1/1) gave Compound 1B as a pale yellow oil. The yield was 53% with a yield of 0.5 g.
1H NMR (CDCl3, ppm): 9.75 (d, J = 1.6 Hz, 1 H), 3.65 (s, 3 H), 3.15 (s, 3 H), 2.52 (td, J = 6.8, 1.6 Hz, 2 H ), 2.47 (t, J = 7.2 Hz, 2 H), 1.95 (quint, J = 2.8 Hz, 2 H).

(Synthesis of Intermediate Compound 1D)

To a tetrahydrofuran (150 mL) solution of compound 1C (16.0 g, 31.7 mmol), a normal butyl lithium hexane solution (2.5 M, 14.0 mL, 34.9 mmol) was added at −78 ° C., and the mixture was stirred for 1.5 hours. Compound 1B (4.8 g, 30.2 mmol) was added to the reaction mixture, and the mixture was stirred for 30 minutes while raising the temperature to 0 ° C., and then stirred at room temperature for 16 hours.
Ice water (100 mL) was added, extracted with dichloromethane (100 mL × 3), and dried over sodium sulfate. By purification by column chromatography (pentane / ethyl acetate = 1/1), Compound 1D was obtained. Yield 4.3g.
1H NMR (CDCl3, ppm): 7.53 (dd, J = 4.0, 2.8 Hz, 2 H), 7.49 (dd, J = 2.4, 2.0 Hz, 1 H), 7.46 (dd, J = 2.0, 1.6 Hz, 1 H), 7.43 (d, J = 1.6 Hz, 3 H), 7.40 (d, J = 1.6 Hz, 2 H), 7.32 (d, J = 2.4 Hz, 1 H), 7.18 (m, 6 H), 7.00 (m, 2 H), 6.93 (m, 2 H), 5.01 (br, 1 H), 4.43 (s, 2 H), 4.39 (d, J = 6.0 Hz, 2 H), 3.09 (dd, J = 6.0, 3.6 Hz, 2 H), 2.58 (br, 1 H), 1.93-1.78 (m, 4 H), 1.38-1.36 (m, 54 H).

(Synthesis of Compound 1 and Compound 2)

To a solution of compound 1D (0.50 g, 0.52 mmol) in tetrahydrofuran (10 mL) was added sodium borohydride (39.8 mg, 1.05 mmol) at room temperature, and the mixture was stirred for 16 hours. After the reaction, an aqueous ammonium chloride solution (20 mL) was added, extracted with ethyl acetate (20 mL × 3), dried over sodium sulfate, and the solvent was distilled off. The crude yield was 0.5 g and the LCMS purity was 62%. Compound 1 and Compound 2 were obtained by purification by column chromatography.
Compound 1.1H NMR (CDCl3, ppm): 7.46 (d, J = 1.6 Hz, 2 H), 7.44 (d, J = 2.0 Hz, 4 H), 7.42 (d, J = 2.4 Hz, 2 H), 7.33 (d, J = 2.4 Hz, 2 H), 7.20 (m, 6 H), 7.01 (m, 4 H), 5.01 (br, 2 H), 4.40 (dd, J = 12.8, 10.8 Hz, 4 H ), 2.31 (br, 2 H), 1.89 (br, 4 H), 1.54 (br, 2 H), 1.38 (s, 18 H), 1.36 (s, 36 H).
Compound 2.1 1H NMR (CDCl3, ppm): 7.47 (m, 2 H), 7.43 (m, 6 H), 7.33 (d, J = 2.4 Hz, 2 H), 7.22 (m, 6 H), 7.01 ( m, 4 H), 5.04 (dd, J = 8.8, 4.4 Hz, 2 H), 4.41 (dd, J = 16.8, 10.4 Hz, 4 H), 2.38 (br, 2 H), 1.9-1.6 (m, 6 H), 1.38 (s, 18 H), 1.36 (s, 36 H).

