JP2018002803A - Manufacturing method of catalyst - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a manufacturing method of a catalyst capable of manufacturing a catalyst which is a metallocene compound by using a ligand with a specific structure containing a fluorene skeleton at high purity and high yield.SOLUTION: A catalyst is manufactured by a method including: a process (I) for reacting a ligand with a specific structure containing a fluorene skeleton and an organic lithium compound with a specific structure of 2.2 to 3.8 mol equivalent based on the ligand; a process (II) for reacting a Ti compound, a Zr compound or an Hf compound having a halogen atom or the like of 1 mol equivalent or more based on the ligand with a product of the process (I); a process (III) for reacting a product of the process (II) and an organic lithium compound with a specific structure so that total of the amount of the organic lithium compound used in the process (I) and the amount of the organic lithium compound used in the process (III) is 4 mol equivalent or more based on the ligand.SELECTED DRAWING: None

Description

  The present invention relates to a method for producing a catalyst.

Conventionally, so-called metallocene catalysts in which various ligands are coordinated to metals have been widely used as catalysts for the polymerization of monomer compounds having unsaturated double bonds. Specifically, for example, a catalyst having the following structure is known as a catalyst that favorably promotes the copolymerization of α-olefin and norbornene (see Non-Patent Document 1).

Note that the catalyst having the above structure described in Non-Patent Document 1 includes a plurality of complexes having different hapto numbers and different coordination forms of Ti and fluorene ligand depending on the equilibrium, as shown below. Can be included. Here, when a fluorene ligand is used, the hapto number ranges from 1 to 5.
In the following, an equilibrium is shown between a complex having a hapto number of 5 (η ⁵ ), a complex having a hapto number of 3 (η ³ ), and a complex having a hapto number of 1 (η ¹ ).

As a method for producing a catalyst having the above structure, a Grignard reagent having a methyl group such as methylated alkali metal compound such as methyl lithium or methylmagnesium bromide with respect to a ligand having the following structure (ligand): After reacting 4 mol equivalents or more, a method of reacting the product of such reaction with a metal compound such as TiCl ₄ has been proposed (see Patent Document 1). Patent Document 1 describes a general formula including a ligand having the following structure.
In Patent Document 1, 4 molar equivalent which is the lower limit of the amount of methyllithium or methylmagnesium bromide used is the minimum stoichiometrically required when a catalyst having the above structure is produced using a ligand having the following structure. Is the amount. Moreover, in patent document 1, manufacture of a catalyst is implemented by operation in one pot.

JP-T-2001-516367

Living polymerization of olefins with ansa-dimethylsilylene (fluorenyl) (amido) dimethyltitanium-based catalysts Takeshi ShionoPolymer, Journal 43. 331-351 Stereospecific polymerization of propylene with group 4 ansa-fluorenylamide dimethyl complexes Takeshi Shiono et al. Journal of Organometallic Chemistry, 2006, vol. 691, p. 193-201

The method described in Patent Document 1 is certainly a method that can produce a metallocene catalyst in a high yield. However, in the case of producing a catalyst having the above structure described in Non-Patent Document 1 or a catalyst having a structure similar to the catalyst, the method described in Patent Document 1 does not necessarily have a good yield and high purity. The catalyst cannot be produced.
Non-Patent Document 2 discloses a method for producing a catalyst having the structure described in Non-Patent Document 1 by reacting 5.3 molar equivalents of methyllithium with a ligand and then reacting TiCl _4. Have been described. However, even with the method described in Non-Patent Document 2, it is difficult to produce a high-purity catalyst in high yield. The specific method described in Non-Patent Document 2 is included in the method described in Patent Document 1.

  The present invention has been made in view of the above problems, and uses a ligand having a specific structure containing a fluorene skeleton to produce a catalyst that is a metallocene compound with high purity and high yield. It aims to provide a method.

The present inventors have a step (I) of reacting a ligand having a specific structure containing a fluorene skeleton with an organolithium compound having a specific structure of 2.2 to 3.8 molar equivalents relative to the ligand. In the step (II) and the step (I), the product of the step (I) is reacted with a Ti compound, a Zr compound, or a Hf compound having a halogen atom or the like at least 1 molar equivalent with respect to the ligand. The product of the step (II) is identified so that the total amount of the organolithium compound used and the amount of the organolithium compound used in the step (III) is 4 molar equivalents or more with respect to the ligand. The present invention has been completed by finding that the above-mentioned problems can be solved by a method comprising the step (III) of reacting an organolithium compound having a structure of
More specifically, the present invention provides the following.

（式（１）中、Ｒ^１、Ｒ^２、Ｒ^３、及びＲ^４は、それぞれ独立に、ヘテロ原子を含んでいてもよい炭素原子数１〜２０の炭化水素基であり、Ｒ^１及びＲ^２は、それぞれＣ−Ｓｉ結合、Ｏ−Ｓｉ結合、Ｓｉ−Ｓｉ結合、又はＮ−Ｓｉ結合によりケイ素原子に結合し、Ｒ^３はＣ−Ｎ結合、Ｏ−Ｎ結合、Ｓｉ−Ｎ結合、又はＮ−Ｎ結合により窒素原子に結合し、Ｒ^４はＣ−Ｍ結合により金属原子Ｍに結合し、Ｒ^５及びＲ^６は、それぞれ独立に、ヘテロ原子を含んでいてもよい炭素原子数１〜２０の有機置換基、又は無機置換基であり、ｍ及びｎは、それぞれ独立に０〜４の整数であり、Ｒ^５及びＲ^６がそれぞれ複数である場合、複数のＲ^５及びＲ^６は異なる基であってもよく、複数のＲ^５のうちの２つの基、又は複数のＲ^６のうちの２つの基が芳香環上の隣接する位置に結合する場合、当該２つの基が相互に結合して環を形成してもよく、Ｍは、Ｔｉ、Ｚｒ、又はＨｆである。）
で表される触媒の製造方法であって、
（Ｉ）下記式（１ａ）：

（式（１ａ）中、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^５、Ｒ^６、ｍ、及びｎについて、前記の通り。）
で表される配位子を、配位子に対して２．２〜３．８モル当量の下記式（１ｂ）：
ＬｉＲ^４・・・（１ｂ）
（式（１ｂ）中、Ｒ^４は、前記の通りであり、Ｃ−Ｌｉ結合によりリチウム原子に結合する。）
で表される化合物と反応させる工程と、
（ＩＩ）工程（Ｉ）で得られる生成物を、配位子に対して１モル当量以上の下記式（１ｃ）：
ＭＲ^７ _４・・・（１ｃ）
（式（１ｃ）中、Ｍは、前記の通りであり、Ｒ^７は、ハロゲン原子、又は−ＯＲ^８で表される基であり、Ｒ^８は、ヘテロ原子を有してもよい炭素原子数１〜２０の炭化水素基であり、Ｒ^８はＣ−Ｏ結合により酸素原子に結合する。）
で表される化合物と反応させる工程と、
（ＩＩＩ）工程（Ｉ）で用いた式（１ｂ）で表される化合物の量と、工程（ＩＩＩ）で用いる式（１ｂ）で表される化合物の量との合計が、配位子に対して４モル当量以上であるように、工程（ＩＩ）の生成物と、式（１ｂ）で表される化合物とを反応させる工程と、を含む、触媒の製造方法。 (1) The following formula (1):

