JPH10218808A - Production of higher alcohol and (poly)alkylene glycol higher alkyl ether and catalyst used therefor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject compound by reacting a long-chain olefin with water or a (poly)alkylene glycol in the presence of a specific solid acid catalyst. SOLUTION: Preferably 8-30C long-chain olefin (e.g. octene) is reacted with water or a (poly)alkylene glycol (e.g. monoethylene glycol) at 50-250 deg.C by using a solid acid catalyst having >=0.06mmol acidity per g catalyst and >=0.6mmol saturated absorption amount of normal propanol per g catalyst (e.g. crystalline metallosilicate or zeolite) to provide the objective higher alcohol [e.g. various isomers of decanol (e.g. 2 to 6-decanol)] or the objective (poly)alkylene glycol higher alkyl ether (e.g. monoethylene glycol monododecyl ether).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing higher alcohols and (poly) alkylene glycol higher alkyl ethers, and a catalyst used therefor. More specifically, a method for producing a higher alcohol by reacting a long-chain olefin with water, and a method for producing a (poly) alkylene glycol higher alkyl ether by reacting a long-chain olefin with a (poly) alkylene glycol. The present invention relates to a method and a catalyst used for the method.

[0002]

2. Description of the Related Art Many catalysts such as sulfuric acid, phosphoric acid, heteropoly acids, ion exchange resins, and inorganic solid acids have been proposed for producing alcohols by reacting olefins with water. For example, Japanese Patent Publication No. 49-36203 proposes a method for producing an alcohol by hydrating an olefin using silicotungstic acid as a catalyst. The example discloses a method for producing alcohol by reacting propylene, butene and water in the presence of silicotungstic acid. Japanese Patent Application Laid-Open No. 6-1736 proposes a method for producing a higher secondary alcohol by reacting an aqueous solution containing 50% by weight or more of a heteropolyacid as a catalyst with a higher α-olefin. Examples include:
A method for producing a higher secondary alcohol by reacting 50% by weight or more of an aqueous solution of a heteropolyacid with decene is disclosed.

With respect to a method for producing a (poly) alkylene glycol monoalkyl ether by reacting an olefin with a (poly) alkylene glycol, the olefin is reacted with the (poly) alkylene glycol in the presence of a strongly acidic cation exchange resin as a catalyst. A method for producing a (poly) alkylene glycol monoalkyl ether by reacting is described in, for example, Japanese Patent Publication No.
0-34935, JP-B-62-17574, and JP-A-2-295941. A method for producing a (poly) alkylene glycol monoalkyl ether by reacting an olefin with a (poly) alkylene glycol in the presence of a heteropolyacid as a catalyst is disclosed in, for example, JP-A-3-148233. A method for producing a (poly) alkylene glycol monoalkyl ether by reacting an olefin with a (poly) alkylene glycol in the presence of benzenesulfonic acid or toluenesulfonic acid as a catalyst is disclosed, for example, in JP-B-61-51570. Is disclosed.

[0004]

In the hydration reaction, in the prior art, for example, when a heteropolyacid is used as a catalyst, the hydration reaction of a long-chain olefin is inherently slow in the reaction rate. To increase the conversion,
It is essential to use the catalyst in a large amount of 50% by weight or more in water, and there is a problem in industrial use. Also, in other catalyst systems, sulfuric acid, phosphoric acid, and the like have a problem in industrial use, such as corrosion of the apparatus and a decomposition reaction occurring when the reaction product is recovered. Reaction rates of ion exchange resins, inorganic solid acids, and the like were slow and were not sufficient for industrial use.

In the reaction of an olefin with a (poly) alkylene glycol, the conversion rate of the olefin is low and the selectivity of the olefin to the (poly) alkylene glycol monoalkyl ether is low due to the low reaction rate of the conventional catalyst. In particular, there is a problem that as the carbon number of the olefin increases, the reaction rate decreases significantly. Furthermore, since the other material, (poly) alkylene glycol, is a dihydric alcohol, its own dehydration-condensation reaction or dehydration-cyclization reaction occurs as a side reaction during the reaction, and the addition reaction to the olefin is selected. There was also a problem that the rate was extremely low.

The problem to be solved by the present invention is to solve the problems of the above-mentioned conventional methods, and to provide a higher alcohol and a (poly) alkylene glycol higher alkyl ether with a high reaction rate, a high selectivity and a high yield. It is an object of the present invention to provide a method for producing it industrially advantageously, and a catalyst used therefor.

[0007]

Means for Solving the Problems The present inventors have conducted intensive studies to solve these problems, and as a result, have developed a catalyst using the acid amount and the hydrophobicity of the solid catalyst as indices. In each reaction of synthesis of higher alcohol and synthesis of (poly) alkylene glycol higher alkyl ether by long chain olefin and (poly) alkylene glycol, the reaction rate is fast, side reactions can be suppressed, selectivity is high, and each purpose is efficient The present inventors have found conditions under which a product can be manufactured, and have completed the present invention.

That is, the present invention is a method for producing a higher alcohol by reacting a long-chain olefin with water in the presence of a catalyst, wherein the catalyst has an acid amount of 0.06 mmol or more per gram of catalyst, A method for producing a higher alcohol, wherein a solid catalyst having a saturated adsorption amount of normal propanol of 0.6 mmol or more per gram of catalyst is used.

In the present invention, the long-chain olefin is at least one selected from the group consisting of olefins having 8 to 30 carbon atoms. The present invention also relates to a solid catalyst used in producing a higher alcohol by reacting a long-chain olefin with water, wherein the acid amount is 0.06 mmol or more per gram of the catalyst, and the saturated adsorption amount of normal propanol is The catalyst is characterized in that the amount is 0.6 mmol or more per gram of the catalyst.

The present invention also relates to a long-chain olefin and (poly)
Reacting with an alkylene glycol in the presence of a catalyst,
A method for producing a (poly) alkylene glycol higher alkyl ether, wherein the catalyst has an acid amount of 0.06 mmol or more per gram of catalyst and a saturated adsorption amount of normal propanol of 0.6 mmol per gram of catalyst.
Characterized by using the above solid catalyst (poly)
This is a method for producing an alkylene glycol higher alkyl ether.

In the present invention, the long-chain olefin is at least one selected from the group consisting of olefins having 8 to 30 carbon atoms. The present invention also provides a solid catalyst used in producing a (poly) alkylene glycol higher alkyl ether by reacting a long-chain olefin with a (poly) alkylene glycol, wherein the acid amount is 0.06 mmol or more per gram of the catalyst. And the saturated adsorption amount of normal propanol is 0.6 per gram of catalyst.
It is a catalyst characterized in that it is at least mmol.