[Synthesis Example 2] Synthesis of Diol Compound 3 (Synthesis of Intermediate Compound 3B)

To a solution of compound 3A (0.50 g, 3.60 mmol) in acetone (10 mL) was added potassium carbonate (0.50 g, 3.60 mmol) and methyl iodide (0.70 g, 4.80 mmol) at 0 ° C. Stir at 0 ° C. for 3 hours.
The reaction was cooled to room temperature and filtered. The solid obtained by filtration was extracted with ethyl acetate (10 mL × 3) and concentrated with the filtrate to obtain a light yellow oily intermediate compound 3B. The yield was 94% with a yield of 0.5 g.
1H NMR (CDCl3, ppm): 7.53 (d, J = 2.4 Hz, 1 H), 7.44 (dd, J = 1.6, 2.0 Hz, 1 H), 7.41 (d, J = 2.0 Hz, 1 H), 7.32 (d, J = 2.4 Hz, 1 H), 3.45 (s, 3 H), 1.38 (s, 18 H), 1.34 (s, 9 H).

(Synthesis of Intermediate Compound 3C)

To a solution of compound 3B (8.0 g, 18.5 mmol) in tetrahydrofuran (80 mL) was added a normal butyl lithium hexane solution (2.5 M, 8.5 mL, 21.3 mmol) at −78 ° C., and the mixture was stirred for 2 hours. Compound 1B (1.50 g, 9.5 mmol) was added to the reaction solution, and the mixture was stirred at room temperature for 12 hours. Ice water (60 mL) was added, extracted with ethyl acetate (100 mL × 3), and dried over sodium sulfate. Purification by column chromatography (pentane / ethyl acetate = 20/1) gave Compound 3C as a white solid. The yield was 13% with a yield of 1.0 g.
1H NMR (CDCl3, ppm): 7.48 (dd, J = 2.4, 7.6 Hz, 1 H), 7.43 (d, J = 2.0 Hz, 1 H), 7.40 (s, 3 H), 7.37 (m, 3 H ), 7.27 (d, J = 4.4 Hz, 1 H), 5.01 (br, 1 H), 3.37 (s, 3 H), 3.33 (s, 3 H), 3.13 (m, 2 H), 1.9-1.8 (m, 4 H), 1.37 (s, 18 H), 1.36 (s, 18 H), 1.33 (s, 18 H).

(Synthesis of Compound 3)

Sodium borohydride (0.14 g, 3.72 mmol) was added to a solution of compound 3C (1.00 g, 1.24 mmol) in tetrahydrofuran (10 mL) at room temperature, and the mixture was stirred for 24 hours. After the reaction, an aqueous ammonium chloride solution (20 mL) was added, extracted with ethyl acetate (10 mL × 3), dried over sodium sulfate, and the solvent was distilled off. 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.
1H NMR (CDCl3, ppm): 7.41 (s, 6 H), 7.35 (d, J = 2.4 Hz, 2 H), 7.27 (m, 2 H), 5.00 (br, 2 H), 3.33 (s, 6 H), 2.61 (dd, J = 5.6, 8.8 Hz, 2 H), 2.0-1.6 (br, 6 H), 1.37 (s, 36 H), 1.37 (s, 18 H).

Synthesis Example 3 Synthesis of Diol Compound 4 (Synthesis of Compound 4)

To a solution of 1-bromo-2-phenoxybenzene (6.0 g, 24.1 mmol) in tetrahydrofuran (60 mL) was added a normal butyl lithium hexane solution (2.5 M, 10.6 mL, 25.6 mmol) at -78 ° C. Stir at room temperature for 2 hours. A solution of phthalaldehyde (1.52 g, 11.4 mmol) in tetrahydrofuran (10 mL) was added to the reaction solution at −78 ° C., and the mixture was stirred at room temperature for 16 hours. Ice water (50 mL) was added, extracted with ethyl acetate (40 mL × 3), and dried over sodium sulfate. Purification by column chromatography (pentane / ethyl acetate = 20/1) gave Compound 4 as a white solid. Yield 0.7g.
1H NMR (DMSO-d6, ppm): 7.45 (m, 2 H), 7.37 (m, 2 H), 7.3-7.1 (m, 8 H), 7.05 (m, 4 H), 6.79 (d, J = 8.0 Hz, 4 H), 6.68 (d, J = 7.2 Hz, 2 H), 5.50 (s, 2 H).

