JP2001114794A - Method for recovering group 8 noble metal and/or organic phosphite compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To recover a group 8 noble metal and/or an organic phosphite compound from a catalyst liquid extracted from a reaction system in a catalytic activity-retaining state in a hydroformylation reaction using a catalyst comprising a group 8 noble metal complex containing the organic phosphite compound as a ligand. SOLUTION: This method for recovering a group 8 noble metal and/or an organic phosphite compound comprises mixing a catalyst liquid with an organic solvent such as methanol or the organic solvent and water, crystallizing the group 8 noble metal and/or the organic phosphite compound from the mixture liquid, and then recovering the crystals by a filtration method.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a hydroformylation reaction catalyzed by a Group 8 noble metal complex having an organic phosphite compound as a ligand, and to a Group 8 noble metal and a solution extracted from a reaction system containing a catalyst. And / or a method for recovering an organic phosphite compound.

[0002]

2. Description of the Related Art Complexes containing an organic phosphite compound as a ligand can be produced by various processes such as hydrogenation of olefins, carbonyl compounds, aromatic compounds, etc. by homogeneous catalytic reaction, hydroformylation of olefins, and hydrocarboxylation. Useful as a catalyst for the reaction. In particular, rhodium-organo phosphite compound-based complexes have been studied a lot because they exhibit high reactivity and selectivity as a catalyst for hydroformylation reaction.

For example, Japanese Patent Application Laid-Open No. 57-123134 discloses a method in which a triaryl phosphite having a substituent at a specific position of a phenyl ring is used as a ligand. JP-A-59-51228 and JP-A-59-51228
No. 5,512,230 discloses a method using a cyclic phosphite ligand containing a phosphorus atom at the bridge head. JP-T-61-501268 discloses a method using a diorganophosphite ligand having a cyclic structure. JP-A-62-116587 discloses that 2
Bidentate phosphite compounds in which one of the two phosphite groups has a cyclic structure are also disclosed in JP-A-62-1165.
No. 35 discloses a bidentate phosphite compound in which both phosphite groups have a cyclic structure. JP-A-4-290551 discloses a method using a bisphosphite ligand having a cyclic structure.
Further, Japanese Patent Application Laid-Open No. 5-339207 by the present applicant discloses a method using a bisphosphite ligand and a polyphosphite ligand having a substituent at a specific site.

In order to use the Group VIII noble metal-organophosphite compound complex catalyst in an industrially advantageous manner, a reaction component containing a reaction product and a catalyst (in the present specification, this is referred to as a catalyst solution) May be separated by distillation, and the catalyst solution is recycled to the reaction zone for reuse, or
It is necessary to perform an operation such as distilling the reaction product out of the reaction zone by gas stripping and separating the reaction product, and continuously performing the reaction with the catalyst liquid remaining in the reaction zone. However, since various high-boiling by-products are generated in the hydroformylation reaction, in order to carry out the reaction continuously, a part of the catalyst solution is continuously or intermittently avoided to avoid accumulation of the high-boiling by-products. It is necessary to extract it out of the reaction system.

Since the extracted catalyst solution contains expensive Group VIII noble metal and organic phosphite compound,
It is extremely important economically to recover this efficiently. In recovering the Group VIII noble metal from the extracted catalyst solution, it is desirable to recover the noble metal of the Group 8 in a form active for the reaction so that the recovered material can be used as it is as a catalyst.
Various studies have been made on methods for separating and recovering Group 8 noble metals from the extracted catalyst solution.

[0006] In the method disclosed in JP-A-51-63388, a distillation residue from a hydroformylation reaction is treated with a mineral acid and hydrogen peroxide to extract contained rhodium or iridium into an aqueous phase. This aqueous phase is then
Treated with carbon monoxide in the presence of a secondary phosphine and a hydrohalic acid or an alkali halide, and the regenerated complex is recovered by crystallization. This method is disadvantageous in that the use of a halide requires the use of a halogen-resistant material in the equipment, which increases the equipment cost. Further, in the case of a non-halogen-based complex catalyst, it cannot be applied because halogen causes deactivation of the catalyst.

In the method disclosed in JP-A-54-26218, rhodium is recovered from the distillation residue of a hydroformylation reaction using triaryl phosphite as a ligand. Collect as a monovalent precipitate. However, this method requires complicated chemical treatment in order to regenerate the recovered metal into an active catalyst. JP-A-2-145439 discloses a method in which a distillation residue of a hydroformylation reaction is extracted with an aqueous solution containing triphenylphosphine monosulfonate, and rhodium is recovered in an aqueous phase. However, water-soluble phosphines are expensive and are only applicable to limited systems.

[0008] JP-A-3-146423 discloses that rhodium is recovered by treating a distillation residue from a hydroformylation reaction with oxygen gas in the presence of a carboxylic acid and an alkali salt of the carboxylic acid, and then extracting the resulting product with water. The method is shown. However, it is known that when an alkali metal salt is mixed into the reaction system of the hydroformylation reaction, the formation of high-boiling substances is promoted. Therefore, when the recovered rhodium is reused as a catalyst, the alkali metal must be removed in advance, but it is not easy to remove the alkali metal to such an extent that the reaction is not affected.

No. 4,390,473 discloses that in a low-pressure hydroformylation reaction, a solution containing rhodium and cobalt used as a catalyst is brought into contact with an aqueous formic acid solution, a gas containing oxygen is passed, and the phases are separated. A method for recovering metals in the aqueous phase is shown. In this method, rhodium is partially metallized because formic acid acts reductively. This metallized rhodium is substantially lossy.
German Patent No. 381203 discloses a method of extracting and recovering a metal contained in a mixed solution of an aliphatic carboxylic acid having 3 to 10 carbon atoms generated by a hydrocarboxylation reaction of ethylene by washing with water. Regarding a solution of a complex containing a water-insoluble organic phosphorus ligand such as a hydroformylation reaction, regardless of the presence or absence of a carboxylic acid, the catalyst metal cannot be recovered only by washing with water.

[0010]

SUMMARY OF THE INVENTION Accordingly, the present invention avoids the above-mentioned disadvantages of the prior art, and efficiently and efficiently removes a Group VIII noble metal and / or an organic phosphite from a catalyst solution withdrawn from a hydroformylation reaction by a simple operation. An object of the present invention is to provide a method for separating and recovering a compound.

