JP2002371090A - Method for separating palladium-containing compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for simply separating a palladium-containing compound from a solution containing a telomerization catalyst comprising a palladium compound and an organophosphorus compound with a high efficiency. SOLUTION: This method for separating the palladium-containing compound is characterized by bringing the solution containing the telomerization catalyst comprising the palladium compound and the organophosphorus compound into contact with a polymer containing thiourea groups.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a method for efficiently separating a palladium-containing compound from a solution containing a telomerization catalyst containing a palladium compound and an organic phosphorus compound.

[0002]

2. Description of the Related Art A palladium complex containing a palladium compound and an organic phosphorus compound is useful as a catalyst for a telomerization reaction of a conjugated alkadiene, and is useful as a raw material for various polymer compounds, medicines and agricultural chemicals. It is used for the synthesis of alkadiene compounds having various functional groups such as 1-ol, 1,7-octadien-3-ol, 1-acetoxy-2,7-octadiene, and 1-amino-2,7-octadiene.

However, since the palladium used for the catalyst is expensive, it is necessary to recover the catalyst component from the reaction mixture after the reaction. As the method, conventionally, an extraction separation recovery method, a distillation separation recovery method and the like have been adopted. ing. Although the catalyst recovered in these methods can be reused, it is not possible to recover all the catalyst components in the recovery step, and loss of a small amount of catalyst components is inevitable. On an industrial scale, this loss is not negligible from an economic point of view and requires a method for separating palladium-containing compounds from a solution containing a palladium catalyst.

As a method for efficiently separating a noble metal complex, a method for selectively separating a noble metal complex using a polymer having a special functional group has been developed. For example, Japanese Patent Application Laid-Open No. 50-62936 discloses a method of separating a noble metal complex belonging to Group VIII using a resin having a thiol group, and the recovery rate is about 10 to 50%. It is not always said that they are collected efficiently. JP-A-9-173835 discloses a method of recovering a noble metal using a vinylpyridine-based resin containing a pyridine ring, and the noble metal-containing compound adsorbed on the resin is an organic phosphorus compound or the like. Desorption is reported by addition of a ligand compound.

[0005]

In a reaction using a noble metal complex as a catalyst, such as a telomerization reaction, an organophosphorus compound for stabilizing the catalyst, a product, A solvent and various additives are present, and a method for separating a noble metal complex from a solution having such a complicated composition with high efficiency and convenience has not been known.

An object of the present invention is to provide a method for efficiently and easily separating a palladium-containing compound from a solution containing a telomerization catalyst containing a palladium compound and an organic phosphorus compound.

[0007]

SUMMARY OF THE INVENTION The present invention provides a palladium-containing compound characterized by contacting a solution containing a telomerization catalyst containing a palladium compound and an organic phosphorus compound with a polymer containing a thiourea group. It is a separation method.

In a preferred embodiment, the above organophosphorus compound has the general formula (I)

[0009]

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(Wherein, R ¹ and R ² each represent a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, and R ³ has a hydrogen atom or a substituent. Represents a hydrocarbon group having 1 to 5 carbon atoms which may be represented by R ⁴ , R
⁵ and R ⁶ are each a hydrocarbon group having 1 to 8 carbon atoms which may have a substituent, and at least 1
X represents a phenyl group which may have a substituent, and X represents a hydroxyl group, a hydroxycarbonyloxy group, an alkylcarbonyloxy group, a sulfonic acid group or a carboxylic acid group. ) (Hereinafter sometimes abbreviated as phosphonium salt (I)) and a compound represented by the general formula (I
I)

[0011]

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(Wherein R ⁷ , R ⁸ and R ⁹ each represent a hydrocarbon group having 1 to 8 carbon atoms which may have a substituent) [hereinafter, phosphine (I)
I).

In a preferred embodiment, the solution containing the telomerization catalyst is obtained by reacting butadiene with water, alcohol, ammonia, amine or carboxylic acid.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION In the above general formula, examples of the hydrocarbon group having 1 to 12 carbon atoms represented by R ¹ and R ² include, for example, methyl group, ethyl group, n-propyl group, n-butyl group and n-butyl group. Alkyl groups such as -pentyl group and n-octyl group; aliphatic hydrocarbon groups such as alkenyl groups such as 2-propenyl group, 3-butenyl group and 4-pentenyl group; alicyclic groups such as cycloalkyl groups such as cyclohexyl group. Formula hydrocarbon group; aryl group such as phenyl group and tolyl group; aromatic hydrocarbon group such as aralkyl group such as benzyl group; These hydrocarbon groups may have a substituent, such as a fluorine atom,
Halogen atoms such as chlorine atom, bromine atom and iodine atom;
A hydroxyl group; an alkoxyl group such as a methoxy group, an ethoxy group, a propoxy group, and a butoxy group; an amino group such as an amino group, a dimethylamino group, and a dibutylamino group.