[Synthesis Example 4] Synthesis of Diol Compound 5 (Synthesis of Intermediate Compound 5B)

  A solution of 2,6-diisopropylphenol (20.0 g, 156 mmol), 2-fluorobenzonitrile (18.9 g, 156 mmol) and potassium carbonate (23.6 g, 172 mmol) in dimethylformamide (150 mL) was heated at 120 ° C. for 16 hours. did. After the reaction, ice water (200 mL) was added, extracted with ethyl acetate (150 mL × 3), washed with saturated brine (150 mL), and dried over sodium sulfate. After filtration and concentration, purification by column chromatography (pentane) gave Compound 5B. The yield was 69% with a yield of 30.0 g.

(Synthesis of Intermediate Compound 5C)

  To a toluene (50 mL) solution of compound 5B (14.0 g, 50.2 mmol) was added DIBAL-H toluene solution (1.0 M, 60.2 mL, 60.2 mmol) at room temperature, and the mixture was stirred for 16 hours. After the reaction, ice water (100 mL) was added, extracted with ethyl acetate (100 mL × 3), and dried over sodium sulfate. After filtration, the filtrate was concentrated and purified by column chromatography (pentane / ethyl acetate = 100/1) to obtain Compound 5C as a white solid. The yield was 7.5 g and the yield was 63%.

(Synthesis of Intermediate Compound 5D)

  Toluene solution (2.0 M, 0.95 mL, 1.90 mmol) of isopropylmagnesium chloride was added to 1-bromo-2-iodobenzene (0.44 g, 1.57 mmol) at −40 ° C., and the raw material disappeared by HPLC. Stir until confirmed. To this reaction solution was added a solution of compound 5C (0.4 g, 1.42 mmol) in tetrahydrofuran (1 mL), and the mixture was stirred at room temperature for 16 hours. After the reaction, ice water (10 mL) was added, extracted with ethyl acetate (15 mL × 3), washed with water (15 mL × 3), and dried over sodium sulfate. After filtration, the filtrate was concentrated and purified by column chromatography (pentane / ethyl acetate = 20/1) to obtain Compound 5D as a white solid. The yield was 0.49 g and the yield was 78%.

(Synthesis of Compound 5)

To a solution of compound 5D (3.3 g, 7.52 mmol) in tetrahydrofuran (30 mL), a normal butyl lithium hexane solution (2.5 M, 7.5 mL, 18.8 mmol) was added at −78 ° C., and at −78 ° C. for 2 hours. Stir. A solution of intermediate 5C (3.18 g, 11.3 mmol) in tetrahydrofuran (10 mL) was added to the reaction solution at −78 ° C., and the mixture was stirred at room temperature for 16 hours. Ice water (50 mL) was added, extracted with ethyl acetate (50 mL × 3), and dried over sodium sulfate. After filtration, the mixture was concentrated and purified by column chromatography (pentane / ethyl acetate = 10/1) to obtain Compound 5 as a white solid. The yield was 1.1 g and the yield was 22%.
1H NMR (CDCl3, ppm): 7.64 (d, J = 7.6 Hz, 2 H), 7.3-7.2 (m, 8 H), 7.2-7.1 (m, 4 H), 6.98 (m, 2 H), 6.82 (d, J = 4.0 Hz, 2 H), 6.30 (d, J = 7.6 Hz, 2 H), 3.70 (d, J = 4.0 Hz, 2 H), 2.99 (m, 2 H), 2.42 (m, 2 H), 1.11 (s, 6 H), 1.09 (d, J = 1.2 Hz, 6 H), 0.90 (s, 3 H), 0.89 (s, 3 H), 0.71 (s, 3 H), 0.70 (s, 3 H).