[0011]

According to the present invention, an organic solvent or an organic solvent and water are mixed with a catalyst solution for a hydroformylation reaction containing a Group 8 noble metal complex having an organic phosphite compound as a ligand. To crystallize at least one of the Group VIII noble metal complex and the organic phosphite compound,
Then, by separating the crystallized product from the liquid phase, the Group VIII noble metal and / or the organic phosphite compound in the catalyst solution can be efficiently recovered.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, as an organic phosphite compound of a ligand of a Group VIII noble metal complex used as a catalyst, triaryl phosphite which has been conventionally known to be used for the preparation of this complex is used. , Including trialkyl phosphites, arylalkyl phosphites,
Any organic phosphite compound such as a bisphosphite compound or a polyphosphite compound having these combinations in the same molecule can be used.

Specifically, the monophosphite compound includes a phosphite compound having a cyclic structure and a phosphorus atom contained in the cyclic structure, and a phosphite compound having no cyclic structure containing a phosphorus atom. However, any of them can be used. Among them, the latter, that is, a phosphite compound having no cyclic structure containing a phosphorus atom, is preferably represented by the general formula (1).

[0014]

Embedded image P (OR ¹ ) (OR ² ) (OR ³ ) (1)

(Where R¹, R^TwoAnd R^ThreeRespectively
Independently, it may have 1 to 30 carbon atoms which may have a substituent.
Hydrocarbon group or heteroaromatic hydrocarbon having 5 to 30 carbon atoms
Represents a group. Substituents that do not interfere with the reaction
Any one may be used, but usually it has 1 to 20 carbon atoms.
Alkyl group, cycloalkyl group, alkoxy group, alkyl
Amino group, acyl group, acyloxy group, alkoxyca
Among the organic phosphite compounds represented by the general formula (1).
But preferred is R ¹, R^TwoAnd R^ThreeAt least one of
One is a substituted aryl group represented by the general formula (2).
It is.

[0016]

Embedded image

(Where R^FourIs CR⁹R^TenR¹¹Or a substituent
Represents an aryl group optionally having⁹, R^Tenas well as
R¹¹Are each independently a hydrogen atom or a fluorinated
Represents an optionally substituted hydrocarbon group. R^FourIs an isopropyl group
It is preferable to show the above steric hindrance. R^Five,
R⁶, R⁷And R⁸Are each independently a hydrogen atom or
Represents an organic group. Note that R^FiveOr R⁸Adjacent to
Stuff, for example R⁶And R ⁷Are bonded to each other to form a fused aromatic ring
Alternatively, a condensed heterocyclic ring may be formed. )

Specific examples of these compounds include diphenyl (2,4-ditert-butylphenyl) phosphite, diphenyl (2-isopropylphenyl) phosphite, and bis (2-tert-butyl-4-methylphenyl) phenyl. Phosphite, diphenyl (3,6
-Di-tert-butyl-2-naphthyl) phosphite, bis (2-naphthyl) (3,6-di-tert-butyl-2-naphthyl) phosphite, bis (3,6,8)
-Tritertiary-butyl-2-naphthyl) phenyl phosphite; bis (3,6,8-tritertiary-butyl-2-naphthyl) (2-naphthyl) phosphite;

Among the organic phosphite compounds of the general formula (1) having a substituted aryl group represented by the general formula (2), R ¹ and R ² in the general formula (1) are particularly preferable.
And R ³ are all organic phosphite compounds which are substituted aryl groups represented by the general formula (2). Specific examples of these compounds include tris (2,4-ditert-butylphenyl) phosphite, tris (2-tert-butyl-4-methylphenyl) phosphite,
Tris (2-tert-butyl-4-methoxyphenyl) phosphite, tris (o-phenylphenyl) phosphite, tris (o-methylphenyl) phosphite, bis (3,6-ditert-butyl-2-naphthyl) (2,4-di-tert-butylphenyl) phosphite, bis (3,6-di-tert-butyl-2-naphthyl) (2-tert-butylphenyl) phosphite, tris (3,6-di-tert-butyl-2-butyl) Naphthyl) phosphite, tris (3,6-ditert-amyl-2-naphthyl) phosphite and the like. Among the monophosphite compounds, a phosphite compound having a cyclic structure and a phosphorus atom included in the cyclic structure, which is another compound group, includes a phosphite compound represented by the following formula.

[0020]

Embedded image

(Wherein, Z represents a divalent hydrocarbon group which may contain a heteroatom in the carbon chain and may have a substituent, and Y represents a substituent Represents a hydrocarbon group or a heteroaromatic hydrocarbon group.)

Representative examples of the divalent organic group represented by Z in the general formula (3) are a divalent aliphatic group or a divalent aromatic group. Examples of the divalent aliphatic group include an alkylene group, an alkylene-oxy-alkylene group, an alkylene-NR ¹² -alkylene group (R ¹² represents a hydrogen atom or a hydrocarbon group), an alkylene-S-alkylene group, and a cycloalkyl group. Alkylene groups and these similar divalent aliphatic groups are mentioned. Examples of the divalent aromatic group include an arylene group, a biarylene group, an arylene-alkylene group, an arylene-alkylene-arylene group, an arylene-oxy-arylene group, an arylene-oxy-alkylene group, an arylene-NR ¹² -arylene group and an arylene- NR ¹²
-Alkylene group, arylene-S-alkylene group and arylene-S-arylene group. Preferred examples of the phosphite compound having such a cyclic structure and having a phosphorus atom contained in the cyclic structure include those represented by the general formula (4).

[0023]

Embedded image

(Wherein R ¹³ may be different from each other and represents a hydrogen atom or an optionally substituted alkyl group, cycloalkyl group, or aryl group, and n represents 0 to
Represents an integer of 4. Y represents an organic group)

Representative examples of the substituent represented by R ¹³ in the general formula (4) include a methyl group, an ethyl group, a phenyl group, a tolyl group, a benzyl group, a naphthyl group, a hydroxymethyl group and a hydroxyethyl group. And a trifluoromethyl group. Preferred as the phosphite compound represented by the general formula (4) is an aryl group having a substituent at a carbon atom adjacent to a carbon atom bonded to an oxygen atom, wherein Y is represented by the general formula (2). There is something. Another preferable example of the phosphite compound having a cyclic structure and having a phosphorus atom contained in the cyclic structure includes a compound represented by the general formula (5).