Examples of the hydrocarbon group having 1 to 5 carbon atoms represented by R ³ include alkyl groups such as methyl group, ethyl group and propyl group; and aliphatic hydrocarbon groups such as alkenyl group such as allyl group and 4-pentenyl group. And the like. These hydrocarbon groups may have a substituent, such as a fluorine atom, a chlorine atom, a bromine atom,
A halogen atom such as an iodine atom; a hydroxyl group; a methoxy group;
An alkoxyl group such as an ethoxy group, a propoxy group and a butoxy group; an amino group such as an amino group, a dimethylamino group and a dibutylamino group.

R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹
Examples of the hydrocarbon group having 1 to 8 carbon atoms represented by are alkyl groups such as methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-octyl group, and cyclohexyl group; Aliphatic hydrocarbon groups such as alkenyl groups such as -propenyl group, 3-butenyl group and 4-pentenyl group; aryl groups such as phenyl group; and aromatic hydrocarbon groups such as aralkyl groups such as benzyl group. These hydrocarbon groups may have a substituent, and examples of the substituent include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom; a hydroxyl group; a methoxy group, an ethoxy group, a propoxy group, Alkoxyl groups such as butoxy groups; cyano groups; sulfonic acid groups and carboxylic acid groups and salts thereof. Examples of the alkylcarbonyloxy group represented by X include an acetyloxy group, a propionyloxy group, a butyryloxy group, and the like.

As the organic phosphorus compound, for example, phosphonium salt, phosphine, phosphinite, phosphonite,
Phosphite and the like are used, and among these, phosphonium salt (I) and phosphine (II) are particularly preferable. Examples of the phosphonium salt (I) include compounds represented by the following formula (III), formula (IV) or formula (V). Hereinafter, the compound represented by the formula (III) may be abbreviated as phosphonium salt (III).

[0018]

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Examples of the phosphine (II) include triphenylphosphine, tri (tolyl) phosphine, tolyldiphenylphosphine, di (tolyl) phenylphosphine, tris (trimethylphenyl) phosphine, and lithium diphenylphosphinobenzene-m-sulfonate. Aryl phosphines; alkyl phosphines such as tributyl phosphine and trioctyl phosphine; cycloalkyl phosphines such as tricyclohexyl phosphine; and alkyl aryl phosphines such as dimethyl phenyl phosphine.

The phosphinite includes, for example, aryl phosphinite such as diphenylphenoxy phosphine and ditolyl trioxy phosphine; alkyl phosphinite such as dibutyl butoxy phosphine; and alkyl aryl phosphinite such as diethyl phenoxy phosphine.

Examples of the phosphonite include aryl phosphonites such as phenyldiphenoxyphosphine; alkyl phosphonites such as butyldibutoxyphosphine; and alkylarylphosphonites such as phenyldibutoxyphosphine.

Examples of the phosphite include aryl phosphites such as triphenyl phosphite; alkyl phosphites such as tributyl phosphite; and alkyl aryl phosphites such as dimethyl phenyl phosphite.

It is also possible to combine these organic phosphorus compounds by using an appropriate spacer and use a compound having two or more phosphorus atoms in one molecule. Such compounds include, for example, 1,3-bis (diphenylphosphino) propane, bis (1,4-diphenylphosphino) butane, 2,2′-bis- (diphenylphosphinomethyl) -1,1′-biphenyl And the like.

It is known that a combination of a palladium compound and an organic phosphorus compound can catalyze various telomerization reactions [Jiro Tsuji, "Palladium Reagents and Catalysts: Innovations in Organic Synthesis" (Palladiu).
m Reagents and Catalysts: I
novations in Organic Synth
esis) "(John Wiley & Sons (JOHN W
ILEY & Sons), 1995, 422 p.
F. Heck, Palladium Reagents in Organic Synthesis (Palladium Rea)
gents in OrganicSynthese
s) "(Academic Press (ACADEMIC PR
ESS), 1985, p. 327)].

Examples of the palladium compound include a palladium (divalent) compound such as palladium acetylacetonate, π-allyl palladium acetate, palladium acetate, palladium carbonate, palladium chloride, bisbenzonitrile palladium chloride; Palladium (0-valent) compounds such as octadiene) palladium and tris (dibenzylideneacetone) dipalladium are exemplified. When a palladium (divalent) compound is used, a reducing agent may be used in combination to reduce divalent palladium to zero-valent palladium. Examples of such a reducing agent include alkali metal hydroxides such as sodium hydroxide, formic acid, sodium phenolate, sodium borohydride, hydrazine, zinc powder, magnesium and the like.