(In the formula ^(1), R ^1, R 2, ^{R 3,} and ^{R 4} are each independently a hydrocarbon group which may having 1 to 20 carbon atoms which may contain a hetero atom, ^{R 1} and R ² is bonded to a silicon atom by a C—Si bond, an O—Si bond, a Si—Si bond, or an N—Si bond, respectively, and R ³ is a C—N bond, an O—N bond, a Si—N bond, or R ⁴ is bonded to the metal atom M by a C—M bond, and R ⁵ and R ⁶ are each independently a carbon atom number 1 to 1 which may contain a hetero atom. 20 organic substituents or inorganic substituents, m and n are each independently an integer of 0 to 4, and when R ⁵ and R ⁶ are plural, the plural R ⁵ and R ⁶ are different. ^{May be} a group, two of a plurality of R ⁵ , or 2 of a plurality of R ⁶ When two groups are bonded to adjacent positions on the aromatic ring, the two groups may be bonded to each other to form a ring, and M is Ti, Zr, or Hf.)
A method for producing a catalyst represented by:
(I) The following formula (1a):

(In formula (1a), R ¹ , R ² , R ³ , R ⁵ , R ⁶ , m, and n are as described above.)
The ligand represented by the following formula (1b): 2.2 to 3.8 molar equivalents relative to the ligand:
LiR ⁴ (1b)
(In formula (1b), R ⁴ is as described above, and is bonded to a lithium atom by a C—Li bond.)
Reacting with a compound represented by:
(II) The product obtained in the step (I) is represented by the following formula (1c) of 1 molar equivalent or more based on the ligand:
MR ⁷ ₄ (1c)
(In Formula (1c), M is as described above, R ⁷ is a halogen atom or a group represented by —OR ⁸ , and R ⁸ is the number of carbon atoms that may have a hetero atom. 1 to 20 hydrocarbon groups, and R ⁸ is bonded to an oxygen atom by a C—O bond.)
Reacting with a compound represented by:
(III) The sum of the amount of the compound represented by formula (1b) used in step (I) and the amount of the compound represented by formula (1b) used in step (III) is based on the ligand. And a step of reacting the product of step (II) with the compound represented by formula (1b) so as to be 4 molar equivalents or more.

で表される化合物である、（１）に記載の触媒の製造方法。 (2) The ligand is represented by the following formula (1a-1):

The method for producing a catalyst according to (1), which is a compound represented by the formula:

(3) The method for producing a catalyst according to (1) or (2), wherein the compound represented by the formula (1c) is TiCl ₄ .

  ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of the catalyst which can manufacture the catalyst which is a metallocene compound with high purity and a high yield using the ligand of the specific structure containing a fluorene skeleton can be provided.

≪Method for producing catalyst≫
In the method for producing a catalyst according to the present invention, a catalyst having a structure represented by the formula (1) described below is produced.
Moreover, the method for producing a catalyst according to the present invention includes:
Step (I), which is a step of reacting a ligand represented by the formula (1a) and a lithium compound represented by the formula (1b), respectively,
Step (II), which is a step of reacting the product obtained in Step (I) with a metal compound represented by Formula (1c) described later,
Step (III), which is a step of reacting the product obtained in Step (II) with the lithium compound represented by Formula (1b).
Hereinafter, the catalyst, step (I), step (II), step (III), and other steps will be described.

<Catalyst>
First, the catalyst produced by the method of the present invention will be described. What is produced by the method of the present invention is a catalyst having a structure represented by the following formula (1) including a ligand having a fluorene skeleton.

In formula (1), R ¹ , R ² , R ³ and R ⁴ are each independently a hydrocarbon group having 1 to 20 carbon atoms which may contain a hetero atom.
R ¹ and R ² are each bonded to a silicon atom by a C—Si bond, an O—Si bond, a Si—Si bond, or an N—Si bond.
R ³ is bonded to the nitrogen atom through a C—N bond, an O—N bond, a Si—N bond, or an NN bond.
R ⁴ is bonded to the metal atom M by a C—M bond.
R ⁵ and R ⁶ are each independently an organic or inorganic substituent having 1 to 20 carbon atoms that may contain a hetero atom, and m and n are each independently an integer of 0 to 4 It is.
When R ⁵ and ^{R 6} are a plurality each of the plurality of ^{R 5} and ^{R 6} may be different groups.
When two groups out of a plurality of R ⁵ or two groups out of a plurality of R ⁶ are bonded to adjacent positions on an aromatic ring, the two groups are bonded to each other to form a ring. Also good.
M is Ti, Zr, or Hf.

  In addition, the metal atom M in Formula (1) can take arbitrary coordination forms with the ligand which has a fluorene skeleton in the range of a hapto number 1-5.

R ¹ , R ² , R ³ and R ⁴ are each independently a hydrocarbon group having 1 to 20 carbon atoms which may contain a hetero atom.
When a hydrocarbon group contains a hetero atom, the kind of hetero atom is not specifically limited in the range which does not inhibit the objective of this invention. Specific examples of the hetero atom include an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, a silicon atom, a selenium atom, and a halogen atom.

When the hydrocarbon group includes a hetero atom, the number of hetero atoms is not particularly limited.
When the hydrocarbon group contains a hetero atom, the total of the number of carbon atoms and the number of hetero atoms is preferably 30 or less, more preferably 25 or less, and particularly preferably 20 or less.
When the hydrocarbon group includes a hetero atom, the number of hetero atoms is preferably 10 or less, more preferably 5 or less, and particularly preferably 3 or less.

Examples of the bond containing a hetero atom that the hydrocarbon group may contain include —O—, —C (═O) —, —C (═O) —O—, and —C (═O) —O—. C (= O)-, -OC (= O) -O-, -C (= O) -N <,> N-C (= O) -N <, -S-, -S (= O )-, -S (= O) _2- , -S-S-, -C (= O) -S-, -C (= S) -O-, -C (= S) -S-, -C. (= S) -N <, -N =, -N <, -N = N-, = N-O-, = N-S-, = N-N <, = N-Se-, -S (= O) _2- N <, -C = N-O-, -P <, -P (= O) < _, -Se- _, -Se (= O)-,> Si <, and a siloxane bond.
The hydrocarbon group may contain a bond containing these heteroatoms alone or in combination of two or more.

R ¹ and R ² are each bonded to a silicon atom by a C—Si bond, an O—Si bond, a Si—Si bond, or an N—Si bond.
Preferable examples of R ¹ and R ² bonded to a silicon atom through an O—Si bond include a group represented by —OR and —O—C (═O) —R.
Preferable examples of R ¹ and R ² bonded to the silicon atom by a Si—Si bond include —SiR ₃ , —Si (OR) R ₂ , —Si (OR) ₂ R, and —Si (OR ₃ ). And the group represented.
Preferable examples of R ¹ and R ² bonded to the silicon atom by an N—Si bond include groups represented by —NHR and —NR ₂ .
Here, each of the above R is a hydrocarbon group.

R ³ is bonded to the nitrogen atom through a C—N bond, an O—N bond, a Si—N bond, or an N—N bond.
Preferable examples of R ³ bonded to a nitrogen atom by an O—N bond include a group represented by —OR and —O—C (═O) —R.
Preferable examples of R ³ bonded to a nitrogen atom by a Si—N bond are represented by —SiR ₃ , —Si (OR) R ₂ , —Si (OR) ₂ R, and —Si (OR ₃ ). Groups.
Preferable examples of R ³ bonded to a nitrogen atom by an NN bond include groups represented by —NHR and —NR ₂ .
Here, each of the above R is a hydrocarbon group.

R ¹ and R ² are preferably the same group because preparation and availability of the compound used as the ligand are easy.