[0026]

Embedded image

(In the formula, R ¹⁴ is an arbitrary substituent at the o, m, and p positions, or R ¹⁴ is condensed with a phenyl ring to which it is bonded to form a condensed aromatic ring such as a naphthyl ring. Y represents a monovalent organic group)

Representative examples of the substituent represented by R ¹⁴ in the general formula (5) may have an alkyl group, a cycloalkyl group, an alkoxy group, an acyl group, an acyloxy group or a substituent. And an aryl group. Examples of the condensed aromatic ring formed by R ¹⁴ and a phenyl ring include a naphthalene ring. Preferred as the phosphite compound represented by the general formula (5) is an aryl group having a substituent at a carbon atom adjacent to the carbon atom bonded to the oxygen atom, wherein Y is represented by the general formula (2). There is something. Further, as still another preferred example of the phosphite compound having a ring structure and a phosphorus atom contained in the ring structure, a phosphite compound represented by the general formula (6) can be mentioned.

[0029]

Embedded image

(Wherein, two Ars may be different from each other, each represents an aryl group which may have a substituent, and two y's each independently represent 0 or 1;
Q is -CR ¹⁵ R ^16- , -O-, -S-, -NR ¹⁷ -,-
SiR ¹⁸ R ¹⁹ — and —CO— (R ¹⁵ and R ¹⁶ each represent an atom or a group selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a phenyl group, a tolyl group, and an anisyl group; R ¹⁷ , R ¹⁸ and R ¹⁹ each represent a hydrogen atom or a methyl group), n represents 0 or 1, and Y represents an organic group.

Preferred as Y in the general formula (6) are, for example, methyl, ethyl, n-propyl, isopropyl, butyl, sec-butyl, t-butyl, t-butylethyl, t-butyl Butylpropyl group, n-
A primary to tertiary group having 1 to 20 carbon atoms such as a hexyl group, an amyl group, a sec-amyl group, a t-amyl group, an isooctyl group, a 2-ethylhexyl group, a decyl group and an octadecyl group;
It is a lower alkyl group or an aryl group which may have a substituent. The aryl group may be an aryl group having a condensed ring such as an α-naphthyl group and a β-naphthyl group. Examples of the substituent of the aryl group include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, an alkoxy group, an alkylamino group, an acyl group, an acyloxy group, an alkoxycarbonyl group, and a halogen atom.

Preferred examples of the phosphite compound represented by the general formula (6) include a phosphite compound represented by the general formula (7) or (8).

[0033]

Embedded image

In the formula, Q and Y are as follows in the general formula (6).
Is the same. R²⁰, R^{twenty one}, R^{twenty two}, R ^{twenty three}, R^{twenty four}And R^{twenty five}When
Is an alkyl group having 1 to 20 carbon atoms, cycloalkyl
Group, alkoxy group, alkylamino group, acyl group,
Ruoxy group, alkoxycarbonyl group, halogen atom,
And a hydrogen atom. Specific examples of these compounds
Examples include compounds as shown in Table 1.

[0035]

[Table 1]

In the present invention, the bisphosphite and polyphosphite ligands used as ligands of the Group VIII noble metal complex include those represented by the general formula (9).

[0037]

Embedded image

Wherein Z contains a heteroatom in the carbon chain
Divalent carbon which may be substituted and may have a substituent
Represents a hydride group, R²⁶And R²⁷Are, independently of each other,
C1-C30 hydrocarbon group which may have a substituent
Or a heteroaromatic hydrocarbon group having 5 to 30 carbon atoms.
Representative examples of the divalent organic group represented by Z include:
Aliphatic groups or aromatic groups as exemplified in the general formula (3) are listed.
I can do it. R²⁶And R ²⁷Inhibits the reaction as a substituent of
Anything can be used, but usually it is not charcoal
Alkyl groups having 1 to 20 atoms, cycloalkyl groups, alcohols
Xyl group, alkylamino group, acyl group, acyloxy
Group, an alkoxycarbonyl group or a halogen atom.
Can be R²⁶And R²⁷As a specific example of the group represented by
For example, a methyl group, an ethyl group, an n-propyl group,
Isopropyl group, n-butyl group, s-butyl group, t-butyl
Group, n-pentyl group, isopentyl group, neopentyl
Group, t-pentyl group, t-hexyl group, etc.
0 linear or branched alkyl groups, cyclopropyl groups,
Cyclohexyl group, cyclooctyl group, adamantyl group
A cycloalkyl group having 3 to 20 carbon atoms such as
Group, α-naphthyl group, β-naphthyl group, methoxyphen
Nyl group, dimethoxyphenyl group, methoxycarbonyl group
Phenyl, cyanophenyl, nitrophenyl, chloro
Rophenyl group, dichlorophenyl group, pentafluorophenyl
Phenyl, methylphenyl, ethylphenyl,
Tylphenyl group, trifluoromethylphenyl group, methyl
Lunaphthyl group, methoxynaphthyl group, chloronaphthyl
Group, nitronaphthyl group, tetrahydronaphthyl group, etc.
Aryl groups and benzyl groups which may have a substituent;
Aralkyl, pyridyl, methylpyridyl, nitropy
Lysyl, pyrazyl, pyrimidyl, benzofuryl
Group, quinolyl group, isoquinolyl group, benzimidazolyl
Groups, hetero element-containing aromatic groups such as indolyl groups, etc.
Can be

W represents a monovalent hydrocarbon group which may contain a hetero atom in the carbon chain and may have a substituent. m ¹ and m ² each represent an integer of 0 to 6,
m = m ¹ + m ² , where m represents an integer of 2 to 6. When m ¹ and m ² are integers of 2 or more, a plurality of Z,
R ²⁶ and R ²⁷ may be different from each other. General formula (9)
In Formula (4), (5)
And a group corresponding to Z in the compound represented by (6). R ²⁶ and R ²⁷ are preferably each independently an aryl group which may have a substituent.
Specific examples thereof include a phenyl group, a 2-methylphenyl group, a 3-methylphenyl group, a 4-methylphenyl group,
2,4-dimethylphenyl group, 2,5-dimethylphenyl group, 2,6-dimethylphenyl group, 2-methoxyphenyl group, 3-methoxyphenyl group, 4-methoxyphenyl group, 2,4-dimethoxyphenyl group, 2,5-dimethoxyphenyl group, 2,6-dimethoxyphenyl group, α-
Examples include a naphthyl group, a 3-methyl-α-naphthyl group, a 3,6-dimethyl-α-naphthyl group, a β-naphthyl group, a 1-methyl-β-naphthyl group, and a 3-methyl-β-naphthyl group.

