JP2004155722A - Method for producing mono(dimethyloctyl) ether - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing a mono(dimethyloctyl) ether of a polyol by which the reaction is efficiently promoted. <P>SOLUTION: The method for producing the mono(dimethyloctyl) ether of the polyol comprises a first step for bringing the following liquid phase (A) into contact with the following liquid phase (B) to afford dimethyloctadienyl ether, and a second step for hydrogenating a dimethyloctadienyl group of the product in the presence of a catalyst containing a group 8-10 element in the periodic table in a hydrogen atmosphere: liquid phase (A) comprises (a<SB>1</SB>) a total 3-6C polyol having 3-4 hydroxy groups, a palladium compound, a water-soluble tertiary phosphine or phosphite, water and an alkali metal hydroxide or alkaline earth metal hydroxide, or (a<SB>2</SB>) the total 3-6C polyol having 3-4 hydroxy groups, a complex of palladium, and the water-soluble tertiary phosphine or phosphite, the water and the alkali metal hydroxide or alkaline earth metal hydroxide; and liquid phase (B) is an oily liquid phase containing isoprene. <P>COPYRIGHT: (C)2004,JPO

Description

[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a method for producing mono (dimethyloctyl) ether of a polyol, especially mono (dimethyloctyl) glycerylether.
[0002]
[Prior art]
Monoalkyl ethers of polyols represented by monoalkyl glyceryl ethers (hereinafter also referred to as monoalkyl ethers) are excellent nonionic surfactants as emulsifiers, dispersants, detergents and the like.
[0003]
As a method for producing a monoalkyl glyceryl ether, (1) a method of synthesizing a glycidyl ether from an alcohol and an epihalohydrin such as epichlorohydrin, and further hydrolyzing it is common. In addition, (2) a method of reacting an alkyl halide and glycerin using a base, (3) a method of directly reacting an alcohol and glycerin with an acid catalyst, and (4) a method of reacting an alcohol and glycidol with an acid or a basic catalyst A method of reacting is also known.
[0004]
However, in the method (1), it is difficult to selectively synthesize glycidyl ether, and there is a possibility that an organic chlorinated compound derived from a raw material may be mixed. In addition, the method (2) has a problem that not only is it difficult to selectively synthesize a monoalkyl glyceryl ether, but also it is necessary to treat a large amount of generated salt, and the product is significantly colored. In the method 3), similarly, it is difficult to selectively synthesize a monoalkyl glyceryl ether, and there is a problem that a by-product of a dialkyl glyceryl ether or a dialkyl ether in which alcohols react with each other cannot be avoided. There is a problem that it is difficult to avoid polymerization of glycidol itself or excessive addition of glycidol to the product.
[0005]
On the other hand, it is known that a conjugated diene is telomerized with an alcohol or a polyol to obtain 1,7- or 2,7-alkadienyl ether. Among them, a secondary alcohol solution such as 2-propanol is used. A method of synthesizing alkadienyl glyceryl ether by telomerization using a conjugated diene and a polyol, particularly glycerin, is disclosed (for example, see Patent Document 1). By hydrogenating this alkadienyl glyceryl ether, an alkyl glyceryl ether is obtained.In this method, alkadienyl glyceryl ether, which is a product of telomerization, is converted into a monoether compound, a diether compound, and a triether compound. And it is difficult to selectively synthesize only the monoalkadienyl glyceryl ether, and it is also difficult to recover and reuse the catalyst.
Furthermore, there is known a method for selectively synthesizing monoalkadienyl glyceryl ether using telomerization of a conjugated diene (for example, see Patent Document 2). However, depending on the type of the conjugated diene, a phenomenon in which the reactivity is reduced has been observed.
[0006]
[Patent Document 1]
Japanese Patent Publication No. 6-509339 [Patent Document 2]
JP-A-2002-53514
[Problems to be solved by the invention]
Therefore, the present invention provides a mono (dimethyloctyl) ether of a polyol, which can proceed the reaction very efficiently even when isoprene which is a conjugated diene whose reactivity decreases in telomerization of a conjugated diene. It is an object to provide a manufacturing method.