As R ¹ , R ² , R ³ , and R ⁴ , a hydrocarbon group that does not contain a hetero atom is preferable because of excellent chemical stability.
Examples of the hydrocarbon group include a linear or branched alkyl group, a linear or branched unsaturated aliphatic hydrocarbon group which may have a double bond and / or a triple bond, and cycloalkyl. Group, cycloalkylalkyl group, aromatic hydrocarbon group, and aralkyl group are preferred.

  Specific examples of the linear or branched alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n- Pentyl group, isopentyl group, tert-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group , N-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group, and n-icosyl group.

Preferred examples of the linear or branched unsaturated aliphatic hydrocarbon group which may have a double bond and / or a triple bond include specific examples of the linear or branched alkyl group. In the group, one or more single bonds are replaced with double bonds and / or triple bonds.
More preferably, a vinyl group, an allyl group, 1-propenyl group, 3-butenyl group, 2-butenyl group, 1-butenyl group, ethenyl group, and propargyl group are mentioned.

  Specific examples of the cycloalkyl group include cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecyl group, cycloundecyl group, cyclododecyl group, cyclotridecyl group, Examples include a cyclotetradecyl group, a cyclopentadecyl group, a cyclohexadecyl group, a cycloheptadecyl group, a cyclooctadecyl group, a cyclononadecyl group, and a cycloicosyl group.

  Specific examples of the cycloalkylalkyl group include a cyclopropylmethyl group, a cyclobutylmethyl group, a cyclopentylmethyl group, a cyclohexylmethyl group, a cycloheptylmethyl group, a cyclooctylmethyl group, a cyclononylmethyl group, a cyclodecylmethyl group, a cyclounone group. Decylmethyl group, cyclododecylmethyl group, cyclotridecylmethyl group, cyclotetradecylmethyl group, cyclopentadecylmethyl group, cyclohexadecylmethyl group, cycloheptadecylmethyl group, cyclooctadecylmethyl group, cyclononadecylmethyl group, 2-cyclopropylethyl group, 2-cyclobutylethyl group, 2-cyclopentylethyl group, 2-cyclohexylethyl group, 2-cycloheptylethyl group, 2-cyclooctylethyl group, 2-cyclononylethyl group, 2- Chlodecylethyl group, 2-cycloundecylethyl group, 2-cyclododecylethyl group, 2-cyclotridecylethyl group, 2-cyclotetradecylethyl group, 2-cyclopentadecylethyl group, 2-cyclohexadecylethyl group Group, 2-cycloheptadecylethyl group, 2-cyclooctadecylethyl group, 3-cyclopropylpropyl group, 3-cyclobutylpropyl group, 3-cyclopentylpropyl group, 3-cyclohexylpropyl group, 3-cycloheptylpropyl group 3-cyclooctylpropyl group, 3-cyclononylpropyl group, 3-cyclodecylpropyl group, 3-cycloundecylpropyl group, 3-cyclododecylpropyl group, 3-cyclotridecylpropyl group, 3-cyclotetradecyl group Propyl group, 3-cyclopentadecylpropyl group, -Cyclohexadecylpropyl group, 3-cycloheptadecylpropyl group, 4-cyclopropylbutyl group, 4-cyclobutylbutyl group, 4-cyclopentylbutyl group, 4-cyclohexylbutyl group, 4-cycloheptylbutyl group, 4- Cyclooctylbutyl group, 4-cyclononylbutyl group, 4-cyclodecylbutyl group, 4-cyclododecylbutyl group, 4-cyclotridecylbutyl group, 4-cyclotetradecylbutyl group, 4-cyclopentadecylbutyl group, And 4-cyclohexadecylbutyl group.

  Specific examples of the aromatic hydrocarbon group include phenyl group, o-tolyl group, m-tolyl group, p-tolyl group, 2,3-dimethylphenyl group, 2,4-dimethylphenyl group, 2,5-dimethyl group. Phenyl group, 2,6-dimethylphenyl group, 3,4-dimethylphenyl group, 3,5-dimethylphenyl group, 2,3,4-trimethylphenyl group, 2,3,5-trimethylphenyl group, 2,3 , 6-trimethylphenyl group, 2,4,5-trimethylphenyl group, 2,4,6-trimethylphenyl group, 3,4,5-trimethylphenyl group, o-ethylphenyl group, m-ethylphenyl group, p -Ethylphenyl group, o-isopropylphenyl group, m-isopropylphenyl group, p-isopropylphenyl group, o-tert-butylphenyl group, 2,3-diisopropylphenyl Nyl group, 2,4-diisopropylphenyl group, 2,5-diisopropylphenyl group, 2,6-diisopropylphenyl group, 3,4-diisopropylphenyl group, 3,5-diisopropylphenyl group, 2,6-di-tert -Butylphenyl group, 2,6-di-tert-butyl-4-methylphenyl group, α-naphthyl group, β-naphthyl group, biphenyl-4-yl group, biphenyl-3-yl group, biphenyl-2-yl Group, anthracen-1-yl group, anthracen-2-yl group, anthracen-9-yl group, phenanthren-1-yl group, phenanthren-2-yl group, phenanthren-3-yl group, phenanthren-4-yl group Phenanthren-9-yl group, pyren-1-yl group, pyren-2-yl group, pyren-3-yl group, and pyrene-4 Yl group.

  Specific examples of the aralkyl group include benzyl group, phenethyl group, 1-phenylethyl group, 3-phenylpropyl group, 2-phenylpropyl group, 1-phenylpropyl group, 2-phenyl-1-methylethyl group, 1- Phenyl-1-methylethyl group (cumyl group), 4-phenylbutyl group, 3-phenylbutyl group, 2-phenylbutyl group, 1-phenylbutyl group, 3-phenyl-2-methylpropyl group, 3-phenyl- 1-methylpropyl group, 2-phenyl-1-methylpropyl group, 2-methyl-1-phenylpropyl group, 2-phenyl-1,1-dimethylethyl group, 2-phenyl-2,2, -dimethylethyl group , Α-naphthylmethyl group, β-naphthylmethyl group, 2-α-naphthylethyl group, 2-β-naphthylethyl group, 1-α-naphthylethyl group, and A 1-β-naphthylethyl group may be mentioned.

Among the groups described above, R ¹ and R ² are preferably an alkyl group having 1 to 20 carbon atoms and an aromatic hydrocarbon group having 6 to 20 carbon atoms, and an alkyl group having 1 to 10 carbon atoms. And an aromatic hydrocarbon group having 6 to 10 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms and a phenyl group, and particularly preferably an alkyl group having 1 to 4 carbon atoms.

R ³ includes an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms, and an aralkyl group having 7 to 20 carbon atoms. preferable.

R ⁴ includes an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms, and Aralkyl groups having 7 to 20 carbon atoms are preferred.

In formula (1), R ⁵ and R ⁶ are each independently an organic substituent having 1 to 20 carbon atoms which may contain a hetero atom, or an inorganic substituent, and m and n are each independently It is an integer of 0-4.
When R ⁵ and ^{R 6} are a plurality each of the plurality of ^{R 5} and ^{R 6} may be different groups.

The organic substituent is not particularly limited as long as it is an organic group that is conventionally known to be substituted on the aromatic ring and does not inhibit the catalyst formation reaction represented by the above formula (1).
Examples of such an organic group include a group having 1 to 20 carbon atoms which may contain a heteroatom, and which does not inhibit the catalyst formation reaction represented by the above formula (1).