W is an alkylene group, an arylene group or an arylene- (CH ₂ ) _y- (Q) _n- (CH ₂ ) _y
-Arylene group- (each arylene group is independently an arylene group which may have a substituent;
-CR ²⁸ R ²⁹ is -, - O -, - S -, - NR 30 -, - S
a bridge selected from the group consisting of iR ³¹ R ³² — and —CO— (R ²⁸ and R ²⁹ each represent a hydrogen atom or an alkyl group, and R ³⁰ , R ³¹ and R ³² each represent a hydrogen atom or a methyl group) And each of y and n independently represents 0 or 1. ) Is preferably a divalent organic group.

Specific examples thereof include 1,2-ethylene group, 1,3-propylene group, 1,3-dimethyl-1,3
-Propylene group, 1,4-butylene group, 1,5-pentylene group, 1,6-hexylene group, 1,8-octylene group, 1,2-phenylene group, 1,3-phenylene group,
2,3-naphthylene group, 1,8-naphthylene group, 1,
1'-biphenyl-2,2'-diyl group, 1,1'-binaphthyl-7,7'-diyl group, 1,1'-binaphthyl-2,2'-diyl group, 2,2'-binaphthyl- 1,
Examples thereof include a 1'-diyl group and a 2,2'-binaphthyl-3,3'-diyl group.

In formula (9), Z is preferably a group corresponding to Z in the compound represented by formula (6), and W is a group represented by formula (10). Things.

[0043]

Embedded image

In the formula, R ³⁷ and R ³⁸ each independently represent an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, an alkoxy group, a silyl group, a siloxy group, a halogen atom or a hydrogen atom. The most common alkyl and alkoxy groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, methoxy, ethoxy, n-propoxy and the like. The halogen atom may be any of a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. R ³⁶ from R ³³ each independently represent alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, an alkoxy group, a silyl group, siloxy group, or a halogen atom or a hydrogen atom. Examples of the alkyl group or the alkoxy group include a methyl group, an ethyl group, an n-propyl group,
Examples include an isopropyl group, an n-butyl group, a t-butyl group, a t-pentyl group, a neopentyl group, a t-hexyl group, a nonyl group, a decyl group, a methoxy group, an ethoxy group, and a t-butoxy group. Further, two adjacent substituents in the general formula (10), that is, R ³⁵ and R ³⁷ and / or R ³⁶
And by R ³⁸ may be bonded to each other to form a part of a cyclic structure consisting of several 3 to 40 carbon atoms. Examples thereof include a 1,1'-binaphthyl-2,2'-diyl group. Q has the same meaning as in general formula (6).

In a preferred example of the polyphosphite ligand represented by the general formula (9), R ²⁶ and R ²⁷ in the general formula (9) may each independently have a substituent. An aryl group, and W is R in the general formula (10)
³³ and R ³⁴ are each independently a branched alkyl group having 3 to 20 carbon atoms, and R ³⁵ and R ³⁶ are each independently an alkyl or alkoxy group having 1 to 20 carbon atoms. It is a substituted arylene-arylene group having a certain 1,1'-biphenyl-2,2'-diyl skeleton or 1,1'-binaphthyl-2,2'-diyl skeleton. Specific examples of such W include 3,3'-di-
t-butyl-1,1'-binaphthyl-2,2'-diyl group, 3,3 ', 6,6'-tetra-t-butyl-1,
1'-binaphthyl-2,2'-diyl group, 3,3'-di-t-butyl-6,6'-di-t-butoxy-1,1 '
-Binaphthyl-2,2'-diyl group, 3,3'-di-t
-Pentyl-1,1'-binaphthyl-2,2'-diyl group, 3,3 ', 6,6'-tetra-t-pentyl-1,
1'-binaphthyl-2,2'-diyl group, 3,3'-di-t-butyl-5,5'-dimethyl-1,1'-biphenyl-2,2'-diyl group, 3,3 ' , 5,5'-Tetra-t-butyl-1,1'-biphenyl-2,2'-diyl group, 3,3 ', 5,5'-tetra-t-pentyl-
1,1'-biphenyl-2,2'-diyl group, 3,3 '
-Di-t-butyl-5,5'-dimethoxy-1,1'-
Biphenyl-2,2'-diyl group, 3,3'-di-t-
Butyl-5,5 ', 6,6'-tetramethyl-1,1'
-Biphenyl-2,2'-diyl group, 3,3 ', 5
5'-tetra-t-butyl-6,6'-dimethyl-1,
1'-biphenyl-2,2'-diyl group, 3,3 ',
5,5'-tetra-t-pentyl-6,6'-dimethyl-1,1'-biphenyl-2,2'-diyl group, 3,
3'-di-t-butyl-5,5'-dimethoxy-6
6'-dimethyl-1,1'-biphenyl-2,2'-diyl group, 3,3 ', 5,5'-tetra-t-butyl-
6,6'-dichloro-1,1'-biphenyl-2,2 '
-Diyl group and the like.

Most preferred as W are R ^{33 to} R ^36.
Is as defined above, and R ³⁷ and R ³⁸ are each independently an alkyl group having 1 to 3 carbon atoms, an alkoxy group, or a halogen atom. That is, R ³⁷ and R ³⁸ represent a methyl group, an ethyl group, an n-propyl group,
It is any of isopropyl, methoxy, ethoxy, n-propoxy, isopropoxy, fluorine, chlorine, bromine and iodine. Examples of such W include 3,3'-di-t-butyl-
5,5 ', 6,6'-tetramethyl-1,1'-biphenyl-2,2'-diyl group, 3,3', 5,5'-tetra-t-butyl-6,6'-dimethyl -1,1'-biphenyl-2,2'-diyl group, 3,3 ', 5,5'-tetra-t-butyl-6,6'-diethyl-1,1'-biphenyl-2,2' -Diyl group, 3,3 ', 5,5'-
Tetra-t-butyl-6,6'-dimethoxy-1,1 '
-Biphenyl-2,2'-diyl group, 3,3'-di-t
-Butyl-5,5'-dimethoxy-6,6'-dichloro-1,1'-biphenyl-2,2'-diyl group, 3,
And 3 ', 5,5'-tetra-t-butyl-6,6'-difluoro-1,1'-biphenyl-2,2'-diyl.