[0012]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. The present invention is directed to reactions of synthesis of a higher alcohol with a long-chain olefin and water and synthesis of a (poly) alkylene glycol higher alkyl ether with a long-chain olefin and (poly) alkylene glycol.

In the synthesis of a higher alcohol from a long-chain olefin and water, a higher alcohol is generated by adding water to the long-chain olefin. The long-chain olefin <=> higher alcohol has an equilibrium relationship of OL + H ₂ O <=> AL (1) (OL: long-chain olefin, AL: higher alcohol), and hydration reaction And the reverse reaction proceed simultaneously. Therefore, the catalyst of the present invention can be used as an effective catalyst for synthesizing long-chain olefins and water by elimination of higher alcohols.

In the synthesis of a (poly) alkylene glycol higher alkyl ether with a long-chain olefin and a (poly) alkylene glycol, the (poly) alkylene glycol higher alkyl ether and the (poly) alkylene glycol mono-higher alkyl ether and (poly) alkylene glycol dialkyl A higher alkyl ether is formed. OL + PAG <=> M ... (2) OL + M <=> D ... between long chain olefin, (poly) alkylene glycol mono-higher alkyl ether and (poly) alkylene glycol di-higher alkyl ether (3) M + M <=> D + PAG (4) (OL: long-chain olefin, PAG: (poly) alkylene glycol, M: (poly) alkylene glycol mono-higher alkyl ether, D: (Poly) alkylene glycol di-higher alkyl ether).
Addition reactions, condensation reactions, and their reverse reactions proceed simultaneously. When synthesizing a (poly) alkylene glycol higher alkyl ether from a long-chain olefin and a (poly) alkylene glycol, first, the (poly) alkylene glycol is added to the long-chain olefin by the reaction of (2) to form a (poly)
An alkylene glycol mono higher alkyl ether is formed. Next, the reaction of (3) or (4) proceeds, and (poly) alkylene glycol di-higher alkyl ether is produced.
Since these are equilibrium reactions, the reverse reactions of (2), (3) and (4) are also progressing. Therefore, the catalyst of the present invention can be used for the synthesis of a long-chain olefin and a (poly) alkylene glycol by the elimination reaction of a (poly) alkylene glycol mono-higher alkyl ether (reverse reaction of (2)), Synthesis of long chain olefin and (poly) alkylene glycol mono higher alkyl ether by elimination reaction (reverse reaction of (3)), (poly) alkylene glycol mono higher alkyl ether and (poly) alkylene glycol It can also be used as an effective catalyst for reactions such as the synthesis of higher alkyl ethers (reverse reaction of (4)).

In addition, a reaction in which the position of the unsaturated bond of the long-chain olefin is isomerized occurs simultaneously with the hydration reaction of the long-chain olefin and the addition reaction of the (poly) alkylene glycol. In general, an inner olefin is more thermodynamically stable than an α-olefin. Therefore, when an α-olefin is used as a raw material, the olefin is isomerized into an inner olefin during the reaction. Therefore, the catalyst of the present invention can be used as an effective catalyst for a long-chain olefin isomerization reaction. The isomerization of long-chain olefins
By performing the reaction in the presence of water and / or an alcohol and in the presence of the catalyst of the present invention, the reaction can be performed more effectively. Specific examples of the alcohol used at this time include:
Methyl alcohol, ethyl alcohol, propyl alcohol, isopropyl alcohol, butyl alcohol, pentyl alcohol, hexyl alcohol, octyl alcohol, decyl alcohol, dodecyl alcohol, monoethylene glycol, diethylene glycol, triethylene glycol, (poly) ethylene glycol, monoethylene glycol monomethyl Ether, monoethylene glycol monoethyl ether, monoethylene glycol monoalkyl ether, propylene glycol, dipropylene glycol, tripropylene glycol, (poly) propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6 -Hexanediol, glycerin, trimethylolpropane and the like. These may be used alone or as a mixture. Among these, water, lower alcohols having 1 to 4 carbon atoms such as methyl alcohol and ethyl alcohol, monoethylene glycol and diethylene glycol,
C1-6 polyols such as propylene glycol are preferably used.

The long-chain olefin used in the present invention is preferably a hydrocarbon having 8 to 30 carbon atoms having an ethylenically unsaturated bond, more preferably a hydrocarbon having 10 to 20 carbon atoms having an ethylenically unsaturated bond. Is raised. Such a long-chain olefin may be a branched olefin, a linear olefin, an acyclic olefin, a cyclic olefin, or a mixture thereof without any particular limitation. it can. For example, octene, decene, dodecene, tetradecene, hexadecene, octadecene, eicosene, dococene and the like can be mentioned. Regarding the position of the unsaturated bond of these long-chain olefins, the α-position or the inner position, or a mixture of α and inner can be used without any particular limitation.

The (poly) alkylene glycol used in the present invention includes monoethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, monopropylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol and 1,3-propanediol. , 1,
2-butanediol, 2,3-butanediol, 1,4
-Butanediol, 1,6-hexanediol, 1,4
-Cyclohexanemethanediol and the like. These may be used alone or as a mixture of two or more.

In the present invention, the higher alkyl group of the higher alcohol obtained by reacting the long-chain olefin with water has 8 carbon atoms.
-30, more preferably 10-20 carbon atoms. Specific examples of the higher alcohol include various isomers of decanol (such as 2-6-decanol), various isomers of undecanol (such as 2-6-undecanol), and various isomers of dodecanol (such as 2-7-dodecanol). , Various isomers of tridecanol (such as 2-7-tridecanol), various isomers of tetradecanol, various isomers of pentadecanol, various isomers of hexadecanol, various isomers of heptadecanol, and octadecanol , Various isomers of nonadecanol, various isomers of eicosanol, and the like.

The higher alkyl group of the (poly) alkylene glycol mono-higher alkyl ether and the (poly) alkylene glycol di-higher alkyl ether obtained by reacting the long-chain olefin with the (poly) alkylene glycol in the present invention has 8 to 30 carbon atoms. , Preferably having 10 carbon atoms
To 20 hydrocarbon groups. As the (poly) alkylene glycol residue of the (poly) alkylene glycol mono-higher alkyl ether and the (poly) alkylene glycol di-higher alkyl ether, monoethylene glycol, diethylene glycol, triethylene glycol,
Polyethylene glycol, monopropylene glycol,
Dipropylene glycol, tripropylene glycol,
Residues such as polypropylene glycol, 1,3-propanediol, 1,2-butanediol, 2,3-butanediol, 1,4-butanediol, 1,6-hexanediol, and 1,4-cyclohexanemethanediol can give.