In the present specification, the palladium-containing compound means the above-mentioned palladium compound, a complex containing the above-mentioned palladium compound and the above-mentioned organophosphorus compound, or these compounds at the time of telomerization reaction, distillation, extraction, It means a compound or the like which has been changed by some action in the treatment step.

The solution containing a telomerization catalyst used in the present invention includes, for example, a reaction mixture after a telomerization reaction, and a residue after distilling off some components such as a solvent from the reaction mixture by distillation or the like. Examples thereof include a residual liquid after separating the catalyst component by a distillation method or an extraction method in order to recycle the liquid and the catalyst component.

As the polymer having a thiourea group, for example, a crosslinked polystyrene or a polymer obtained by introducing a thiourea group into polyvinylamine is used. As a method of introducing a thiourea group, for example, a method of reacting a styrene-divinylbenzene-based copolymer or a polyvinylamine having a haloalkyl group, an aminomethyl group, or the like with a salt of thiourea or thiocyanic acid is used. The form of the polymer is not particularly limited, and various forms of polymers such as beads, fibers, and sheets can be used.However, in terms of removal efficiency of the palladium-containing compound, operability, etc., the bead-like polymer is used. It is preferable to use The particle size of such a beaded polymer is preferably in the range of 0.2 mm to 2.5 mm.

The temperature at which the solution containing the telomerization catalyst is brought into contact with the polymer containing a thiourea group is from room temperature to 8
The temperature is preferably in the range of 0 ° C, more preferably in the range of room temperature to 40 ° C. The amount of the polymer used depends on the concentration of the dissolved palladium-containing compound, the type and concentration of other components such as the organic phosphorus compound, the thiourea group content in the polymer, the form of the polymer, and the contact time between the solution and the polymer. Different, but 0.1% for solutions containing the telomerization catalyst
It is preferably in the range of -20% by weight, more preferably in the range of 1-10% by weight. When the amount of the polymer used is less than 0.1%, the separation efficiency of the palladium-containing compound decreases, and the treatment time becomes longer. In addition to the complicated processing steps for recovering the wastewater, the cost increases, which is not preferable.

The method of bringing the solution containing the telomerization catalyst into contact with the polymer containing a thiourea group is not particularly limited, and a batch method, a flow method, or the like can be used. Further, the palladium-containing compound adsorbed on the polymer can be recovered by a desorption treatment, incineration or the like.

[0031]

EXAMPLES The present invention will be described below in detail with reference to examples, but the present invention is not limited to these examples.

The measurement of the palladium concentration and the phosphorus concentration in the solution was performed using an IPC emission spectrometer (manufactured by Nippon Jarrell Ash).

REFERENCE EXAMPLE 1 A 5 L stainless steel autoclave was charged with 600 mg (2.7 mmol) of palladium acetate, 23 g (44 mmol) of phosphonium salt (III), 280 g (2.8 mol) of triethylamine, 940 g of sulfolane and 780 g of water. Telomerization catalyst solution,
Furthermore, butadiene is continuously supplied to the reactor and the system is reacted at 75 ° C. with carbon dioxide at a total pressure of 14 kg / cm ² , thereby performing a continuous synthesis reaction of 2,7-octadien-1-ol. Was. A portion of the reaction mixture thus obtained was continuously withdrawn, an equal volume of hexane was added and extraction was performed continuously, and the catalyst liquid layer and the hexane layer containing the product were separated. The hexane layer was further washed with hydrous sulfolane containing lithium m- (diphenylphosphino) benzenesulfonate. The recovered catalyst solution was returned to the reactor as it was, and continuous operation was continued. On the other hand, the palladium concentration in the obtained hexane solution was 0.103 ppm.

Example 1 A chelate resin Levatit TP having a thiourea group as a functional group was placed in a three-necked flask having an inner volume of 2 L equipped with a stirrer.
0.5 g of 214 (manufactured by Bayer Japan KK) and 1 L of the hexane solution obtained in Reference Example 1 were added and stirred at room temperature. Table 1 shows the palladium concentration in the solution after stirring for a predetermined time.

Comparative Example 1 In Example 1, instead of the chelating resin TP214,
The same treatment was performed except that TP207 (manufactured by Bayer Japan Ltd.) having iminodiacetic acid as a functional group was used. Table 1 shows the results.