  When a hydrocarbon group contains a hetero atom, the kind of hetero atom is not specifically limited in the range which does not inhibit the objective of this invention. Specific examples of the hetero atom include an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, a silicon atom, a selenium atom, and a halogen atom.

When the hydrocarbon group includes a hetero atom, the number of hetero atoms is not particularly limited.
When the hydrocarbon group contains a hetero atom, the total of the number of carbon atoms and the number of hetero atoms is preferably 30 or less, more preferably 25 or less, and particularly preferably 20 or less.
When the hydrocarbon group includes a hetero atom, the number of hetero atoms is preferably 10 or less, more preferably 5 or less, and particularly preferably 3 or less.
Examples of the bond containing a hetero atom that may be contained in the hydrocarbon group include the bonds described for R ^{1 to} R ⁴ .

Examples of the organic substituent include an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, and an aliphatic acyl group having 2 to 20 carbon atoms. Benzoyl group, α-naphthylcarbonyl group, β-naphthylcarbonyl group, aromatic hydrocarbon group having 6 to 20 carbon atoms, and aralkyl group having 7 to 20 carbon atoms.
Among these organic substituents, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, and an aliphatic acyl having 2 to 6 carbon atoms Group, benzoyl group, phenyl group, benzyl group, and phenethyl group are preferred.
Among the organic substituents, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, methoxy group, ethoxy group, n-propyloxy group , Isopropyloxy group, n-butyloxy group, isobutyloxy group, sec-butyloxy group, tert-butyloxy group, acetyl group, propionyl group, butanoyl group, and phenyl group are more preferable.

The inorganic substituent is not particularly limited as long as it is an inorganic group that is conventionally known to be substituted on the aromatic ring and does not inhibit the catalyst formation reaction represented by the above formula (1).
Specific examples of the inorganic group include a halogen atom, a nitro group, and a cyano group.

When two groups out of a plurality of R ⁵ or two groups out of a plurality of R ⁶ are bonded to adjacent positions on an aromatic ring, the two groups are bonded to each other to form a ring. Also good. Such a ring is a condensed ring that is condensed with an aromatic ring contained in the fluorene skeleton in the formula (1). The condensed ring may be an aromatic ring, an aliphatic ring or an aliphatic ring. The condensed ring may have a hetero atom such as an oxygen atom, a nitrogen atom, and a sulfur atom in the ring.

Specific examples of the fluorene skeleton having a condensed ring formed by two R ⁵ and / or two R ⁶ include the following skeleton.

  In formula (1), M is Ti, Zr, or Hf, and Ti is preferable.

Preferable examples of the catalyst represented by the formula (1) described above include catalysts having the following structure.

（式（１ａ）中、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^５、Ｒ^６、ｍ、及びｎについて、前記の通り。）
で表される配位子を、前記配位子に対して２．２〜３．８モル当量の下記式（１ｂ）：
ＬｉＲ^４・・・（１ｂ）
（式（１ｂ）中、Ｒ^４は、前記の通りであり、Ｃ−Ｌｉ結合によりリチウム原子に結合する。）
で表される化合物と反応させる。 <Process (I)>
In order to produce the catalyst represented by the formula (1), first in the step (I), the following formula (1a):

(In formula (1a), R ¹ , R ² , R ³ , R ⁵ , R ⁶ , m, and n are as described above.)
The ligand represented by the formula (1b) of 2.2 to 3.8 molar equivalents relative to the ligand:
LiR ⁴ (1b)
(In formula (1b), R ⁴ is as described above, and is bonded to a lithium atom by a C—Li bond.)
It is made to react with the compound represented by these.

（式（１ｄ）中、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^５、Ｒ^６、ｍ、及びｎについて、前記の通り。） The intermediate represented by the following formula (1d) is generated by the reaction proceeding in the step (I).

(In formula (1d), R ¹ , R ² , R ³ , R ⁵ , R ⁶ , m, and n are as described above.)

The structure of the ligand represented by the formula (1a) is appropriately selected according to the structure of the catalyst to be produced. Among the ligands represented by the formula (1a), a ligand represented by the following formula (1a-1) is preferable from the viewpoint of good reactivity, easy synthesis and availability, and low cost. .

In step (I), 2.2 to 3.8 molar equivalents of the lithium compound represented by the above formula (1b) are reacted with the ligand represented by the formula (1a).
By reacting an amount of the lithium compound in such a range with the ligand represented by the formula (1a), a high-purity catalyst can be finally produced in a high yield.
The lower limit of the amount of the compound represented by formula (1b) in step (I) is, for example, preferably 2.3 molar equivalents, more preferably 2.4 molar equivalents, and particularly preferably 2.6 molar equivalents.
The upper limit of the amount of the compound represented by formula (1b) in step (I) is, for example, preferably 3.7 molar equivalents, more preferably 3.6 molar equivalents, and particularly preferably 3.4 molar equivalents.

Regarding the lithium compound represented by the formula (1b), as described above, R ⁴ includes an alkyl group having 1 to 20 carbon atoms, a trialkylsilylalkyl group having 4 to 20 carbon atoms, and 2 to 20 carbon atoms. Alkenyl groups, cycloalkyl groups having 3 to 20 carbon atoms, aromatic hydrocarbon groups having 6 to 20 carbon atoms, and aralkyl groups having 7 to 20 carbon atoms are preferable.

  Preferable specific examples of the lithium compound represented by the formula (1b) include methyl lithium, ethyl lithium, n-propyl lithium, isopropyl lithium, n-butyl lithium, isobutyl lithium, sec-butyl lithium, tert-butyl lithium, Examples include n-pentyl lithium, n-hexyl lithium, trimethylsilylmethyl lithium, phenyl lithium, p-tolyl lithium, m-tolyl lithium, o-tolyl lithium, benzyl lithium, vinyl lithium, and allyl lithium.

In step (I), a solvent is usually used. The kind of solvent is not particularly limited as long as the object of the present invention is not impaired. Typically, an aprotic solvent is used.
The type of aprotic solvent is not particularly limited as long as the object of the present invention is not impaired. The aprotic solvent may be a polar solvent or a nonpolar solvent. Preferred aprotic solvents include ether solvents and hydrocarbon solvents.
Specific examples of suitable aprotic solvents include ether solvents such as diethyl ether, di-n-propyl ether, diisopropyl ether, di-n-butyl ether, tetrahydrofuran, and dioxane, pentane, hexane, heptane, and octane. And aliphatic hydrocarbon solvents such as benzene, toluene, and xylene.
Particularly preferably, an aprotic solvent containing diethyl ether is used.
Diethyl ether may be used in combination with an ether solvent other than diethyl ether, may be used in combination with an aliphatic hydrocarbon solvent, or may be used in combination with an aromatic hydrocarbon solvent.

  The amount of the solvent used is not particularly limited as long as the object of the present invention is not impaired. The amount of the solvent used is typically preferably such that the ligand molar concentration is 0.001 to 2 mol / L, more preferably 0.01 to 1 mol / L, and 0.05 to An amount of 0.5 mol / L is particularly preferred.

The temperature at which the ligand represented by the formula (1a) and the compound represented by the formula (1b) are reacted is not particularly limited as long as the object of the present invention is not impaired.
Typically, −78 to 60 ° C. is preferable, 0 to 50 ° C. is more preferable, and 10 to 40 ° C. is particularly preferable.
The reaction temperature may exceed the boiling point of the solvent. When the reaction temperature exceeds the boiling point of the solvent, the reaction may be carried out using a pressure-resistant container that can be sealed.