The catalyst used in the present invention has an acid content of 0.06 mmol or more per gram of the catalyst, and more preferably 0.1% or more.
Is 0.8 mmol or more and the saturated adsorption amount of normal propanol as an indicator of hydrophobicity is 0.6 m per gram of catalyst.
mol or more, more preferably 0.8 mmol or more. 0.06m of acid per gram of catalyst
If the amount is less than mol, the catalytic activity is undesirably reduced. On the other hand, if the saturated adsorption amount of normal propanol per gram of catalyst is less than 0.6 mmol, the catalytic activity is also undesirably lowered. Thus, in the present invention, it is not clear why the solid catalyst having a specific acid amount and a saturated adsorption amount of normal propanol expresses a high activity, but an effective catalytic active site in the reaction system of the present invention is an acid, Long-chain olefins, higher alcohols, (poly) alkylene glycol mono-higher alkyl ethers, (poly) alkylene glycol di-higher alkyl ethers, etc. have relatively high hydrophobicity, and the environment near the catalytic active point needs to be somewhat hydrophobic. It is thought that. Specific examples of the catalyst include crystalline metallosilicate, crystalline metallophosphate, zeolite, metal oxide, composite metal oxide, clay compound, heteropoly compound, ion exchange resin, metal sulfate, metal phosphate, layered phosphonate compound, Among solid catalysts such as strong acids, there can be mentioned those having an acid amount of 0.06 mmol or more per gram of catalyst and a saturated adsorption amount of normal propanol of 0.6 mmol or more per gram of catalyst.

In the present invention, the acid content means the acid content measured by the following measuring method. That is, a 1N aqueous solution of sodium chloride (100 cm ³ per gram of catalyst) was added, the mixture was stirred at 25 ° C. for 1 hour, and the catalyst was filtered off.
After washing with 00 cm ³ of distilled water, the amount of acid contained in the combined filtrate and washing solution was titrated with a 0.1 N aqueous sodium hydroxide solution (factor: F) using an ethanol solution of phenolphthalein as an indicator. It is determined from the required capacity (Acm ³ ) of the aqueous sodium hydroxide solution by the following equation.

Acid amount of catalyst (mmol / g) = A × 0.1
× F / catalyst amount (g) Further, the saturated adsorption amount of normal propanol in the present invention means a value measured by the following measuring method.
That is, 0.3 g of normal propanol is added to water for 20 minutes.
After cooling to 2 ° C., 2 g of the catalyst was added and the mixture was stirred for 1 hour, and the amount of residual normal propanol in the solution (B
mmol) is analyzed by gas chromatography, and from the results, the amount of normal propanol adsorbed on the catalyst is determined by the following equation.

Normal propanol saturated adsorption (mmo)
1 / g) = (amount of normal propanol / 60 × 1)
000-B) / Catalyst amount In the present invention, the catalyst may be used in any form, and a powder, a granule, a molded article having a specific shape, or the like can be used. When a molded body is used, alumina, silica, titania or the like can be used as a carrier or a binder.

In the present invention, each reaction can be performed in the presence or absence of a solvent. As the solvent, a solvent such as nitromethane, nitroethane, nitrobenzene, dioxane, ethylene glycol dimethyl ether, sulfolane, benzene, toluene, xylene, hexane, cyclohexane, decane, and paraffin can be used.

In the present invention, the reaction may be carried out by a commonly used method such as a batch reaction or a flow reaction, and is not particularly limited. Although the molar ratio of the reaction raw materials is not particularly limited, the reaction of the long-chain olefin with water or (poly) alkylene glycol is 0.05 to
200, preferably 0.1 to 50 are used.

The reaction temperature is 50 to 250 ° C., preferably 100 to 200 ° C. The reaction pressure can be reduced, normal pressure or increased pressure.
/ Cm ² is preferred. When a batch reactor is used, the catalyst and the raw material of the present invention are charged into the reactor, and the mixture is stirred at a predetermined temperature and a predetermined pressure to obtain a desired higher alcohol, (poly) alkylene glycol monohigher alkyl ether or ( A mixture comprising a poly) alkylene glycol di-higher alkyl ether is obtained. The amount of the catalyst used is not particularly limited, but it is used in an amount of 0.1 to 100% by weight, preferably 0.5 to 50% by weight, based on the long-chain olefin as a raw material. The reaction time varies depending on the reaction temperature, the type and amount of the catalyst, the raw material composition ratio, etc., but is in the range of 0.1 to 100 hours, preferably 0.5 to 30 hours. After the reaction, the catalyst is separated by a method such as centrifugation or filtration and can be recycled for the next reaction. From the reaction solution from which the catalyst was separated and removed, the target higher alcohol,
(Poly) alkylene glycol mono-higher alkyl ether or (poly) alkylene glycol di-higher alkyl ether can be recovered by extraction or distillation,
The unreacted raw materials can be recycled for the next reaction.

In the present invention, long-chain olefins, higher alcohols, (poly) alkylene glycol mono-higher alkyl ethers, (poly) alkylene glycol di-higher alkyl ethers, and water or (poly) alkylene glycol have only slight solubility to each other. Do not distribute, and
The catalyst is often distributed to the aqueous phase or the (poly) alkylene glycol phase, and the higher alcohol, the (poly) alkylene glycol mono-higher alkyl ether, and the (poly) alkylene glycol di-higher alkyl ether are distributed to the olefin phase. In the case of this type of distribution, the olefin phase is separated from the aqueous phase or the (poly) alkylene glycol phase after the reaction, and the aqueous phase containing the catalyst or the (poly) alkylene glycol phase is the water consumed by the reaction. Alternatively, after supplementing the (poly) alkylene glycol,
Recycle to the next reaction, and the olefin phase is separated from the unreacted raw material and the desired higher alcohol, (poly) alkylene glycol mono-higher alkyl ether,
A process for recovering the (poly) alkylene glycol di-higher alkyl ether can be set up.

When a flow reactor is used, it can be carried out in any of a fluidized bed system, a fixed bed system and a stirred tank system. The reaction conditions at this time vary depending on the raw material composition, the catalyst concentration, and the reaction temperature, but are preferably 0.01 to 50 hr ^-1 as a liquid hourly space velocity (LHSV) obtained by dividing the volume flow rate of the flowing raw material by the volume of the reactor. Is 0.1-20 Hr ^-1
Range. After completion of the reaction, higher alcohol, (poly) alkylene glycol mono-higher alkyl ether and (poly) alkylene glycol di-higher alkyl ether can be recovered by the same operation as in the batch reaction.