Table 2 shows some of the polyphosphite compounds represented by the general formula (9) which are preferable for use in the present invention.

[0048]

[Table 2]

[0049]

[Table 3]

[0050]

[Table 4]

[0051]

[Table 5]

[0052]

[Table 6]

[0053]

[Table 7]

[0054]

[Table 8]

[0055]

[Table 9]

[0056]

[Table 10]

[0057]

[Table 11]

[0058]

[Table 12]

[0059]

[Table 13]

[0060]

[Table 14]

[0061]

[Table 15]

[0062]

[Table 16]

[0063]

[Table 17]

[0064]

[Table 18]

[0065]

[Table 19]

[0066]

[Table 20]

[0067]

[Table 21]

[0068]

[Table 22]

[0069]

[Table 23]

[0070]

[Table 24]

[0071]

[Table 25]

[0072]

[Table 26]

[0073]

[Table 27]

One kind of the organic phosphite compound is usually used, but if desired, two or more kinds may be used in combination. For example, a monophosphite and a bisphosphite or polyphosphite compound may be used in combination. Although the amount of the organic phosphite compound is not particularly limited, it is generally about 0.1 to 0.1 mol per mol of the Group 8 noble metal.
To 500 mol, preferably 0.1 to 100 mol, more preferably 1 to 30 mol.

The Group VIII noble metal complex used as a catalyst in the present invention may be used by forming a complex from a Group VIII noble metal compound and an organic phosphite compound in advance.
A group VIII noble metal compound serving as a precursor and an organic phosphite compound may be added to the reaction system to generate the compound in the system. The preparation of the complex from the Group VIII noble metal compound and the organic phosphite compound can be easily performed by a known method. Rhodium is preferably used as the Group 8 noble metal. Examples of the rhodium source include rhodium chloride, rhodium nitrate, rhodium acetate, rhodium formate, sodium rhodate, and inorganic or organic acid salts of rhodium such as potassium rhodate, alumina, silica, and activated carbon. Rhodium metal, rhodium dicarbonyl acetylacetonate, rhodium chelating compound such as rhodium (1,5-cyclooctadiene) acetylacetonate, tetrarhodium dodecacarbonyl, hexarhodium hexadecacarbonyl, μ, μ′-dichloro Rhodium tetracarbonyl, [Rh (OAc) (CO
D)] ₂ (COD represents 1,5-cyclooctadiene) and a rhodium carbonyl complex compound such as [Rh (μ-St-Bu) (CO) ₂ ] ₂ . The concentration of the Group VIII noble metal complex in the reaction zone is usually 0.05 mg to 1 liter of the reaction medium in terms of metal atoms.
5 g. 0.5 mg to 1 g, especially 10 mg to 500
It is preferably in the range of mg.

Since the hydroformylation reaction is carried out in a liquid phase, it is preferable that an inert solvent is present in the reaction system. As the solvent, for example, toluene, xylene,
Aromatic hydrocarbons such as dodecylbenzene, ketones such as acetone, diethyl ketone, and methyl ethyl ketone, ethers such as tetrahydrofuran and dioxane, and esters such as ethyl acetate and di-n-octyl phthalate are used. An aldehyde generated by the reaction, a high-boiling component mixture by-produced in the reaction of the aldehyde condensate, or the like can be used as the solvent. Further, the raw material olefinic compound itself can be used as a solvent. Preferably, a mixture of an aromatic hydrocarbon such as toluene and xylene, an aldehyde generated in the reaction, and a high-boiling component produced as a by-product in the reaction is used as the solvent.

In the present invention, the hydroformylation reaction itself may be performed according to a conventional method. The reaction temperature is usually 15 to 150 ° C, but 30 to 130 ° C, particularly 50 ° C.
Preferably it is ~ 110 ° C. The reaction pressure is usually from normal pressure to 200 atm, but from 1 to 100 atm, particularly from 3 to 100 atm.
Preferably it is 50 atm. The molar ratio of hydrogen to carbon monoxide (H ₂ / CO) in oxo gas is usually 10/1 to 1/1.
0, preferably selected from the range of 1/1 to 6/1.

The olefinic compound as a raw material for the hydroformylation reaction is not particularly limited as long as it is an organic compound having at least one olefinic double bond in the molecule. For example, it may be any olefinic compound having a linear, branched or cyclic structure, and the double bond may be either internal or terminal. Olefins usually used as raw materials are those having 2 to 20 carbon atoms, and have substantially no influence on the hydroformylation reaction, carbonyl group, acyl group, acyloxy group, hydroxy group, alkoxycarbonyl group, halogen atom, alkoxy group, It may have a substituent such as an aryl group or a haloalkyl group. Examples of olefin compounds include:
α-olefins, internal olefins, alkyl alkenoates, alkenyl alkanoates, alkenyl alkyl ethers, alkenols and the like.

Illustrating some of these compounds:
Ethylene, propylene, butene, butadiene, pentene, hexene, 1,4-hexadiene, octene, 1,
Olefins such as 7-octadiene, nonene, decene, hexadecene, octadecene, eicosene, dococene, styrene, α-methylstyrene, 3-phenyl-1-propene, 3-cyclohexyl-1-butene and cyclohexene; propylene-butene mixtures, -Lower olefin mixtures such as butene-2-butene-isobutylene mixture, 1-butene-2-butene-isobutylene-butadiene mixture; dimers-tetramers of lower olefins such as propylene, n-butene and isobutylene Olefin oligomer isomer mixture; acrylonitrile, allyl alcohol, 1-hydroxy-2,7-octadiene, 3-hydroxy-1,7-octadiene, oleyl alcohol,
1-methoxy-2,7-octadiene, methyl acrylate, methyl methacrylate, methyl oleate, oct-1-en-4-ol, vinyl acetate, allyl acetate, 3-butenyl acetate, allyl propionate, vinylethyl Examples include polar group-substituted olefins such as ether, vinyl methyl ether, allyl ethyl ether, n-propyl-7-octenoate, 3-butenenitrile, and 5-hexenamide. Of these, preferred as raw materials are monoolefin-based compounds having only one olefinic double bond in the molecule. Among them, hydrocarbon olefins having 2 to 20 carbon atoms are preferred, and most preferred are propylene, 1-butene, 2-butene, isobutene and mixtures thereof, 1-octene, and mixed octene.