Although the atmosphere at the time of making the ligand represented by Formula (1a) and the compound represented by Formula (1b) react is not specifically limited, Since it is easy to suppress a side reaction, an inert gas atmosphere is preferable. .
Examples of the inert gas include nitrogen and argon.

In step (I), the time for reacting the ligand represented by the formula (1a) and the compound represented by the formula (1b) is not particularly limited.
The reaction time in step (I) varies depending on the amount of the compound represented by formula (1b), the amount of solvent used, the reaction temperature, etc., but is typically 1 to 24 hours. 4 hours is preferred.

The reaction product of the ligand represented by the formula (1a) and the compound represented by the formula (1b) obtained by the method described above is subjected to step (II).
The reaction product may be supplied to step (II) as a reaction solution of step (I), or may be supplied to step (II) in a state separated and recovered from the reaction solution of step (I). . In the point that there is no loss of the product in the separation and recovery operation, it is preferable that the reaction liquid of step (I) is subjected to step (II).
Further, the reaction solution may be concentrated or diluted as necessary before being subjected to step (II).

<Process (II)>
In the step (II), the product obtained in the step (I) is used in the following formula (1c) of 1 molar equivalent or more with respect to the above-mentioned ligand:
MR ⁷ ₄ (1c)
(In Formula (1c), M is as described above, R ⁷ is a halogen atom or a group represented by —OR ⁸ , and R ⁸ is the number of carbon atoms that may have a hetero atom. 1 to 20 hydrocarbon groups, and R ⁸ is bonded to an oxygen atom by a C—O bond.)
It is made to react with the compound represented by these.

（式（１ｅ）中、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^５、Ｒ^６、Ｒ^７、ｍ、及びｎについて、前記の通り。）
で表される中間体が生成する。
かかる中間体が、前述の式（１ｂ）で表されるリチウム化合物と反応すると、Ｒ^７がＲ^４に置き換わり、式（１）で表される触媒が生成する。 In the step (II), the following formula (1e) is obtained by reacting the intermediate represented by the above formula (1d) with the compound represented by the formula (1c):

(In formula (1e), R ¹ , R ² , R ³ , R ⁵ , R ⁶ , R ⁷ , m, and n are as described above.)
An intermediate represented by
When such an intermediate reacts with the lithium compound represented by the above formula (1b), R ⁷ is replaced with R ⁴ to produce a catalyst represented by the formula (1).

In the compound represented by the formula (1c), R ⁷ is a halogen atom. The halogen atom is not particularly limited as long as the desired reaction proceeds, but a chlorine atom or a bromine atom is preferable.
When R ⁷ is —OR ⁸ , R ⁸ is a hydrocarbon group having 1 to 20 carbon atoms that may have a hetero atom, and is bonded to an oxygen atom through a C—O bond.
As described for R ^{1 to} R ⁴ in formula (1), the hydrocarbon group having 1 to 20 carbon atoms which may have a heteroatom is bonded to an oxygen atom by a C—O bond. It is.
R ⁸ is preferably a hydrocarbon group containing no hetero atom, and is preferably an alkyl group, an aralkyl group, or an aromatic hydrocarbon group.
Preferred specific examples of —OR ⁸ include methoxy group, ethoxy group, n-propyloxy group, isopropyloxy group, n-butyloxy group, isobutyloxy group, sec-butyloxy group, tert-butyloxy group, phenoxy group, and benzyl. An oxy group is mentioned.

Preferable specific examples of the compound represented by formula _{(1c), TiCl 4, ZrCl} 4, HfCl 4, TiBr 4, ZrBr 4, HfBr 4, Ti (OMe) 4, Zr (OMe) 4, Hf (OMe ) ₄ , Ti (OEt) ₄ , Zr (OEt) ₄ , Hf (OEt) ₄ , Ti (On-Pr) ₄ , Zr (On-Pr) ₄ , Hf (On-Pr) ₄ , Ti (Oi-Pr) ) ₄ , Zr (Oi-Pr) ₄ , Hf (Oi-Pr) ₄ , Ti (OPh) ₄ , Zr (OPh) ₄ , Hf (OPh) ₄ , Ti (On-Bu) ₄ , Zr (On-Bu) ) ₄ , Hf (On-Bu) ₄ , Ti (OBn) ₄ , Zr (OBn) ₄ , and Hf (OBn) ₄ .
Among these, to obtain a point and is easy _{to, TiCl 4, ZrCl 4, HfCl} 4, TiBr 4, ZrBr 4, and HfBr ₄ is preferred from such that reactivity is _good, TiCl _4, ZrCl 4, HfCl ₄ is more preferable, and TiCl ₄ is particularly preferable.

The compound represented by the formula (1c) is used in an amount of 1 molar equivalent or more based on the amount of the ligand used in the step (I). By using the compound represented by the formula (1c) in such an amount, the side reaction in the step (II) is suppressed, and as a result, the purity and yield of the finally obtained catalyst are good.
The compound represented by the formula (1c) may be used as it is, or may be used in a state suspended or dissolved in a solvent. The compound represented by the formula (1c) is preferably used as a solution from the viewpoint of easily suppressing the side reaction in the step (II). Although the kind of solvent in which the compound represented by Formula (1c) is dissolved is not particularly limited, an aprotic solvent is preferable. As an aprotic solvent, the solvent demonstrated about process (I) can be used preferably.
The upper limit of the amount of the compound represented by formula (1c) is not particularly limited as long as the object of the present invention is not impaired. The upper limit of the amount of the compound represented by formula (1c) is preferably 1.5 molar equivalents, more preferably 1.25 molar equivalents, and particularly preferably 1 molar equivalent.
The catalyst can be produced even when the compound represented by the formula (1c) is used in excess of 1.5 molar equivalents. However, the effect of improving the yield and / or purity of the catalyst corresponding to the increase in cost is not achieved, and the purification of the catalyst may be somewhat difficult, and the compound represented by the formula (1c) is 1. There is no particular need to use more than 5 molar equivalents.

  In step (II), the preferred type of solvent and the preferred range of the amount of solvent used are the same as in step (I). When the reaction product of step (I) is separated from the reaction solution of step (I) and used, the reaction product of step (I) is used in a state dissolved in a desired amount of solvent.

Regarding the reaction carried out in the step (II), the temperature is not particularly limited as long as the object of the present invention is not impaired. Typically, −78 to 60 ° C. is preferable.
The reaction temperature may exceed the boiling point of the solvent. When the reaction temperature exceeds the boiling point of the solvent, the reaction may be carried out using a pressure-resistant container that can be sealed.

The atmosphere for carrying out the reaction carried out in the step (II) is not particularly limited, but an inert gas atmosphere is preferred because side reactions are easily suppressed.
Examples of the inert gas include nitrogen and argon.

  The time for the reaction carried out in step (II) is not particularly limited. The reaction time in step (II) is typically 1 to 24 hours. From the viewpoint of preventing decomposition of the product, the reaction time is preferably not excessively long.

In step (II), a by-product salt may precipitate as the reaction proceeds. Further, the by-product salt can be precipitated by concentrating the reaction solution in step (II).
When the by-product salt is precipitated and removed by concentration, the solvent may be distilled off from the filtrate after removal of the by-product salt to obtain a residue, and the residue may be dissolved again in the solvent to precipitate the by-product salt again. The operations of obtaining such residue and reprecipitation of by-product salt may be repeated.
Removal of the deposited by-product salt is performed by a known method such as filtration or decantation.
For this reason, it is preferable to wash | clean the removed byproduct salt with a solvent, and to collect | recover the reaction product of the process (II) adhering to a byproduct salt. The washing operation of the by-product salt with the organic solvent may be performed a plurality of times as necessary.
The cleaning liquid recovered after the cleaning using the solvent is combined with the reaction liquid in the step (II) and provided to the step (III).