[0008]
[Means for Solving the Problems]
The invention comprises the following liquid phases (A) and (B):
(A) (a ₁ ) a polyol having 3 or 4 hydroxyl groups and a total of 3 to 6 carbon atoms, a palladium compound, a water-soluble tertiary phosphine or phosphite, water, and an alkali metal hydroxide or alkaline earth metal Hydroxide, or (a ₂ ) a polyol having 3 to 4 hydroxyl groups and having 3 to 4 carbon atoms, a complex of palladium with a water-soluble tertiary phosphine or phosphite, water, and an alkali metal hydroxide or An aqueous liquid phase containing an alkaline earth metal hydroxide,
(B) After contacting an oily liquid phase containing isoprene to obtain a dimethyloctadienyl ether having a dimethyloctadienyl group in which isoprene is dimerized, the obtained dimethyloctadienyl is reacted with hydrogen. Performing a second step of hydrogenating a dimethyloctadienyl group in the presence of a catalyst containing an element selected from Groups 8 to 10 of the periodic table in an atmosphere, the method for producing a mono (dimethyloctyl) ether of the polyol. To provide.
[0009]
BEST MODE FOR CARRYING OUT THE INVENTION
<First step>
Specific examples of the polyol having 3 to 6 hydroxyl groups and having 3 to 4 carbon atoms include triols such as glycerin, trimethylolmethane, trimethylolethane and trimethylolpropane, and tetraols such as pentaerythritol. , Triol is preferred, and glycerin is particularly preferred.
The ratio of polyol to water in the aqueous liquid phase in the first step is preferably 0.01 to 10 times by weight, more preferably 0.1 to 20 times by weight, and particularly preferably 2 to 10 times by weight.
[0010]
Examples of the palladium compound contained in the aqueous liquid phase (A) (a ₁ ) include palladium compounds such as bis (acetylacetonato) palladium (II), palladium (II) acetate and palladium (II) chloride. Of these, bis (acetylacetonato) palladium (II) and palladium acetate are preferred. One or more of these palladium compounds can be used.
In the present invention, a complex of palladium and a water-soluble tertiary phosphine or phosphite can be used as a component equivalent to the palladium compound and the water-soluble tertiary phosphine or phosphite. Preferred examples of such a complex include a mono-, di-, tri- or higher sulfonate such as tetrakis (triphenylphosphine) palladium (0), or a metal salt thereof. One or more of these palladium complexes can be used.
The amount of the palladium compound or the complex of palladium and the water-soluble tertiary phosphine or phosphite is preferably 0.0001 to 0.1 mol times, more preferably 0.001 to 0.1 mol times, relative to the polyol. More preferably, the amount is 0.001 to 0.01 times by mole.
[0011]
As the water-soluble tertiary phosphine or phosphite contained in the aqueous liquid phase (A), various tertiary phosphines or sulfonated phosphites or alkali metal salts thereof are preferable. Mono-, di- or tri-sulfonated aliphatic (preferably C1 to C20) phosphines or their alkali metal salts; triphenylphosphine, dimethylphenylphosphine, methyldiphenylphosphine, diethylphenylphosphine, ethyldiphenyl Mono-, di-, tri- or more sulfonated aromatic or aromatic-aliphatic (preferably C8-C32) phosphine such as phosphine, or alkali metal salts thereof; 1,2-bis (diphenylphospho) Fino) ethane, 1,3-bis (diff A third bidentate ligand such as nylphosphino) propane, 1,4-bis (diphenylphosphino) butane, 1,4-bis (dimethylphosphino) butane, or 1,2-bis (dimethylphosphino) ethane; Mono-, di-, tri-, tetra- or higher sulfonates of primary phosphines or alkali metal salts thereof; sulfonates of phosphites having the same structure as these, or alkali metal salts thereof. These tertiary phosphines or phosphites act as ligands for some or all of the palladium atoms derived from the palladium compound, and can dissolve some or all of the palladium compound in the aqueous liquid phase. Further, compounds having a carboxyl group as a substituent in place of part or all of the sulfonic acid groups of these phosphines or phosphites are also preferable. The sulfonic acid groups or carboxyl groups contained in these tertiary phosphines or phosphites need to contain sulfonic acid groups or carboxyl groups in such an amount that these tertiary phosphines or phosphites are easily dissolved in water. It is. Of these, sulfonated aromatic tertiary phosphines or phosphites (including compounds that become bidentate ligands) or alkali metal salts thereof are preferable, for example, triphenylphosphine trisulfonic acid and its trisodium salt. , Triphenylphosphine disulfonic acid and its dipotassium salt.
[0012]
When the water-soluble tertiary phosphine or phosphite is used in the palladium compound, the tertiary phosphine or phosphite sulfonate (or carboxylate) or the alkali metal salt thereof is used in the palladium compound. The amount is preferably 0.1 to 4 times by mole, particularly preferably 1 to 4 times by mole. In the case of a tertiary phosphine or a phosphite serving as a bidentate ligand, the amount is preferably 0.1 to 2 times, more preferably 0.5 to 2 times, the molar amount of the palladium compound.