The product of the hydroformylation reaction is separated and recovered from the reaction medium containing the catalyst by stripping with an unreacted gas, distillation or the like according to the reaction system. In each case, part of the reaction medium containing the catalyst is:
In order to avoid accumulation of high-boiling by-products, the catalyst is continuously or intermittently extracted from the reaction system and extracted as a catalyst solution, and new amounts of the Group VIII noble metal and organic phosphite compound corresponding to the extracted amount are newly added. Is supplied to the reaction system.

In the present invention, the extracted catalyst solution
A group noble metal complex and / or an organic phosphite compound is recovered. When the present invention is applied to the extracted catalyst solution, it is preferable that the solution is previously distilled and concentrated. In particular, when a large amount of a reaction solvent that is a good solvent for the Group VIII noble metal complex and / or the organic phosphite compound is contained,
Distillation should be performed beforehand. Distillation temperature 50-250
C. and a pressure of 0.5 to 1000 mmHg. More preferably, some of the high-boiling by-products are also removed by the same operation. Usually, the concentration of the Group VIII noble metal complex in
The present invention is applied after converting to 10 mg / L or more in terms of group noble metal atoms. Preferably, the present invention is applied after concentration to 100 mg / L or more, particularly 500 mg / L or more.

In the present invention, an organic solvent or an organic solvent and water are mixed with the extracted catalyst solution having undergone the above-mentioned treatment to crystallize the Group VIII noble metal complex and / or the organic phosphite compound, and separate and collect them. Examples of the organic solvent to be mixed with the extraction catalyst liquid include, for example, methyl alcohol, ethyl alcohol, propyl alcohol, butyl alcohol, amyl alcohol, hexyl alcohol, heptyl alcohol,
Octyl alcohol, ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, alcohols having 1 to 8 carbon atoms such as glycerin, acetonitrile, N-methylpiperidone, polar compounds such as diethyl ether, pentane, hexane, heptane, octane, etc. Non-polar compounds are mentioned. Preferably, methyl alcohol, ethyl alcohol, propyl alcohol, butyl alcohol, ethylene glycol,
Alcohols having 1 to 4 carbon atoms such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether are used. Most preferably, methyl alcohol is used. These organic solvents may be used alone or as a mixture thereof. In the present invention, the above-mentioned organic solvent or the organic solvent and water are mixed with the extracted catalyst solution. The mixing amount of the organic solvent or the organic solvent and water is usually 0.1 to the total amount of the organic solvent and water with respect to the extracted catalyst solution. It is at least 1 time by weight, preferably about 1 to 50 times by weight. The ratio of water to organic solvent (water / organic solvent) is preferably 0/100 to 50/50 by weight. Generally, both the Group VIII noble metal complex and the organic phosphite compound are easily dissolved in an organic solvent such as methanol. However, when the polarity of the solvent is increased by adding water, the solubility of the Group VIII noble metal complex and the organic phosphite compound decreases. It becomes easy to crystallize. This tendency is remarkable especially for the Group 8 noble metal complex, and water should be added when crystallizing the complex. The method of mixing the organic solvent or the organic solvent and water is optional, and the organic solvent or the organic solvent and water may be added to the extracted catalyst solution, or the extracted catalyst solution may be added to the organic solvent or the organic solvent and water. Good. Further, an organic solvent may be added to the extracted catalyst solution, and finally water may be added.

The crystallization operation of the Group VIII noble metal complex and / or the organic phosphite compound is performed using carbon dioxide, nitrogen, a rare gas,
It is preferable to carry out in a non-oxidizing atmosphere such as methane. Since the presence of oxygen oxidizes the Group VIII noble metal complex and / or the organic phosphite compound, it is desirable to control the presence of oxygen as little as possible. The crystallization operation is preferably performed in an atmosphere containing hydrogen, most preferably in an atmosphere containing hydrogen and carbon monoxide. The composition of the crystallized Group 8 noble metal complex is affected by the atmosphere. In a nitrogen atmosphere, a complex in which carbon monoxide or an organic phosphite compound is coordinated with two atoms of the Group 8 noble metal is formed. It appears that a complex in which carbon monoxide or an organic phosphite compound is coordinated to one atom of a Group 8 noble metal. In the case of an atmosphere containing carbon monoxide and hydrogen, the crystallization amount of the Group VIII noble metal complex tends to be the largest because the coordination of carbon monoxide to the complex is sufficiently performed.

The crystallization operation can be performed at any temperature as long as the group VIII noble metal complex and / or the organic phosphite compound is not decomposed, but is usually at -20 to 150 ° C, preferably at 0 to 70 ° C. Perform in a range. The pressure for the crystallization operation is also arbitrary, but is usually 0.001 atm or more, preferably 1 to 100 atm in absolute pressure. The time for the crystallization operation is usually several minutes or more, preferably in the range of several minutes to several hours. The crystallized Group VIII noble metal complex and / or organic phosphite compound can be recovered by solid-liquid separation by a usual solid separation method, for example, a centrifugal filtration method, a centrifugal separation method, a pressure filtration method and the like. Group 8 noble metal complex separated and recovered and / or
Alternatively, the organic phosphite compound has sufficient catalytic activity to be used as a catalyst for the hydroformylation reaction.
Therefore, the separated and recovered Group VIII noble metal complex and / or organic phosphite compound is directly supplied to the reaction zone,
It can be reused as a catalyst.

As described above in detail, according to the method of the present invention, a Group VIII noble metal complex and / or
Alternatively, the organic phosphite compound can be efficiently recovered by a simple operation, and the recovered Group VIII noble metal complex and / or organic phosphite compound have sufficient activity as a catalyst,
In addition, the present invention has an extremely large industrial value because it contains substantially no impurities unfavorable for the reaction and can be supplied to the reaction zone as it is and reused. Next, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist.

[0086]

EXAMPLES Example 1 As a rhodium compound, di-μ-acetato-bis (1,5
-Cyclooctadiene) dirhodium (I) ([Rh (C
₈ H ₁₂ ) (μ-CH ₃ CO ₂ )] ₂ ) complex and an organic phosphite compound in Table 2. A hydroformylation reaction of propylene was performed using the 53 compounds to obtain a withdrawn catalyst liquid having the following composition.