The reaction product of step (II) obtained by the method described above is subjected to step (III).
The reaction product may be supplied to step (III) as a reaction solution of step (II), or may be supplied to step (III) in a state separated and recovered from the reaction solution of step (II). .
From the viewpoint of easily obtaining a high-purity catalyst, it is preferable to subject the reaction product separated and recovered from the reaction solution of step (II) to step (III). Moreover, it is also preferable to use the reaction liquid of process (II) for process (III) at the point which does not have the loss of the product in a separation / recovery operation.
When the reaction product separated and recovered from the reaction liquid in step (II) is in a solid state, it is preferable to dissolve the reaction product in a solvent and then subject the resulting solution to step (III). The preferred type of solvent used for dissolving the reaction product and the preferred range of the amount of solvent used are the same as the preferred type of solvent and the preferred range of the amount of solvent described for step (I). It is.
As the solvent for dissolving the reaction product, the solvent described in the step (I) can be used, but an aromatic hydrocarbon solvent is preferable. Examples of the aromatic hydrocarbon solvent include toluene, xylene, mesitylene and the like, and toluene is preferable.
In addition, the reaction solution may be concentrated or diluted as necessary before being subjected to step (III).

<Step (III)>
In step (III), the product obtained in step (II) is reacted with the compound represented by the aforementioned formula (1b).
In the step (III), the compound represented by the formula (1b) is a coordination in which the sum of the amount used in the step (I) and the amount used in the step (III) is used in the step (I). The amount used is 4 molar equivalents or more based on the amount of the child.
The sum of the amount of the compound represented by formula (1b) used in step (I) and the amount used in step (III) is based on the amount of the ligand used in step (I). 4 molar equivalents or more are preferable, and 4.6 molar equivalents or more are more preferable.

  In step (III), the desired catalyst can be produced with high purity and high yield by using the compound represented by formula (1b) in an amount that satisfies the above conditions.

The amount of the compound represented by the formula (1b) used in the step (I), which is a condition for determining the amount of the compound represented by the formula (1b) in the step (III), and the step (III) The upper limit of the total amount used with is not particularly limited.
The upper limit of the total amount is preferably 6.5 molar equivalents, more preferably 6 molar equivalents, and particularly preferably 5.5 molar equivalents with respect to the amount of the ligand used in step (I).
The catalyst can be produced even when the compound represented by the formula (1b) is used in an amount exceeding 6.5 molar equivalents as the sum of the amount used in Step (I) and the amount used in Step (III).
However, the effect of improving the yield and / or purity of the catalyst commensurate with the increase in cost is not achieved, and the purification of the catalyst may be somewhat difficult, and the compound represented by the formula (1b) There is no particular need to use more than 6.5 molar equivalents relative to the amount of ligand used in step (I) as the sum of the amount used in (I) and the amount used in step (III).

  About the compound represented by Formula (1b), it is as having mentioned above about process (I). When the reaction product of step (II) is used separated from the reaction solution of step (II), as described above, the reaction product of step (II) is used in a state dissolved in a desired amount of solvent. Is done.

In step (III), the preferred type of solvent and the preferred range of the amount of solvent used are the same as in step (I).
Particularly preferably, an aprotic solvent containing an aromatic hydrocarbon solvent such as toluene is used. Examples of the aromatic hydrocarbon solvent include toluene, xylene, mesitylene and the like, and toluene is preferable.
An aromatic hydrocarbon solvent such as toluene may be used in combination with an ether solvent, or may be used in combination with an aliphatic hydrocarbon solvent.

Regarding the reaction carried out in step (III), the temperature is not particularly limited as long as the object of the present invention is not impaired. Typically, −78 to 60 ° C. is preferable.
The reaction temperature may exceed the boiling point of the solvent. When the reaction temperature exceeds the boiling point of the solvent, the reaction may be carried out using a pressure-resistant container that can be sealed.

The atmosphere for carrying out the reaction carried out in the step (III) is not particularly limited, but an inert gas atmosphere is preferable because side reactions are easily suppressed.
Examples of the inert gas include nitrogen and argon.

  The time for the reaction carried out in step (III) is not particularly limited. The reaction time in step (III) is typically 1 to 24 hours. The reaction time is preferably not excessively long from the viewpoint of preventing the decomposition of the product.

The catalyst having the structure represented by the formula (1) produced by the method including the step (I), the step (II) and the step (III) described above is purified or reacted as necessary. After being separated and recovered from the liquid, it is used as a catalyst for the polymerization reaction.
Since the catalyst produced through the step (I), the step (II), and the step (III) usually contains impurities such as a salt, for example, after being purified through other steps described later, the polymerization reaction It is preferable to be used for.

<Other processes>
In addition to step (I), step (II), and step (III) described above, the synthesized catalyst is recovered from the reaction solution of step (III) by performing other steps. Can do.

For example, after extracting the catalyst with an organic solvent from the residue obtained by concentrating the reaction solution in step (III), the insoluble by-product in the residue is separated from the extract containing insoluble matter by a method such as filtration, Next, a purified catalyst is obtained by precipitating the catalyst from the extract containing the catalyst.
At that time, for the purpose of catalyst purification, a so-called Grignard reagent such as methylmagnesium bromide may be added to the reaction solution of step (III) before concentrating the reaction solution obtained in step (III).
When the crystallinity of the synthesized catalyst is low, the crystallinity is improved by adding a Grignard reagent, and purification by recrystallization can be performed. In this case, after removing the solvent from the reaction solution to which the Grignard reagent has been added to obtain a residue containing a catalyst, an organic solvent is added to the obtained residue, and insoluble matter in the organic solvent is removed by filtration, decantation, etc. By separating by the method, Grignard reagent and by-products can be removed. After the addition of the organic solvent, the catalyst dissolves in the organic solvent and a by-product is precipitated. The organic solvent for dissolving the catalyst contained in the residue is preferably an aliphatic hydrocarbon solvent such as pentane, hexane, heptane, octane, etc. in that the Grignard reagent and by-products are easily precipitated.
Such a by-product removal operation may be repeated until a catalyst having a desired purity is obtained.
Although the usage-amount of a Grignard reagent is not specifically limited, 0.5-4 molar equivalent is preferable with respect to a ligand, and 1-2 molar equivalent is preferable.

As described above, the reaction liquid obtained in step (III) is concentrated, or the filtrate after removal of insoluble by-products using the Grignard reagent is concentrated to obtain catalyst crystals.
The catalyst crystals thus obtained may be used in the polymerization reaction as they are, but it is preferable to use a catalyst purified to a desired purity in the polymerization reaction.
The method for purifying the catalyst to the desired purity is not particularly limited, but typically recrystallization with an organic solvent is preferred.
As the recrystallization solvent, a solvent that can be used in step (I) to step (III) can be used. The method for precipitating crystals during recrystallization is not particularly limited, and examples thereof include methods such as cooling and concentration. After recrystallization, a purified catalyst is obtained by collecting the precipitated crystals by a method such as filtration or decantation.

The yield determined by the internal standard method by NMR (based on ethylbenzene) of the catalyst obtained through the above steps is preferably 40% or more, more preferably 45% or more, based on the amount of ligand used.
Further, the purity of the catalyst at the end of the step (III) determined by the internal standard method by NMR (ethylbenzene standard) is preferably 90% or more, and particularly preferably 95% or more. In addition, since it is the purity defined by the internal standard method by NMR, purity may exceed 100%.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these.