[0013]
Examples of the alkali metal hydroxide or alkaline earth metal hydroxide contained in the aqueous liquid phase (A) include sodium hydroxide, potassium hydroxide, lithium hydroxide, magnesium hydroxide, and calcium hydroxide. No. These can be used alone or in combination of two or more.
The amount of the alkali metal hydroxide or alkaline earth metal hydroxide used is such that the concentration of the aqueous liquid phase is 0.01 to 20% by weight, further 0.1 to 10% by weight, particularly 1 to 5% by weight. Is preferred.
[0014]
As the solvent for the oily liquid phase (B) of the present invention, isoprene used in the reaction is preferably used as it is, but other solvents can be used if necessary. As such another solvent, a solvent which dissolves isoprene used in the reaction and dimethyloctadienyl ether to be formed and is immiscible with the aqueous liquid phase is preferable, and a hydrocarbon solvent or glycol diethers is preferable. In particular, when a polyol other than glycerin is used, it is preferable to use a glycol diether for controlling the reaction.
Examples of the hydrocarbon solvent include C _{6 to} C ₂₀ saturated hydrocarbons such as hexane, heptane, octane, nonane, decane, undecane, dodecane, tridecane, tetradecane, pentadecane, hexadecane, heptadecane, octadecane, nonadecane, and icosane. It is also preferable to use the above isoprene to be reacted as a solvent as it is.
When the above glycol diethers are used as a solvent, those having a total carbon number of 20 or less are preferable, and specifically, glycol diethers such as ethylene glycol dialkyl ether and diethylene glycol dialkyl ether are preferable. Dibutyl ether, ethylene glycol butyl methyl ether, ethylene glycol butyl ethyl ether, diethylene glycol dibutyl ether and the like are more preferred.
[0015]
The hydrocarbon solvent phase containing isoprene may be charged at once in a reaction vessel such as an autoclave or may be continuously introduced, but isoprene is added to the polyol in the aqueous liquid phase in an amount of 1.0 to 10. It is preferable to charge so as to be 0 mole times, particularly 1.0 to 6.0 mole times.
[0016]
The reaction temperature in the first step is preferably maintained at 10 to 100C, particularly preferably 60 to 100C.
[0017]
In the first step of the present invention, since the catalyst is mostly present in the aqueous liquid phase, the aqueous liquid phase containing the catalyst, unreacted polyol, etc. can be recovered after the reaction, if necessary, and can be reused. It is.
[0018]
<Second step>
Examples of the catalyst containing an element selected from Groups 8 to 10 of the Periodic Table used in the hydrogenation of the dimethyloctadienyl group in the second step include Fe, Co, Ni, Ru, Rh, Pd, Os, Ir and Pt. And metals containing Pd, Rh, Ru, Ni, Pt and the like in a low oxidation state. Particularly, these metals include carbon, zeolite, silica alumina and the like. Preferred are those loaded with 10 to 10% by weight, Raney nickel, and oxides of these metals. The amount of the catalyst to be used is preferably 0.01 to 10% by weight, particularly preferably 0.1 to 5% by weight, based on dimethyloctadienyl ether. The hydrogen pressure is not particularly limited, but is preferably in the range of normal pressure to 20 MPa.
[0019]
The dimethyloctyl group of the mono (dimethyloctyl) ether of the polyol obtained in the present invention may be bonded to a hydroxyl group at any position of the polyol, but usually, the bonding to the primary hydroxyl group of the polyol is preferred. .
Further, when glycerin is used as the polyol, mono (dimethyloctyl) glyceryl ether which is excellent as a nonionic surfactant can be produced.
[0020]
【Example】
Example 1
In a 500 mL autoclave, glycerin 70 g (0.76 mol), bis (acetylacetonato) palladium (II) 0.14 g (0.46 mmol), triphenylphosphine-3,3 ′, 3 ″ -trisulfonic acid trisodium salt After adding and dissolving 0.60 g (1.05 mmol) and 20 g of water, 2.0 g (0.035 mol) of potassium hydroxide was further added to form an aqueous phase, 224 g (3.3 mol) of isoprene was added, and the atmosphere was replaced with nitrogen. Then, the temperature was raised to 70 ° C., and the mixture was stirred for 15 hours at 70 ° C. After allowing to cool to room temperature, unreacted isoprene and a small amount of dimethyloctatriene and dimethyloctadienol by-produced were distilled off under reduced pressure. And washed with water to give 125 g of mono (dimethyloctadienyl) glyceryl ether as a clear yellow oil ( Yield 72%).