Rhodium complex concentration (in terms of rhodium atom) 135 mg / L organic phosphite compound 0.5% by weight Butyraldehyde 28.4% by weight High-boiling by-product 71% by weight

95 g of the extracted catalyst solution and 800 g of aqueous methyl alcohol containing 30% by weight of water were placed in a 2 liter autoclave containing a magnetic stirrer in a nitrogen gas atmosphere and sealed. The mixture was stirred at a temperature of 25 ° C. and a normal pressure for 2 hours. Thereafter, solid-liquid separation was performed by filtration with a 0.2 μm Teflon filter to obtain a crystallized product. The recovery of rhodium was 95%, and the recovery of organic phosphite compounds was 100%.

Example 2 95 g of the extracted catalyst solution of Example 1 and 800 g of hydrated methyl alcohol containing 30% by weight of water were placed in a 2 liter autoclave containing a magnetic stirrer in a nitrogen gas atmosphere, and sealed. Thereafter, a mixed gas of hydrogen: carbon monoxide = 1: 1 was injected at 25 ° C. so as to be 8 atm. The mixture was stirred for 2 hours while maintaining this pressure. Then, the autoclave was released and immediately separated into solid and liquid by filtration with a 0.2 μm Teflon filter to obtain a crystallized product.
The recovery of rhodium was 100%, and the recovery of the organic phosphite compound was also 100%.

Example 3 Example 2 was repeated with the exception that hydrated methyl alcohol having 20% by weight of water was used instead of hydrated methyl alcohol having 30% by weight of water.
The crystallization operation was performed in exactly the same manner as described above. As a result, the recovery of rhodium was 87%, and the recovery of the organic phosphite compound was 100%.

Example 4 A crystallization operation was carried out in exactly the same manner as in Example 2, except that the hydrous methyl alcohol was replaced by hydrous propyl alcohol having 30% by weight of water.
As a result, the recovery of rhodium was 85%, and the recovery of the organic phosphite compound was 99%.

Example 5 As a rhodium compound, di-μ-acetato-bis (1,5
-Cyclooctadiene) dirhodium (I) ([Rh (C
₈ H ₁₂ ) (μ-CH ₃ CO ₂ )] ₂ ) complex and an organic phosphite compound in Table 2. Using 65 compounds, a propylene hydroformylation reaction was carried out to obtain an extracted catalyst liquid having the following composition.

Rhodium complex concentration (in terms of rhodium atom) 134 mg / L Organic phosphite compound 0.5% by weight Butyraldehyde 29.4% by weight High-boiling by-product 70% by weight

95 g of the extracted catalyst solution and 800 g of hydrous methyl alcohol containing 30% by weight of water
Was placed in a 2 liter autoclave containing a magnetic stirrer in a nitrogen gas atmosphere, and sealed. The mixture was stirred at a temperature of 25 ° C. and a normal pressure for 2 hours. Thereafter, solid-liquid separation was performed by filtration with a 0.2 μm Teflon filter to obtain a crystallized product. The recovery of rhodium was 93%. The recovery of the organic phosphite compound was 100%.

Example 6 95 g of the extracted catalyst solution of Example 5 and 800 g of hydrated methyl alcohol containing 30% by weight of water were placed in a 2 liter autoclave containing a magnetic stirrer in a nitrogen gas atmosphere, and sealed. Thereafter, a mixed gas of hydrogen: carbon monoxide = 1: 1 was injected at 25 ° C. so as to be 8 atm. The mixture was stirred for 2 hours while maintaining this pressure. Then, the autoclave was released and immediately separated into solid and liquid by filtration with a 0.2 μm Teflon filter to obtain a crystallized product. The recovery of rhodium was 100%, and the recovery of the organic phosphite compound was also 100%.

Example 7 A crystallization operation was carried out in exactly the same manner as in Example 6, except that the hydrated methyl alcohol was changed to hydrated methyl alcohol having 20% by weight of water. As a result, the recovery rate of rhodium was 88%. Also,
The recovery of the organic phosphite compound was 100%.

Example 8 A crystallization operation was performed in the same manner as in Example 6, except that the hydrated methyl alcohol was changed to methyl alcohol. As a result, only the organic phosphite compound was recovered at a recovery rate of 98%.

Reference Example The following experiment was conducted to test the catalytic activity of the recovered crystallized product for the hydroformylation reaction. The crystallized product recovered in Examples 1 and 2 was converted to rhodium atoms by 125 mg.
/ L in toluene. The propylene hydroformylation reaction was performed using each toluene solution, and the reaction rate, apparent reaction rate constant, and selectivity to butyraldehyde were determined. Also, for comparison, di-μ-acetato-bis (1,5-cyclooctadiene)
Dirhodium (I) ([Rh (C ₈ H ₁₂ ) (μ-CH ₃ C
O ₂ )] ₂ ) The complex is 125 mg in terms of rhodium atom.
/ L and dissolved in toluene.
No. The reaction was carried out under the same conditions using a toluene solution (hereinafter, referred to as a standard adjustment solution) in which the compound No. 53 was added to be 0.5% by weight with respect to toluene.

The hydroformylation reaction was carried out in an internal volume of 200 m
The above-mentioned toluene solution (50 mL) and propylene (4 g) were charged into an L-type electromagnetically stirred autoclave, heated to 70 ° C., and then oxo gas (H ₂ / CO = 1 (molar ratio)) was injected. Started. During the reaction, the autoclave and the oxo gas accumulator were connected via an automatic constant pressure device so that the pressure was kept constant, and oxo gas consumed by the reaction was supplied. After 2.5 hours, the autoclave was quenched and the residual propylene in the gas phase and the liquid phase and the butyraldehyde formed were analyzed by gas chromatography. Further, an apparent reaction rate constant (first order) was obtained from a decrease curve of the oxo gas pressure in the accumulator. Table 3 shows the results.