The catalyst of the present invention can be used to synthesize a long-chain olefin by elimination of a higher alcohol, a long-chain olefin by elimination of a (poly) alkylene glycol mono-higher alkyl ether, Synthesis of long-chain olefin and (poly) alkylene glycol mono-higher alkyl ether by elimination of ether, (poly) from (poly) alkylene glycol di-higher alkyl ether and (poly) alkylene glycol
The same applies to the synthesis of alkylene glycol mono-higher alkyl ethers and the isomerization of long-chain olefins.

That is, when a batch reactor is used, the catalyst and the raw material of the present invention are charged into the reactor, and the mixture is stirred at a predetermined temperature and a predetermined pressure to obtain a desired long-chain olefin and an isomerized long-chain. A mixture containing olefins or (poly) alkylene glycol mono-higher alkyl ethers is obtained. The amount of the catalyst used is not particularly limited, but may be 0.1 to 1 with respect to the raw material higher alcohol, (poly) alkylene glycol mono-higher alkyl ether or (poly) alkylene glycol di-higher alkyl ether.
00% by weight, preferably 0.5 to 50% by weight, is used. The reaction time varies depending on the reaction temperature, the type and amount of the catalyst, the raw material composition ratio, etc., but is in the range of 0.1 to 100 hours, preferably 0.5 to 30 hours. After the reaction, the catalyst is separated by a method such as centrifugation or filtration and can be recycled for the next reaction. From the reaction solution from which the catalyst has been separated and removed, the desired long-chain olefin, isomerized long-chain olefin or (poly) alkylene glycol mono-higher alkyl ether can be recovered by extraction or distillation. It can be recycled for the reaction.

Similarly, long-chain olefins, higher alcohols, (poly) alkylene glycol mono-higher alkyl ethers, (poly) alkylene glycol di-higher alkyl ethers, and water or (poly) alkylene glycol have only slight solubility to each other. Not distributed, and the catalyst is distributed to the aqueous phase or (poly) alkylene glycol phase, higher alcohol, (poly) alkylene glycol mono higher alkyl ether, (poly) alkylene glycol dihigher alkyl ether, long chain olefin is distributed to olefin phase. Often do. In the case of such a distribution system, the olefin phase and the aqueous phase or the (poly) alkylene glycol phase are separated after the completion of the reaction, and the aqueous phase containing the catalyst or the (poly) alkylene glycol phase contains water or After the (poly) alkylene glycol is separated, it is recycled to the next reaction, and the olefin phase is separated from the unreacted raw material and the desired long-chain olefin, isomerized long-chain olefin or (poly) alkylene glycol monoester by a separation method such as distillation. A process can be set up to recover higher alkyl ethers.

Similarly, when a flow-type reactor is used,
Implement in any of bed type, fixed bed type and stirred tank type
be able to. The reaction conditions at this time were the raw material composition, catalyst concentration
Depends on the temperature and the reaction temperature.
Liquid hourly space velocity (LHSV) divided by the volume of the reactor
0.01 to 50 hours^-1, Preferably 0.1 to 20 hours ^-1
Range. After the reaction is completed, the same operation as for batch reaction
Longer chain olefin, isomerized long chain olefin or
Is (poly) alkylene glycol mono higher alkyl ester
Tell can be collected.

Higher alcohols produced according to the invention,
(Poly) alkylene glycol mono-higher alkyl ethers are industrially useful as raw materials for surfactants. Further, the (poly) alkylene glycol di-higher alkyl ether produced by the present invention can be used as a raw material for a lubricant, a plasticizer, a wax and the like. Also, long-chain olefins are industrially useful as surfactant raw materials.

[0034]

The present invention will be described below in more detail with reference to Examples and Comparative Examples. However, this embodiment is one aspect of the present invention, and the present invention is not limited to this. In the examples, the yields of products and by-products were calculated according to the following equations.

Yield of monoethylene glycol monoalkyl ether (Y-EMA (mol%)) = (mol number of monoethylene glycol monoalkyl ether produced / mol number of supplied olefin) × 100 of monoethylene glycol dialkyl ether Yield (Y
−EDA (mol%)) = (mol number of monoethylene glycol dialkyl ether produced × 2 / mol number of supplied olefin) × 100 alcohol yield (mol%) = (mol number of produced alcohol / supplied) Number of moles of olefin) × 100 Yield of diethylene glycol (Y-DEG (mol%))
= (Mol number of diethylene glycol produced × 2 / mol number of monoethylene glycol supplied) × 100 Yield of triethylene glycol (Y-TEG (mol%)) = (mol number of produced triethylene glycol ×
3 / mol number of monoethylene glycol supplied) × 10
0 <Preparation of Catalyst> Example 1 (Catalyst (1)) The following two solutions A and B were prepared. Solution A water glass (JIS No. 3) 55.6 g distilled water 69.3 g solution B anhydrous aluminum sulfate 1.61 g concentrated sulfuric acid 4.62 g tetrapropylammonium bromide 6.95 g sodium chloride 16.4 g distilled water 94.6 g 500 ml beaker while stirring solution B The solution A was dropped into the solution B to obtain a mixed gel. The resulting mixed gel was charged in an autoclave, the space was replaced with nitrogen, and the mixture was heated at 120 ° C. for 72 hours with stirring.
The temperature was raised to ° C., and the mixture was further heated for 5 hours.

After cooling to room temperature, the formed solid was taken out together with the solution, and the supernatant was removed by decantation. The resulting solids remove ammonium salts,
Washing with distilled water and washing were performed. 13 solids after washing
After drying at 0 ° C. overnight, it was calcined at 550 ° C. in the air to obtain a Na ⁺ type crystalline aluminosilicate catalyst. Further, the catalyst was ion-exchanged to an NH ₄ ⁺ type using an aqueous ammonium chloride solution. After ion exchange, wash with water at 80 ° C. until chlorine is no longer observed, and dry at 130 ° C. overnight.
The mixture was calcined at 0 ° C. for 2 hours to obtain a catalyst (1).

The obtained catalyst (1) was subjected to fluorescent X-ray (XRF)
As a result of composition analysis, the atomic ratio of Si to Al was 2
It was 6. The acid amount was 0.45 mmol / g, and the saturated adsorption amount of normal propanol was 1.40 mmol / g. The specific surface area was 390 m ² / g. The obtained catalyst (1) was of MFI type, and the result of X-ray diffraction analysis is shown in Table 1. Comparative Example 1 (catalyst (2)) FAU type zeolite manufactured by PQ (trade name: VALFOR)
CBV-780) was used as catalyst (2). The catalyst (2) had an atomic ratio of Si to Al of 40 and a specific surface area of 430 m ² / g. The acid amount is 0.13 mmo.
1 / g, the saturated adsorption amount of normal propanol is 0.5
It was 5 mmol / g. Example 2 (catalyst (3)) BEA type zeolite manufactured by PQ (trade name: VALFOR)
CP 811BL-25) was used as catalyst (3).
In the catalyst (3), the atomic ratio of Si to Al was 12.5, and the specific surface area was 750 m ² / g. The acid amount is 0.6
At 7 mmol / g, the saturated adsorption amount of normal propanol was 1.00 mmol / g. Example 3 (catalyst (4)) BEA type zeolite manufactured by PQ (trade name: VALFOR)
CP 811BL-25) in 15 ml of 0.
After treating with 1N hydrochloric acid at 40 ° C. for 3 hours to remove a part of Al in the zeolite, washing with distilled water and washing were performed. Thereafter, the catalyst was dried at 120 ° C. overnight and calcined in air at 400 ° C. for 3 hours to obtain a catalyst (4).