[0036]

[Table 1]

Reference Example 2 In a stainless steel autoclave having an inner volume of 5 L, 600 mg (2.7 mmol) of palladium acetate, 23 g (44 mmol) of phosphonium salt (III), 280 g (2.8 mol) of triethylamine, 940 g of sulfolane and 780 g of water were added. Telomerization catalyst solution,
Further, butadiene is continuously supplied to the reactor, and the system is reacted at 75 ° C. with carbon dioxide at a total pressure of 14 kg / cm ² , thereby performing a continuous synthesis reaction of 2,7-octadien-1-ol. Was. After extracting a part of the reaction mixture thus obtained, low-boiling components such as butadiene are distilled off, whereby the palladium concentration becomes 264.
ppm solution was obtained.

Example 2 A 2 L three-necked flask equipped with a stirrer was charged with the solution obtained in Reference Example 2 and 2 g of Levatit TP214 (as described above), and stirred at room temperature for 4 days. The palladium concentration in the obtained solution was 29 ppm, and the separation rate of the palladium-containing compound was 89%.

REFERENCE EXAMPLE 3 Referring to WO92 / 10450, 7.2 mg (0.02 mmol) of palladium acetylacetonate, 12 mg (0.05 mmol) of triphenylphosphine, and 50 mg of sodium methoxide were placed in a 1 L stainless steel autoclave. (0.93 mmol) and a telomerization catalyst solution consisting of 150 g of methanol, and further, butadiene was supplied to the reactor, and the system was reacted with nitrogen at a total pressure of 14 kg / cm ² at 80 ° C. for 3 hours. Methoxyocta-2,7-diene was synthesized. After the completion of the reaction, a part of butadiene and methanol was distilled off from the obtained reaction mixture to obtain a concentrated liquid. The palladium concentration in this concentrated liquid was 16 ppm.

Example 3 A 200 ml three-necked flask equipped with a stirrer was
0.3 g of Levatit TP214 resin (as described above) and 40 ml of the concentrate obtained in Reference Example 3 were added, and the mixture was stirred at room temperature for 24 hours. The palladium concentration in the obtained solution was 1.4 ppm, and the separation rate of the palladium-containing compound was 91%.

Reference Example 4 Referring to JP-A-11-189557, palladium acetate 3 was added to a stainless steel autoclave having an internal volume of 1 L.
A telomerization catalyst solution consisting of 0 mg (0.13 mmol), 420 mg (1.4 mmol) of tri (o-tolyl) phosphine, 18 g (0.18 mol) of triethylamine, 110 g of acetone and 36 g of water was added, and then butadiene was added to the reactor. The mixture was supplied, the system was pressurized with carbon dioxide to a total pressure of 10 kg / cm ² , and reacted at 75 ° C. for 3 hours to synthesize 2,7-octadien-1-ol. After the completion of the reaction, the low-boiling components were distilled off from the obtained reaction mixture, and the product was removed by distillation. The obtained residue was extracted with water. The palladium concentration in the obtained aqueous solution was 2 ppm.

Example 4 A 200-ml three-necked flask equipped with a stirrer was charged with
0.15 g Levatit TP214 resin (as described above)
Then, 20 ml of the aqueous solution obtained in Reference Example 4 was added, and the mixture was stirred at room temperature for 24 hours. The palladium concentration in the obtained solution was 0.44 ppm, and the separation rate of the palladium-containing compound was 78%.

[0043]

According to the present invention, a palladium-containing compound can be separated and recovered with high efficiency.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C07C 33/02 C07C 33/02 41/06 41/06 43/15 43/15 F-term (Reference) 4H006 AC21 AC41 AC43 BA25 BA32 BA45 BA51 BA53 BA83 BB23 BB31 GN21 GP01 4H039 CA29 CF10 4H050 AD17 AD33 WB13 WB19 4J015 DA23 EA02

Claims (3)

[Claims] 1. A method for separating a palladium-containing compound, which comprises contacting a solution containing a telomerization catalyst containing a palladium compound and an organic phosphorus compound with a polymer containing a thiourea group. 2. The organic phosphorus compound represented by the general formula (I): (Wherein, R ¹ and R ² each represent a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, and R ³ may have a hydrogen atom or a substituent. Represents a hydrocarbon group having 1 to 5 carbon atoms, and represents R ⁴ , R ⁵ and R ⁶
Is a hydrocarbon group having 1 to 8 carbon atoms which may have a substituent, at least one of which represents a phenyl group which may have a substituent, X is a hydroxyl group, hydroxycarbonyloxy Represents an alkylcarbonyloxy group, a sulfonic acid group or a carboxylic acid group. And a phosphonium salt represented by the general formula (II): (Wherein R ⁷ , R ⁸ and R ⁹ each represent an optionally substituted hydrocarbon group having 1 to 8 carbon atoms) selected from the group consisting of phosphines represented by the following formula: Separation method as described. 3. The solution containing a telomerization catalyst,
3. The separation method according to claim 1, wherein the separation method is obtained by reacting butadiene with water, alcohol, ammonia, amine or carboxylic acid.