[0100]

[Table 28]

As can be seen from Table 3, the rhodium complex recovered in the present invention has sufficient catalytic activity for the olefin hydroformylation reaction and contains substantially no impurities harmful to the hydroformylation reaction. It can be seen that the desired reaction result and reaction rate can be obtained even if the reaction system is recycled.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat ゛ (Reference) C07F 9/141 C07F 9/141 9/142 9/142 9/144 9/144 9/145 9/145 9 / 6574 9/6574 Z // C07B 61/00 300 C07B 61/00 300 (72) Inventor Kazuyuki Yokoyama 3-10 Ushidori, Kurashiki-shi, Okayama Prefecture Mitsubishi Chemical Corporation Mizushima Plant (72) Inventor Akio Nakanishi Mitsubishi Chemical Co., Ltd. Mizushima Office F-term (reference) 4G069 AA10 BA27A BA27B BA27C BC65A BC65B BC65C BC69A BC69B BC69C BC71B BE25A CB61 FB61 FB10 GA08 GA10 GA13 GA16 4H006 BAA24 BA4883 BE20 BE40 4H039 CA62 CF10 CL45 4H050 AA03 AA05 AB40 AD15 BB14 BB31 WB16 WB19 WB20 WB21

Claims (13)

[Claims] 1. A hydroformylation reaction in which an olefinic double bond is reacted with carbon monoxide and hydrogen to form an aldehyde in a liquid phase containing a Group VIII noble metal complex catalyst having an organic phosphite compound as a ligand. In the reaction
A method for recovering a Group VIII noble metal and / or organic phosphite compound from a solution containing a Group VIII noble metal complex catalyst extracted from a reaction system, wherein an organic solvent or an organic solvent is added to the solution containing a Group VIII noble metal complex. A method comprising mixing water to crystallize at least one of a Group VIII noble metal complex and an organic phosphite compound, and then separating the crystallized product from a liquid phase. 2. The method according to claim 1, wherein the Group VIII noble metal is rhodium. 3. The method according to claim 1, wherein the organic solvent is an alcohol having 1 to 8 carbon atoms. 4. The method according to claim 1, wherein the organic solvent is an alcohol having 1 to 4 carbon atoms. 5. The method according to claim 1, wherein the organic solvent is methanol. 6. The organic phosphite compound represented by the general formula (1)
The method according to any one of claims 1 to 5, wherein the method is represented by: Embedded image P (OR ¹ ) (OR ² ) (OR ³ ) (1) (wherein R ¹ , R ² and R ³ each independently have a substituent. It represents a good hydrocarbon group having 1 to 30 carbon atoms or a heteroaromatic hydrocarbon group having 5 to 30 carbon atoms.) 7. R ¹ , R ² and R in the general formula (1)
^The substituent which ³ may have is selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, an alkoxy group, an alkylamino group, an acyl group, an acyloxy group, an alkoxycarbonyl group or a halogen atom. The method of claim 6, wherein 8. R ¹ , R ² and R in the general formula (1)
7. The method according to claim 6, wherein each ³ is independently a substituted aryl group represented by the general formula (2). Embedded image (In the formula, R ⁴ represents —CR ⁹ R ¹⁰ R ¹¹ or an aryl group which may have a substituent, and R ⁹ , R ¹⁰ and R ¹¹ are each independently a hydrogen atom or a fluorinated group. R ⁵ , R ⁶ , R ⁷ and R ⁸ each independently represent a hydrogen atom or an organic group.
Adjacent ones of ⁵ to R ⁸ may combine with each other to form a condensed aromatic ring or a condensed heterocyclic ring. ) 9. The organic phosphite compound represented by the general formula (3)
The method according to any one of claims 1 to 5, wherein the method is represented by: Embedded image (In the formula, Z represents a divalent hydrocarbon group which may contain a hetero atom in the carbon chain and may have a substituent, and Y represents a carbon atom which may have a substituent. Represents a hydrogen group or a heteroaromatic hydrocarbon group.) 10. The organic phosphite compound represented by the general formula (9).
6. The method according to any one of claims 1 to 5. Embedded image (In the formula, Z represents a divalent hydrocarbon group which may contain a hetero atom in the carbon chain and may have a substituent, and R ²⁶ and R ²⁷ each independently represent Represents an optionally substituted hydrocarbon group having 1 to 30 carbon atoms or a heteroaromatic hydrocarbon group having 5 to 30 carbon atoms, W may include a hetero atom in the carbon chain, and may have a substituent represents an m monovalent hydrocarbon group .m ¹ and m ² are .m = m ¹ + m ² respectively represent an integer of 0 to 6,
And m represents an integer of 2 to 6. ) 11. Z in the general formulas (3) and (9)
Is selected from the group consisting of an alkylene group, an alkylene-oxy-alkylene group, an alkylene-NR ¹² -alkylene group (R ¹² represents a hydrogen atom or a hydrocarbon group), an alkylene-S-alkylene group, and a cycloalkylene group divalent aliphatic group, or an arylene group, biarylene group, an arylene - alkylene group, an arylene - alkylene - arylene group, an arylene - oxy - arylene group, an arylene - oxy - alkylene group, an arylene -NR ¹² -
An alkylene group (R ¹² represents a hydrogen atom or a hydrocarbon group), an arylene-S-alkylene group and an arylene-
The method according to claim 9 or 10, wherein the method is a divalent aromatic group or an aromatic-aliphatic group selected from the group consisting of S-arylene groups. 12. R ²⁶ and R in the general formula (9)
²⁷ are each independently an aryl group which may have a substituent, and W is an arylene group represented by the general formula (10).
The described method. Embedded image (Wherein, R ³³ and R ³⁴ each independently represent a C 3
Represents 20 branched alkyl group, R ³⁵ and R ³⁶ each independently represent an alkyl group or an alkoxy group having 1 to 20 carbon atoms, R ³⁷ and R ³⁸ are each independently C 1 -C To 12 alkyl groups, cycloalkyl groups, alkoxy groups, silyl groups, siloxy groups, halogen atoms or hydrogen atoms. Q is -CR ¹⁵ R ^16- , -O-, -S-,-
A cross-linking group that is NR ¹⁷ — or —SiR ¹⁸ R ¹⁹ —. In this bridging group, R ¹⁵ and R ¹⁶ are each independently
A hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a phenyl group,
It represents a tolyl group or an anisyl group, and R ^{17 to} R ¹⁹ each independently represent a hydrogen atom or a methyl group. n represents 0 or 1. ) 13. A substituent which R ²⁶ and R ²⁷ in the general formula (9) may have is an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, an alkoxy group, an alkylamino group, an acyl group, The method according to any one of claims 10 to 12, wherein the method is selected from the group consisting of an acyloxy group, an alkoxycarbonyl group, and a halogen atom.