When the composition of the obtained catalyst (4) was analyzed by fluorescent X-ray, the atomic ratio of Si to Al was 23.
The obtained catalyst (4) retained the BEA type, and the result of the X-ray diffraction analysis is shown in Table 2. The acid content is 0.51
In terms of mmol / g, the saturated adsorption amount of normal propanol was 1.45 mmol / g. Example 4 (catalyst (5)) BEA-type zeolite manufactured by PQ (trade name: VALFOR)
CP 811BL-25) at 15 ml / g of 3N
After treatment with hydrochloric acid at 100 ° C. for 3 hours to remove a part of Al in the zeolite, washing with distilled water and washing were performed. Thereafter, the catalyst is dried at 120 ° C. overnight, and dried at 400 ° C. in air for 3 hours.
After calcining for an hour, a catalyst (5) was obtained.

When the composition of the obtained catalyst (5) was analyzed by X-ray fluorescence, the atomic ratio of Si to Al was 200. X-ray diffraction analysis of the resulting catalyst (5) showed that the catalyst had the BEA type. The acid content is 0.09 mmol / g.
And the saturated adsorption amount of normal propanol is 1.46 mm
ol / g. Comparative Example 2 (catalyst (6)) BEA type zeolite manufactured by PQ (trade name: VALFOR)
CP 811BL-25) at 15 ml / g of 6N
After treatment with hydrochloric acid at 100 ° C. for 3 hours to remove a part of Al in the zeolite, washing with distilled water and washing were performed. Thereafter, the catalyst is dried at 120 ° C. overnight, and dried at 400 ° C. in air for 3 hours.
After calcining for an hour, a catalyst (6) was obtained.

When the composition of the obtained catalyst (6) was analyzed by X-ray fluorescence, the atomic ratio of Si to Al was 1200. The obtained catalyst (6) was found to have a BEA type as a result of X-ray diffraction analysis. The acid content is 0.05 mmol / g
The saturated adsorption amount of normal propanol is 1.17 mm
ol / g. <Production of (poly) alkylene glycol monoalkyl ether> Example 5 60 g (0.36 mol) of 1-dodecene, 22 g (0.35 mol) of monoethylene glycol and catalyst (1)
5 g was charged into a 200 ml glass reactor equipped with a stirring blade and a reflux condenser, the gas phase was replaced with nitrogen, and then kept in a nitrogen atmosphere at normal pressure.

Then, the temperature was raised to 150 ° C. while stirring at a rotation speed of 650 rpm, and the reaction was carried out at the same temperature for 2 hours. Thereafter, the reaction solution was cooled to room temperature, and the olefin phase and the glycol phase were analyzed by gas chromatography. The olefin phase contained the produced monoethylene glycol monododecyl ether, and the glycol phase contained diethylene glycol and triethylene glycol, which were dehydration condensates resulting from a side reaction of monoethylene glycol. The analysis results are shown in Table 3. Examples 6 to 9 In Example 5, instead of 2.5 g of catalyst (1), Table 3 was used.
A method similar to that of Example 5 except that 2.5 g of each of the catalysts (1), (3), (4), and (5) described in Table 3 was used, and the reaction temperature and the reaction time were changed to the conditions shown in Table 3. The reaction was performed.

After the reaction, analysis was performed in the same manner as in Example 5. The results are shown in Table 3. Comparative Examples 3 and 4 In Example 5, Table 6 was used instead of 2.5 g of the catalyst (1).
The reaction was carried out in the same manner as in Example 5 except that 2.5 g of each of the catalysts (2) and (6) described in (1) was used, and the reaction temperature and the reaction time were changed to the conditions shown in Table 6.

After the reaction, analysis was performed in the same manner as in Example 5. The results are shown in Table 6. Examples 10 to 12 In Example 5, 66 g (1.06 mol) of monoethylene glycol was used instead of 22 g of monoethylene glycol, and 7.5 g of catalyst (4) was used instead of 2.5 g of catalyst (1).
The reaction was conducted in the same manner as in Example 5 except that the reaction temperature and the reaction time were changed to the conditions shown in Table 4 using g.

After the reaction, analysis was carried out in the same manner as in Example 5. The results are shown in Table 4. Example 13 1-dodecene 60 g (0.36 mol), monoethylene glycol 22 g (0.35 mol), sulfolane 42 g
(0.35 mol) and 2.5 g of the catalyst (4) were charged into a 200-ml glass reactor equipped with a stirring blade and a reflux condenser, and the gas phase was replaced with nitrogen, and then kept in a nitrogen atmosphere at normal pressure. .

Next, the temperature was raised to 150 ° C. while stirring at a rotation speed of 650 rpm, and the reaction was carried out at the same temperature for 3 hours. Thereafter, the reaction solution was cooled to room temperature, and monoethylene glycol monododecyl ether generated by gas chromatography,
Diethylene glycol and triethylene glycol were analyzed. The analysis results are shown in Table 5. Example 14 Example 13 was repeated except that 60 g (0.35 mol) of dodecane was used instead of 42 g of sulfolane.
The reaction was carried out in the same manner as described above.

After the reaction, analysis was carried out in the same manner as in Example 13. Table 5 shows the results. Example 15 A reaction was carried out in the same manner as in Example 13, except that 216 g (2.45 mol) of dioxane was used instead of 42 g of sulfolane, and the reaction time was changed to 6 hours.

After the reaction, analysis was carried out in the same manner as in Example 13. Table 5 shows the results. Comparative Example 5 In Example 5, Du was used in place of 2.5 g of the catalyst (1).
Pont's strong acid cation exchange resin (Nafion
NR-50: acid amount: 0.87 mmol / g, normal propanol saturated adsorption amount: 0.16 mmol / g) 2.5
The reaction was carried out in the same manner as in Example 5 except that the reaction time was changed to 4 hours using g.