[Example 1]
(Process (I))
In a glove box replaced with a dry nitrogen atmosphere, 50 mL of diethyl ether and 1.56 g (5.28 mmol) of a ligand having the following structure were added to a Schlenk flask. After dissolving the ligand in diethyl ether, the Schlenk flask was charged with 12.3 mL of methyllithium in diethyl ether (1.12 M, methyllithium content: 13.8 mmol (2.6 molar equivalents to the ligand). )), The ligand and methyllithium were reacted at room temperature for 2.5 hours.

(Process (II))
50 mL of hexane and 0.58 mL of TiCl ₄ (5.29 mmol (1.0 molar equivalent (to ligand))) were added to the two-necked flask replaced with a nitrogen atmosphere.
Next, the reaction solution obtained in the step (I) was dropped into a two-necked flask using a cannula. After the dropping, the contents of the two-necked flask were stirred at room temperature for 14 hours to react the reaction product of step (I) with TiCl ₄ . A dark brown reaction liquid was obtained by the reaction.
The solvent was distilled off from the resulting reaction solution to obtain a black powder as a residue. The obtained black powder was suspended in 20 mL of toluene, and the reaction product of step (II) was extracted in toluene. Insoluble components were removed from the suspension through a glass filter. For the insoluble matter removed from the suspension, the same extraction operation was further repeated three times using 20 mL of toluene. The obtained filtrate (extract) was dried under reduced pressure to obtain 1.99 g of a reaction product of step (II).

(Step (III))
The reaction product of Step (II) and 50 mL of toluene were added to the flask, and the reaction product was dissolved in toluene.
Next, 9.4 mL of methyllithium solution in diethyl ether (1.12 M, methyllithium content: 10.5 mmol (2.0 molar equivalent (to ligand))) was added to the solution of the reaction product of step (II). Then, the reaction product of step (II) was reacted with methyllithium at room temperature for 15 hours. A catalyst having the following structure was produced by the reaction in the step (III).

(Other processes)
A diethyl ether solution of 3 mL of MeMgBr (concentration 3M, 9 mmol) was added to the reaction solution in the flask obtained in step (III). The contents of the flask were then stirred at room temperature for 1 hour.
From the contents of the flask, the solvent was distilled off under reduced pressure to obtain a residue as a black powder. The resulting black powder was suspended in 40 mL of hexane, and the catalyst was extracted into hexane. Insoluble components were removed from the suspension through a glass filter. For the insoluble components removed from the suspension, the same extraction operation was further repeated once using 40 mL of hexane and twice using 20 mL of hexane. The obtained filtrate (catalyst extract) was dried under reduced pressure to obtain 918 mg of catalyst.
The yield of the obtained catalyst determined by the internal standard method by NMR (based on ethylbenzene) relative to the amount of ligand used is 47%, and the purity of the catalyst is also determined by the internal standard method by NMR (based on ethylbenzene). Was over 99%.

NMR analysis was performed by ¹ H-NMR using a Bruker spectrometer AVANCE III 400 and using heavy toluene as a heavy solvent.
As a measurement sample tube, a J-YOUNG NMR sample tube was used.
Quantitative analysis by NMR uses ethylbenzene having a purity of 99% or more as an internal standard substance, the amount used, the peak of 2.44 ppm (triple line, 2H) of ethylbenzene, and 7.71 ppm (double line, 2H of catalyst). ) And calculating the integration ratio with the peak.

[Example 2]
1039 mg of catalyst was obtained in the same manner as in Example 1 except that the amount of methyllithium used in Step (I) was changed to 15.9 mmol (3.0 molar equivalent (to ligand)).
The yield of the obtained catalyst determined by the internal standard method by NMR (based on ethylbenzene) relative to the amount of ligand used is 53%, and the purity of the catalyst is also determined by the internal standard method by NMR (based on ethylbenzene). Was over 99%.

Example 3
1125 mg of catalyst was obtained in the same manner as in Example 1 except that the amount of methyllithium used in Step (I) was changed to 18.1 mmol (3.4 molar equivalent (to ligand)).
The yield of the obtained catalyst determined by the internal standard method by NMR (based on ethylbenzene) is 57% based on the amount of ligand used, and the purity of the catalyst is also determined by the internal standard method by NMR (based on ethylbenzene). Was over 99%.

[Comparative Example 1]
Except for changing the amount of methyllithium used to 10.5 mmol (2.0 molar equivalents (vs. ligand)), in the same manner as in Step (I) of Example 1, the ligand, methyllithium, The reaction solution was obtained.

50 mL of hexane and 0.58 mL of TiCl ₄ (5.29 mmol (1.0 molar equivalent (to ligand))) were added to the two-necked flask replaced with a nitrogen atmosphere.
Subsequently, the reaction liquid of a ligand and methyllithium was dripped in the 2 necked flask using the cannula. After the dropwise addition, the contents of the two-necked flask were stirred at room temperature for 17 hours to react the reaction product of the ligand and methyllithium with TiCl ₄ . A dark brown reaction liquid was obtained by the reaction.
The solvent was distilled off from the resulting reaction solution to obtain a black powder as a residue. The obtained black powder was suspended in 20 mL of toluene, and the reaction product was extracted in toluene. Insoluble components were removed from the suspension through a glass filter. For the insoluble matter removed from the suspension, the same extraction operation was further repeated three times using 20 mL of toluene. The obtained filtrate (extract) was dried under reduced pressure to obtain 1.90 g of a reaction product.

The reaction product obtained using TiCl ₄ and 45 mL of toluene were added to the flask, and the reaction product was dissolved in toluene.
Next, 9.4 mL of methyl lithium in diethyl ether (1.12 M, methyl lithium content: 10.5 mmol (2.0 molar equivalents (to ligand))) was added to the reaction product solution, The reaction product and methyllithium were reacted at room temperature for 12 hours to form a catalyst.

A diethyl ether solution of 3 mL of MeMgBr (concentration 3M, 9 mmol) was added to the reaction solution containing the catalyst in the flask. The contents of the flask were then stirred at room temperature for 1 hour.
From the contents of the flask, the solvent was distilled off under reduced pressure to obtain a residue as a black powder. The resulting black powder was suspended in 40 mL of hexane, and the catalyst was extracted into hexane. Insoluble components were removed from the suspension through a glass filter. For the insoluble components removed from the suspension, the same extraction operation was further repeated once using 40 mL of hexane and twice using 20 mL of hexane. The obtained filtrate (catalyst extract) was dried under reduced pressure to obtain 933 mg of catalyst.
The yield of the obtained catalyst determined by the internal standard method by NMR (based on ethylbenzene) relative to the amount of ligand used is 38%, and the purity of the catalyst is also determined by the internal standard method by NMR (based on ethylbenzene). Was 81%.

  From Comparative Example 1, when the amount of methyllithium initially reacted with the ligand is 2.0 molar equivalents relative to the ligand, a total of 4.0 molar equivalents of methyllithium is reacted relative to the ligand. It can be seen that a catalyst with excellent purity cannot be obtained in a high yield even if it is allowed to be used.

[Comparative Example 2]
Except for changing the amount of methyllithium used to 28.0 mmol (5.3 molar equivalents (vs. ligand)), in the same manner as in step (I) of Example 1, the ligand, methyllithium, The reaction solution was obtained.