[Example 1]
50 μmol of tetrabenzylzirconium and diol compound 1 were weighed into a 30-mL flask sufficiently purged with nitrogen, dehydrated toluene (10 mL) was added, and this was 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 MAO (10 mmol) were introduced into the autoclave under a purified nitrogen atmosphere (total amount 700 mL). After maintaining the polymerization temperature at 50 ° C. and the ethylene pressure of 2.0 MPa, the previously prepared complex solution was injected to initiate the 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.

[Examples 2 to 5, Comparative Example 1 (ethylene polymerization)]
In Examples 2 to 5, N, N′-bis (3-tert-butyl-5--5) was synthesized with reference to compounds 2 to 5 and in Comparative Example 1 with reference to known literature (Non-Patent Document 1 described above in paragraph 0007). A polymer was produced in the same manner as in Example 1, except that methoxy-2-hydroxyphenylmethyl) -N, N′-dimethylethylenediamine (Compound 6) was used. Table 1 summarizes the polymerization conditions and the physical property evaluation results of the obtained polymer.

[Example 6 (propylene polymerization)]
20 μmoles of tetrabenzylzirconium and diol 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 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 MAO (10 mmol) were introduced into the autoclave under a purified nitrogen atmosphere (total amount 700 mL). Polymerization temperature 50
After maintaining at 0 ° C. and a propylene pressure of 1.0 MPa, the previously prepared complex solution was injected to initiate 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 matter obtained by filtration was filtered. After washing with ethanol, it was recovered by drying under reduced pressure at 80 ° C. for 3 hours.

[Examples 7 and 8]
A polymer was produced in the same manner as in Example 6 except that Compound 2 was used in Example 7 and Compound 3 was used in Example 8. Table 2 summarizes the polymerization conditions and the physical property evaluation results of the obtained polymer.

[Consideration by comparison of results of Examples and Comparative Examples]
In Examples 1 to 5, the polyethylene obtained showed a low MFR value or a molecular weight of 200,000 or more so as not to exhibit fluidity in a high-temperature molten state, whereas the polymer obtained in Comparative Example 1 had high fluidity. The result was too much. This polymer fluidity is known to have a close relationship with its molecular weight, suggesting that the polyethylene obtained in this example has a high molecular weight.
In Examples 6 to 8, it was clarified that polypropylene having a molecular weight exceeding 70,000 can be obtained.
As described above, polyethylene and polypropylene having a high molecular weight could be obtained by using the metal complex of the present invention. 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 (6)

A metal complex represented by the following general formula (2):

(In General Formula (2), Q1 to Q3 are each independently a divalent hydrocarbon group having 1 to 20 carbon atoms, a divalent hydrocarbon group having 1 to 20 carbon atoms substituted with a hydroxyl group, and carbon. A divalent hydrocarbon group having 2 to 20 carbon atoms substituted with an alkoxy group having 1 to 10 carbon atoms, a divalent hydrocarbon group having 4 to 20 carbon atoms substituted with a silyl group having 3 to 18 carbon atoms, halogen The substituent selected from the group which consists of a C1-C20 bivalent hydrocarbon group substituted by the atom is shown.
Q4 and Q5 are each independently a hydrogen atom, a halogen 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 an alkoxy group having 1 to 10 carbon atoms. A group consisting of a hydrocarbon group having 2 to 20 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, or a silyl group substituted with a hydrocarbon group having 1 to 20 carbon atoms. The substituent selected from more is shown.
T1 and T2 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 amino group, and a halogen.
M represents a metal atom selected from the group consisting of 4 to 10 group transition metals, and X1 and X2 each independently represent a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a carbon atom having 1 to 10 carbon atoms. And a substituent selected from the group consisting of an alkoxy group having 6 to 20 carbon atoms and an aryloxy group or halogen. ) An olefin polymerization catalyst component comprising the metal complex according to claim 1 . An olefin polymerization catalyst comprising the following components (A) and (B), and (C) as necessary.
Component (A): Metal complex according to claim 1 Component (B): Compound or ion-exchange layered silicate that reacts with component (A) to form an ion pair Component (C): Organoaluminum compound 4. The olefin polymerization catalyst according to claim 3, wherein the component (B) is an aluminoxane. 4. The olefin polymerization catalyst according to claim 3, 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 3 to 5 .