50 g of the obtained mono (dimethyloctadienyl) glyceryl ether and 3 g of 5% Pd-C (manufactured by NE Chemcat) were added to a 500 mL autoclave, and the mixture was stirred at 50 ° C. for 12 hours under a hydrogen atmosphere at a pressure of 5 MPa. After the completion of the reaction, the catalyst was removed by filtration to obtain 49 g of mono (dimethyloctyl) glyceryl ether as a colorless transparent oil. The positions of methyl groups such as dimethyloctyl group, 3,7-dimethyl-1-octyl group and 3,6-dimethyl-1-octyl group of this mono (dimethyloctyl) glyceryl ether are different by GC (gas chromatography) analysis. It was a mixture of isomers, the purity as mono (dimethyloctyl) glyceryl ether was 99%, and the content of di (dimethyloctyl) glyceryl ether was 1%.
[0021]
Comparative Example 1
In a 500 mL autoclave, glycerin 70 g (0.76 mol), bis (acetylacetonato) palladium (II) 0.14 g (0.46 mmol), triphenylphosphine-3,3 ′, 3 ″ -trisulfonic acid trisodium salt 0.60 g (1.05 mmol) and 20 g of water were added to form an aqueous phase, 224 g (3.3 mol) of isoprene was added, the atmosphere was replaced with nitrogen, the temperature was raised to 70 ° C, and the mixture was stirred at 70 ° C for 15 hours. After cooling to room temperature, unreacted isoprene and a small amount of by-produced dimethyloctatriene were distilled off under reduced pressure, and the residue was washed with water to obtain 16 g of mono (dimethyloctadienyl) glyceryl ether (yield). 9%).
[0022]
Example 2
In a 500 mL autoclave, 70 g (0.76 mol) of glycerin, 0.10 g (0.45 mmol) of palladium (II) acetate, 0.60 g of triphenylphosphine-3,3 ′, 3 ″ -trisulfonic acid trisodium salt (1 After dissolving by adding 20 g of water and further adding 2.0 g (0.035 mol) of potassium hydroxide to form an aqueous phase, adding 224 g (3.3 mol) of isoprene and purging with nitrogen, and then 70 ° C. Then, the mixture was stirred for 15 hours at 70 ° C. After cooling to room temperature, unreacted isoprene and a small amount of dimethyloctatriene and dimethyloctadienol by-produced were distilled off under reduced pressure and washed with water. And 130 g of mono (dimethyloctadienyl) glyceryl ether were obtained as a yellow transparent oil (yield 75%).
The obtained mono (dimethyloctadienyl) glyceryl ether was hydrogenated in the same manner as in Example 1 to obtain mono (dimethyloctyl) glyceryl ether having a purity of 98% according to GC analysis. The content of di (dimethyloctyl) glyceryl ether was 2%.
[0023]
Example 3
The reaction was carried out in the same manner as in Example 2 except that potassium hydroxide in Example 2 was changed to 2.1 g of sodium hydroxide. As a result, the yield of mono (dimethyloctadienyl) glyceryl ether was 121 g (yield 70%).
The obtained mono (dimethyloctadienyl) glyceryl ether was hydrogenated in the same manner as in Example 1 to obtain mono (dimethyloctyl) glyceryl ether having a purity of 98% according to GC analysis. The content of di (dimethyloctyl) glyceryl ether was 2%.
[0024]
Example 4
4.0 g (20 mmol) of diphenylmethylphosphine and 9.5 g (60 mmol) of a pyridine / SO ₃ complex were dissolved in 150 mL of benzene and refluxed for 12 hours. After the reaction, the precipitated white solid was removed by filtration, the solvent was distilled off, and then 500 mL of 1N sulfuric acid was added, followed by stirring at room temperature. After extraction with chloroform, the mixture was further washed with water and the solvent was distilled off to obtain 2.0 g of a sulfonated product of diphenylmethylphosphine as a white solid.
¹ H NMR (Heavy DMSO)
Diphenylmethylphosphine methyl proton σ: 1.6
Aromatic ring proton σ: 7.3 (multiple line)
Diphenylmethylphosphine sulfonate methyl proton σ: 2.0
Aromatic ring proton σ: 7.5, 7.7
In a 500 mL autoclave, 70 g (0.76 mol) of glycerin, 0.10 g (0.45 mmol) of palladium (II) acetate, 0.41 g (1.14 mmol) of the above sulfonate, 20 g of water, and 3.0 g of potassium hydroxide (0 g) (0.054 mol) was added to obtain an aqueous solution phase. After adding 224 g (3.3 mol) of isoprene and purging with nitrogen, the temperature was raised to 70 ° C., and the mixture was stirred at 70 ° C. for 15 hours. After allowing to cool to room temperature, unreacted isoprene and a small amount of dimethyloctatriene and dimethyloctadienol by-produced are distilled off under reduced pressure, washed with water, and 116 g of mono (dimethyloctadienyl) glyceryl ether is yellowed. Obtained as a clear oil (67% yield).