After the reaction, analysis was carried out in the same manner as in Example 5. The results are shown in Table 6. Comparative Example 6 In Example 5, instead of 2.5 g of the catalyst (1), a strongly acidic cation exchange resin manufactured by Rohm and Haas (Amberlyst 15: acid amount: 4.12 mmol / g, saturated amount of normal propanol) 0.00 mmol / g)
Example 5 except that 84 g was used and the reaction time was 4 hours.
The reaction was carried out in the same manner as described above.

After the reaction, analysis was carried out in the same manner as in Example 5. The results are shown in Table 6. Comparative Example 7 In Example 5, instead of 2.5 g of the catalyst (1), a Y-type zeolite manufactured by Mizusawa Chemical Industries (Mizuka Sieve LC: acid amount: 0.40 mmol / g, normal propanol saturated adsorption amount: 0.00 mmol / g) The reaction was carried out in the same manner as in Example 5 except that 2.5 g was used and the reaction time was changed to 4 hours.

After the reaction, analysis was carried out in the same manner as in Example 5. The results are shown in Table 6. Example 16 In Example 5, 60 g of innerdodecene (1.8 mol% of 1-dodecene in dodecene by NMR analysis) was used instead of 1-dodecene, and 2.5 g of catalyst (1) was replaced with a catalyst ( 4) The reaction was carried out in the same manner as in Example 5, except that 2.5 g was used and the reaction time was changed to 3 hours.

After the reaction, analysis was carried out in the same manner as in Example 5. The results are shown in Table 7. Example 17 In Example 5, 1-dodecene was replaced by 1-dodecene instead of 60 g.
78 g (0.35 mol) of hexadecene, catalyst (1)
2.5 g of catalyst (4) was used instead of 5 g, and the reaction time was 6
The reaction was carried out in the same manner as in Example 5 except that the time was changed.

After the reaction, monoethylene glycol monohexadecyl ether, diethylene glycol and triethylene glycol were analyzed in the same manner as in Example 5. The results are shown in Table 7. Example 18 In Example 5, 1-dodecene was replaced by 60 g with 1-
88 g (0.35 mol) of octadecene, catalyst (1)
2.5 g of catalyst (4) was used instead of 5 g, and the reaction time was 6
The reaction was carried out in the same manner as in Example 5 except that the time was changed.

After the reaction, monoethylene glycol monooctadecyl ether, diethylene glycol and triethylene glycol were analyzed in the same manner as in Example 5. The results are shown in Table 7. <Production of Alcohol> Example 19 119.0 g (0.708 mol) of 1-dodecene, 65.8 g (3.66 mol) of distilled water, and 5.0 g of catalyst (4) were charged in a 500 ml stainless steel autoclave. Next, after the inside of the autoclave was replaced with nitrogen, the autoclave was closed at normal pressure, and the temperature was raised to 150 ° C. while stirring at 600 rpm. Four hours after the temperature was raised, a part of the reaction solution in the autoclave was sampled, and the olefin phase was analyzed using a gas chromatograph. The olefin phase contained the produced alcohol, and the yield was 2.50%. When the reaction was continued for further 10 hours, the yield of alcohol was 3.95%. No by-products were found in the reaction solution other than the starting material and the product alcohol. Example 20 119.0 g (0.708 mol) of 1-dodecene, 65.8 g (3.66 mol) of distilled water, and 5.0 g of the catalyst (1) were charged in a 500 ml stainless steel autoclave. Next, after the inside of the autoclave was replaced with nitrogen, the autoclave was closed at normal pressure, and the temperature was raised to 150 ° C. while stirring at 600 rpm. Four hours after the temperature was raised, a part of the reaction solution in the autoclave was sampled, and the olefin phase was analyzed using a gas chromatograph. The olefin phase contained the produced alcohol, and the yield was 0.18%. Example 21 30.0 g (0.179 mol) of 1-dodecene, 3.2 g (0.178 mol) of distilled water, 1,4-dioxane 11
0.0g and 1.26 g of catalyst (4)
It was charged in a 0 ml autoclave. Next, after replacing the inside of the autoclave with nitrogen, the autoclave was closed at normal pressure, and 600 r.
The temperature was raised to 150 ° C. while stirring at pm. After the temperature was raised, a part of the reaction solution in the autoclave was sampled at predetermined time intervals and analyzed using a gas chromatograph. The reaction solution contained the produced alcohol, and the yield was 5.62%. When the reaction was continued for further 9 hours, the alcohol yield was 8.21%. No by-products were found in the reaction solution other than the starting material and the product alcohol. Comparative Example 8 10.0 g (0.595 mol) of 1-dodecene, 53.6 g (2.98 mol) of distilled water, and 10.0 g of phosphomolybdic acid (manufactured by Nippon Inorganic Chemical Industry Co., Ltd.) as a catalyst were made of glass. In a 1000 ml autoclave. Next, after the inside of the autoclave was replaced with nitrogen, the autoclave was closed at normal pressure, and the temperature was raised to 155 ° C. while stirring at 600 rpm. The reaction was carried out for 4 hours after the temperature was raised, but no production of alcohol was confirmed. <Production of (poly) alkylene glycol dialkyl ether> Example 22 60.0 g (0.36 mol) of 1-dodecene, 22.0 g (0.35 mol) of monoethylene glycol, catalyst (4)
2.5 g was charged into a 200-ml glass reactor equipped with a thermometer, a condenser, and a stirrer. After the inside of the reactor was replaced with nitrogen, the reactor was kept under a normal pressure and a nitrogen atmosphere. Then 600
While stirring at rpm, the temperature was raised to 150 ° C. and maintained at the same temperature. After the reaction for 5 hours, sample a part of the reaction solution,
The olefin phase was analyzed by gas chromatography. The yield of monoethylene glycol monododecyl ether is 3
The yield of 1.1 mol% and monoethylene glycol didodecyl ether was 1.9 mol%. Comparative Example 9 DuPont was used in Example 22 instead of the catalyst (4).
The reaction was carried out in the same manner as in Example 22 except that 2.5 g of a strong acid ion exchange resin (Nafion NR-50) manufactured by KK was used and the reaction time was changed to 12 hours. After 8 hours and 12 hours, the reaction solution was sampled and analyzed in the same manner as in Example 22. The yield of monoethylene glycol monododecyl ether was 4.1 mol% after 8 hours and 5.8 mol% after 12 hours, and no monoethylene glycol didodecyl ether was detected. Comparative Example 10 The reaction was carried out in the same manner as in Example 22, except that 0.8 g of benzenesulfonic acid was used instead of the catalyst (4) and the reaction time was changed to 12 hours. After 12 hours, the reaction solution was sampled and analyzed in the same manner as in Example 22. The yield of monoethylene glycol monododecyl ether was 1.4 mol%, and no monoethylene glycol didodecyl ether was detected. Example 23 1-dodecene 60.0 g (0.36 mol), monoethylene glycol 66.0 g (1.06 mol), catalyst (4)
7.5 g was charged into a 200-ml glass reactor equipped with a thermometer, a condenser and a stirrer. After the inside of the reactor was replaced with nitrogen, the reactor was kept in a nitrogen atmosphere at normal pressure. Then 600
While stirring at rpm, the temperature was raised to 150 ° C. and maintained at the same temperature. After the reaction for 5 hours, sample a part of the reaction solution,
The olefin phase was analyzed by gas chromatography. The yield of monoethylene glycol monododecyl ether is 2
The yield of 2.4 mol% and monoethylene glycol didodecyl ether was 9.1 mol%. Example 24 60.0 g (0.36 mol) of innerdodecene (containing 1.8 mol% of 1-dodecene), 66.0 g (1.06 mol) of monoethylene glycol, 7.5 g of catalyst (4)
Is a glass 20 equipped with a thermometer, a cooling pipe and a stirrer.
After charging into a 0 ml reactor and purging the reactor with nitrogen,
It was kept in a nitrogen atmosphere at normal pressure. Next, the temperature was raised to 150 ° C. while stirring at 600 rpm, and maintained at the same temperature. 5
After the reaction, a part of the reaction solution was sampled, and the olefin phase was analyzed by gas chromatography. The yield of monoethylene glycol monododecyl ether was 9.8 mol%, and the yield of monoethylene glycol didodecyl ether was 1.4 mol%. Example 25 336.0 g (2.0 mol) of 1-dodecene, 372.0 g (6.0 mol) of monoethylene glycol, catalyst (3)
41.3 g was charged into a glass 1000 ml reactor equipped with a thermometer, a cooling tube and a stirrer. After the inside of the reactor was replaced with nitrogen, the reactor was kept under a nitrogen atmosphere at normal pressure. Then 5
While stirring at 00 rpm, the temperature was raised to 135 ° C. and maintained at the same temperature. Over time after the start of the reaction, a part of the reaction solution was sampled, and the olefin phase was analyzed by gas chromatography. Table 8 shows the yield of monoethylene glycol monododecyl ether and the yield of monoethylene glycol didodecyl ether. Example 26 A reaction was carried out in the same manner as in Example 25 except that the reaction temperature was changed to 150 ° C. Table 8 shows the yield of monoethylene glycol monododecyl ether and the yield of monoethylene glycol didodecyl ether. Example 27 In Example 25, a method similar to that of Example 25 was used, except that innerdodecene (containing 1.8 mol% of 1-dodecene) was used instead of 1-dodecene, and the reaction temperature was changed to 150 ° C. The reaction was performed. Table 8 shows the yield of monoethylene glycol monododecyl ether and the yield of monoethylene glycol didodecyl ether. Example 28 In Example 25, the catalyst (4) was used instead of the catalyst (3).
The reaction was carried out in the same manner as in Example 25, except that was used. Table 8 shows the yield of monoethylene glycol monododecyl ether and the yield of monoethylene glycol didodecyl ether.