50 mL of hexane and 0.58 mL of TiCl ₄ (5.29 mmol (1.0 molar equivalent (to ligand))) were added to the two-necked flask replaced with a nitrogen atmosphere.
Subsequently, the reaction liquid of a ligand and methyllithium was dripped in the 2 necked flask using the cannula. After the dropwise addition, the contents of the two-necked flask and stirred for 22 hours at room temperature, and reacted with the reaction product of ligand and methyl lithium, and TiCl _4. A dark brown reaction liquid was obtained by the reaction.
The solvent was distilled off from the resulting reaction solution to obtain a black powder as a residue. The obtained black powder was suspended in 40 mL of hexane, and the reaction product was extracted into hexane. Insoluble components were removed from the suspension through a glass filter. The same extraction operation was further repeated once using 40 mL of hexane and twice using 20 mL of hexane for the insoluble matter removed from the suspension. The obtained filtrate (extract) was dried under reduced pressure to obtain a reaction product.

To the obtained reaction product, 120 mL of hexane and a diethyl ether solution of 3 mL of MeMgBr (concentration 3M, 9 mmol) were added, followed by stirring at room temperature for 5 hours.
The solvent was distilled off under reduced pressure from the stirred solution to obtain a residue as a black powder. The resulting black powder was suspended in 40 mL of hexane, and the catalyst was extracted into hexane. Insoluble components were removed from the suspension through a glass filter. For the insoluble components removed from the suspension, the same extraction operation was further repeated once using 40 mL of hexane and twice using 20 mL. The obtained filtrate (catalyst extract) was dried under reduced pressure to obtain 958 mg of catalyst.
The yield of the obtained catalyst determined by the internal standard method by NMR (based on ethylbenzene) relative to the amount of ligand used is 39%, and the purity of the catalyst is also determined by the internal standard method by NMR (based on ethylbenzene). Was 80%.

According to Comparative Example 2, the ligand is reacted with 5.3 molar equivalents of methyllithium, which exceeds the stoichiometric minimum of 4.0 molar equivalents to obtain a catalyst of the desired structure. After that, even when TiCl ₄ is reacted, it can be seen that a catalyst having excellent purity cannot be obtained in a high yield.
Comparative Example 2 corresponds to the method described in Non-Patent Document 2.

[Comparative Example 3]
Except for changing the amount of methyllithium used to 21.1 mmol (4.0 molar equivalents (vs. ligand)), in the same manner as in step (I) of Example 1, the ligand and methyllithium The reaction solution was obtained.

50 mL of hexane and 0.58 mL of TiCl ₄ (5.29 mmol (1.0 molar equivalent (to ligand))) were added to the two-necked flask replaced with a nitrogen atmosphere.
Subsequently, the reaction liquid of a ligand and methyllithium was dripped in the 2 necked flask using the cannula. After the dropwise addition, the contents of the two-necked flask were stirred at room temperature for 17 hours to react the reaction product of the ligand and methyllithium with TiCl ₄ . A dark brown reaction liquid was obtained by the reaction.
The solvent was distilled off from the resulting reaction solution to obtain a black powder as a residue. The obtained black powder was suspended in 20 mL of toluene, and the catalyst was extracted in toluene. Insoluble components were removed from the suspension through a glass filter. For the insoluble matter removed from the suspension, the same extraction operation was further repeated three times using 20 mL of toluene. The obtained filtrate (catalyst extract) was dried under reduced pressure to obtain 2.271 g of a catalyst.
The yield of the obtained catalyst based on the amount of ligand used, determined by the internal standard method by NMR (based on ethylbenzene), was 41%.
Similarly, when the composition of the obtained catalyst was examined by NMR, the amount of the catalyst having the desired structure (Nc) in the catalyst and the intermediate represented by the above formula (1e) corresponded. The ratio (Nc: Ni) of the intermediate substance amount (Ni) in which two chlorine atoms were bonded to the titanium atom was 66:34.
That is, the catalyst obtained in Comparative Example 3 contained a large amount of intermediate and had a low purity.

According to Comparative Example 3, after reacting 4.0 mole equivalent of methyllithium, which is the minimum stoichiometric amount for obtaining a catalyst having a desired structure, with respect to a ligand, TiCl ₄ is reacted. It can be seen that the catalyst cannot be produced with good purity.

[Comparative Example 4]
In Example 1, 1064 mg of catalyst was obtained in the same manner as in Example 1 except that 1.99 g of the reaction product in the step (II) was changed to 2.271 g of the catalyst obtained in Comparative Example 3.
That is, in Comparative Example 4, 2.0 molar equivalents of methyllithium were further reacted with the ligand obtained in Comparative Example 3.
The yield of the obtained catalyst determined by the internal standard method by NMR (based on ethylbenzene) relative to the amount of ligand used is 35%, and the purity of the catalyst is also determined by the internal standard method by NMR (based on ethylbenzene). Was 65%.
According to Comparative Example 4, even if methyllithium is further reacted with the catalyst obtained in Comparative Example 3 containing a large amount of intermediate, it is difficult to produce a high-purity catalyst in high yield. I understand that.

Claims (3)

Following formula (1):

(In the formula ^(1), R ^1, R 2, ^{R 3,} and ^{R 4} are each independently a hydrocarbon group which may having 1 to 20 carbon atoms which may contain a hetero atom, ^{R 1} and R ² is bonded to a silicon atom by a C—Si bond, an O—Si bond, a Si—Si bond, or an N—Si bond, respectively, and R ³ is a C—N bond, an O—N bond, a Si—N bond, or R ⁴ is bonded to the metal atom M by a C—M bond, and R ⁵ and R ⁶ are each independently a carbon atom number 1 to 1 which may contain a hetero atom. 20 organic substituents or inorganic substituents, m and n are each independently an integer of 0 to 4, and when R ⁵ and R ⁶ are plural, the plural R ⁵ and R ⁶ are different. ^{May be} a group, two of a plurality of R ⁵ , or 2 of a plurality of R ⁶ When two groups are bonded to adjacent positions on the aromatic ring, the two groups may be bonded to each other to form a ring, and M is Ti, Zr, or Hf.)
A method for producing a catalyst represented by:
(I) The following formula (1a):

(In formula (1a), R ¹ , R ² , R ³ , R ⁵ , R ⁶ , m, and n are as described above.)
The ligand represented by the formula (1b) of 2.2 to 3.8 molar equivalents relative to the ligand:
LiR ⁴ (1b)
(In formula (1b), R ⁴ is as described above, and is bonded to a lithium atom by a C—Li bond.)
Reacting with a compound represented by:
(II) The product obtained in the step (I) is represented by the following formula (1c) of 1 molar equivalent or more with respect to the ligand:
MR ⁷ ₄ (1c)
(In Formula (1c), M is as described above, R ⁷ is a halogen atom or a group represented by —OR ⁸ , and R ⁸ is the number of carbon atoms that may have a hetero atom. 1 to 20 hydrocarbon groups, and R ⁸ is bonded to an oxygen atom by a C—O bond.)
Reacting with a compound represented by:
(III) The sum of the amount of the compound represented by the formula (1b) used in the step (I) and the amount of the compound represented by the formula (1b) used in the step (III) A method for producing a catalyst, comprising a step of reacting the product of the step (II) with the compound represented by the formula (1b) so as to be 4 molar equivalents or more based on a ligand. The ligand is represented by the following formula (1a-1):

The manufacturing method of the catalyst of Claim 1 which is a compound represented by these. Wherein a compound represented by formula (1c) is TiCl _4, process for preparing a catalyst according to claim 1 or 2.