The obtained mono (dimethyloctadienyl) glyceryl ether was hydrogenated in the same manner as in Example 1 to obtain mono (dimethyloctyl) glyceryl ether having a purity of 98% according to GC analysis. The content of di (dimethyloctyl) glyceryl ether was 2%.
[0025]
Example 5
4.0 g (9.7 mmol) of 1,3-bisdiphenylphosphinopropane and 10.0 g (63 mmol) of a pyridine / SO ₃ complex were dissolved in 150 mL of benzene and refluxed for 12 hours. After the reaction, the precipitated white solid was collected by filtration and further washed with benzene. After drying, 500 mL of 1N sulfuric acid was added, and the mixture was stirred at room temperature. After extraction with chloroform, the product was washed with water and dried to obtain a sulfonated product of 1,3-bisdiphenylphosphinopropane as 2.5 g of a pale yellow-white solid.
¹ H NMR (Heavy DMSO)
1,3-bisdiphenylphosphinopropane methylene proton σ: 3.3, 3.6
Aromatic ring proton σ: 8.3 (multiple line)
1,3-bisdiphenylphosphinopropane sulfonate methylene proton σ: 3.4
Aromatic ring proton σ: 8.4, 8.6
In a 500 mL autoclave, 70 g (0.76 mol) of glycerin, 0.10 g (0.45 mmol) of palladium (II) acetate, 0.35 g (0.48 mmol) of the above sulfonate, 20 g of water, and 3.0 g of potassium hydroxide (0 g) (0.054 mol) was added to obtain an aqueous solution phase. After adding 224 g (3.3 mol) of isoprene and purging with nitrogen, the temperature was raised to 70 ° C., and the mixture was stirred at 70 ° C. for 15 hours. After allowing to cool to room temperature, unreacted isoprene and a small amount of by-produced dimethyloctatriene were distilled off under reduced pressure and washed with water to obtain 110 g of mono (dimethyloctadienyl) glyceryl ether as a yellow transparent oil. (Yield 64%).
The obtained mono (dimethyloctadienyl) glyceryl ether was hydrogenated in the same manner as in Example 1 to obtain mono (dimethyloctyl) glyceryl ether having a purity of 98% according to GC analysis. The content of di (dimethyloctyl) glyceryl ether was 2%.
[0026]
【The invention's effect】
According to the present invention, mono (dimethyloctyl) ether can be produced more selectively, conveniently and economically, and the catalyst can be recovered and reused.

Claims (4)

The following liquid phases (A) and (B):
(A) (a ₁ ) a polyol having 3 or 4 hydroxyl groups and a total of 3 to 6 carbon atoms, a palladium compound, a water-soluble tertiary phosphine or phosphite, water, and an alkali metal hydroxide or alkaline earth metal water Oxide, or (a ₂ ) a polyol having 3 to 4 hydroxyl groups and having 3 to 4 carbon atoms, a complex of palladium with a water-soluble tertiary phosphine or phosphite, water, and an alkali metal hydroxide or alkaline earth An aqueous liquid phase containing a class of metal hydroxides,
(B) After contacting an oily liquid phase containing isoprene to obtain a dimethyloctadienyl ether having a dimethyloctadienyl group in which isoprene is dimerized, the obtained dimethyloctadienyl ether is A method for producing mono (dimethyloctyl) ether of the above polyol, wherein a second step of hydrogenating a dimethyloctadienyl group is carried out in a hydrogen atmosphere in the presence of a catalyst containing an element selected from Groups 8 to 10 of the periodic table. . The method for producing mono (dimethyloctyl) ether according to claim 1, wherein the polyol is glycerin, and the oily liquid phase (B) is a hydrocarbon solvent containing isoprene. 3. The process for producing mono (dimethyloctyl) ether according to claim 1, wherein isoprene is used as a solvent for the oily liquid phase (B) in the first step. The water-soluble tertiary phosphine or phosphite of the aqueous liquid phase (A) in the first step is a sulfonated aromatic tertiary phosphine or phosphite, or an alkali metal salt thereof. The method for producing mono (dimethyloctyl) ether according to claim 1.