In Examples 25 to 28, when looking at the time-dependent changes in the reaction, dodecene and monoethylene glycol react in the presence of a catalyst to first produce monoethylene glycol monododecyl ether, and later delay monoethylene glycol didodecyl ether. It can be seen that ether was formed. This indicates that monoethylene glycol monododecyl ether produced as an intermediate is condensed or monoethylene glycol monododecyl ether is added to dodecene to produce monoethylene glycol didodecyl ether. <Elimination reaction of higher alcohol> The yield of the product is calculated according to the following formula.

The yield of dodecene (mol%) = (mol number of dodecene formed / mol number of 2-dodecanol supplied)
× 100 Reference Example 1 66.4 g (0.36 mol) of 2-dodecanol and 2.5 g of the catalyst (3) were charged into a 200-ml glass reactor equipped with a thermometer, a cooling pipe and a stirrer, and the inside of the reactor was filled with nitrogen. , And kept in a nitrogen atmosphere at normal pressure. Then
While stirring at 600 rpm, the temperature was raised to 150 ° C. and maintained at the same temperature. After the reaction for 2 hours, a part of the reaction solution was sampled and analyzed by gas chromatography. The yield of dodecene was 98.5 mol%. Example 29 <Production of (poly) alkylene glycol di-higher alkyl ether> 840.0 g (5 mol) of 1-dodecene, 930.0 g (15 mol) of monoethylene glycol, and 103.3 g of catalyst (4) were cooled with a thermometer and cooled. A glass-made 2000 ml reactor equipped with a tube and a stirrer was charged, and the inside of the reactor was replaced with nitrogen. Next, the temperature was raised to 135 ° C. while stirring at 500 rpm, and the temperature was maintained for 20 hours. After 20 hours, the reaction solution was cooled and the olefin phase was separated. As a result of analysis by gas chromatography, the olefin phase contained 276 g of monoethylene glycol monododecyl ether and 199 g of monoethylene glycol didodecyl ether. This olefin phase is decompressed and a distillation column (height 5)
00 mm, inner diameter 20 mm, and filled with 1.5 mmφ stainless steel Dickson packing as a filler).
The mixture was transferred to a 00 ml flask, and dodecene, monoethylene glycol monododecyl ether and monoethylene glycol didodecyl ether contained in the olefin phase were separated and recovered by distillation under reduced pressure. The vapor pressure of monoethylene glycol didodecyl ether was 193 ° C. and 1 mmHg.
The yield of the obtained monoethylene glycol didodecyl ether was 150 g, and the purity calculated from the area ratio of the gas chromatograph was 93.5%. <Elimination reaction of (poly) alkylene glycol di-higher alkyl ether> The yield of the product is calculated according to the following formula.

Residual amount (mol%) of monoethylene glycol didodecyl ether = (mol number of remaining monoethylene glycol didodecyl ether / mol number of supplied monoethylene glycol didodecyl ether) × 100 monoethylene glycol monododecyl ether Amount (mol%) = ((number of moles of monoethylene glycol monododecyl ether generated) / (number of moles of monoethylene glycol didodecyl ether supplied × 2)) × 10
0 Amount (mol%) of dodecene = ((mol number of generated dodecene) / (mol number of supplied monoethylene glycol didodecyl ether × 2)) × 100 Reference Example 2 Monoethylene obtained in Example 29 85.1 g (0.2 mol) of glycol didodecyl ether, 62.0 g (1.0 mol) of monoethylene glycol, 7.1 of catalyst (4)
g of glass 2 equipped with thermometer, cooling tube and stirrer.
After charging into a 00 ml reactor and replacing the inside of the reactor with nitrogen,
It was kept in a nitrogen atmosphere at normal pressure. Next, the temperature was raised to 150 ° C. while stirring at 600 rpm, and maintained at the same temperature. After the start of the reaction, a part of the reaction solution was sampled with time and analyzed by gas chromatography. Table 9 shows the results. It can be seen that monoethylene glycol didodecyl ether reacts to produce monoethylene glycol monododecyl ether and dodecene, and that monoethylene glycol monododecyl ether is once accumulated and then decomposed into dodecene. <Olefin isomerization> The α-olefin ratio and the olefin polymer yield are calculated according to the following formulas.

Α-olefin ratio (mol%) = (α-olefin concentration in reaction liquid / total olefin concentration in reaction liquid) × 100 Ratio of olefin polymer (mol%) = (weight of olefin polymer produced) / Weight of supplied olefin) × 10
0 Reference Example 3 336.0 g (2 mol) of 1-dodecene, 372.0 g (6 mol) of monoethylene glycol, 41.3 of catalyst (3)
g of glass 1 equipped with thermometer, cooling tube and stirrer.
After charging into a 000 ml reactor, the inside of the reactor was purged with nitrogen, and then kept in a nitrogen atmosphere at normal pressure. Then, 500 rp
The temperature was raised to 150 ° C. while stirring at m. 3 hours and 20 hours after the temperature was raised, a part of the reaction solution in the reactor was sampled, and the olefin phase was analyzed by gas chromatography and NM.
The olefin polymer (olefin dimer) and α-olefin ratio were analyzed using R. The results are shown in Table 10. After 20 hours, the reaction solution was cooled, the olefin phase was separated and removed from the reaction solution, and 1-dodecene 33 was newly added to the monoethylene glycol phase containing the remaining catalyst (3).
6.0 g (2 mol) was added to carry out a second reaction. 3
Table 10 shows the results obtained by sampling the reaction solution for 20 hours and 20 hours, and analyzing it in the same manner as the first time. Reference Example 4 13.0 g (2 mol) of 1-dodecene, 124.0 g (2 mol) of monoethylene glycol, catalyst (4) 14.1
g of glass 1 equipped with thermometer, cooling tube and stirrer.
After charging into a 000 ml reactor, the inside of the reactor was purged with nitrogen, and then kept in a nitrogen atmosphere at normal pressure. Then, 500 rp
The temperature was raised to 185 ° C. while stirring at m. Fifteen hours after the temperature was raised, a part of the reaction solution in the reactor was sampled, and the olefin phase was analyzed in the same manner as in Reference Example 3. The yield of the olefin polymer was 0.4 mol%, and the α-olefin ratio was 3.9.
Mole%. Reference Example 5 In Reference Example 4, the reaction temperature was 150 ° C., and the reaction time was 2
The reaction was carried out in the same manner as in Reference Example 4 except that the time was changed to 3 hours. After the reaction, the result of analysis in the same manner as in Reference Example 4 showed that
The yield of the olefin polymer was 0.5 mol%, and the α-olefin ratio was 5.9 mol%. Reference Example 6 81.3 g (0.32 mol) of 1-octadecene, 20.0 g (0.32 mol) of monoethylene glycol, and 2.3 g of the catalyst (4) were made of glass equipped with a thermometer, a cooling pipe, and a stirrer. The reactor was charged into a 200 ml reactor, and the inside of the reactor was purged with nitrogen, and then kept in a nitrogen atmosphere at normal pressure. Then, 6
The temperature was raised to 170 ° C. while stirring at 00 rpm. Fourteen hours after the temperature was raised, a part of the reaction solution in the reactor was sampled, and the olefin phase was analyzed in the same manner as in Reference Example 3. The yield of the olefin polymer was 0.4 mol%, and the α-olefin ratio was 12.6 mol%. Reference Example 7 1-dodecene 60.0 g (0.36 mol), monoethylene glycol 22.0 g (0.35 mol), catalyst (1)
2.5 g was charged into a 200-ml glass reactor equipped with a thermometer, a condenser, and a stirrer, and the inside of the reactor was purged with nitrogen, and then kept at a normal pressure in a nitrogen atmosphere. Then, 600r
The temperature was raised to 185 ° C. while stirring at pm. After heating, 1
After a lapse of 7 hours, a part of the reaction solution in the reactor was sampled, and the olefin phase was analyzed in the same manner as in Reference Example 3. After 1 hour, the α-olefin ratio was 79.9 mol%,
After 7 hours, the α-olefin ratio was 43.6 mol%. Reference Example 8 119.0 g (0.708 mol) of 1-dodecene, 65.8 g (3.66 mol) of distilled water, and 5.0 g of the catalyst (4) were charged in a stainless steel autoclave. Next, after the inside of the autoclave was replaced with nitrogen, the autoclave was closed at normal pressure, and
The temperature was raised to 150 ° C. while stirring at rpm. After the temperature rise,
The reaction was carried out for 10 hours, a part of the reaction solution in the reactor was sampled, and the olefin phase was analyzed in the same manner as in Reference Example 3.
The α-olefin ratio was 80.6 mol%, and no olefin polymer was detected. Reference Example 9 1-dodecene 60.0 g (0.36 mol), catalyst (4)
2.5 g was charged into a 200-ml glass reactor equipped with a thermometer, a condenser, and a stirrer, and the inside of the reactor was purged with nitrogen, and then kept at a normal pressure in a nitrogen atmosphere. Then, 600r
The temperature was raised to 150 ° C. while stirring at pm. After heating, 1
After allowing time, the reaction solution was cooled, a part of the reaction solution was sampled, and the olefin phase was analyzed in the same manner as in Reference Example 3. The olefin phase contained a large amount of an olefin polymer, and the yield was 13.5 mol%. The α-olefin ratio was 14.4 mol%. Comparative Reference Example 1 60.0 g (0.36 mol) of 1-dodecene, 22.0 g (0.35 mol) of monoethylene glycol, and 6.0 g of a strongly acidic ion exchange resin (Nafion NR-50) manufactured by DuPont were heated at a temperature of 200m glass made with meter, condenser and stirrer
After the reactor was charged and the atmosphere in the reactor was replaced with nitrogen, the reactor was maintained at a normal pressure in a nitrogen atmosphere. Next, the temperature was raised to 150 ° C. while stirring at 600 rpm. After heating, 4 hours and 8 hours later, a part of the reaction solution in the reactor was sampled,
The olefin phase was analyzed in the same manner as in Reference Example 3. The α-olefin ratio after 4 hours was 96.8 mol%,
The olefin ratio was 93.0 mol%.

[0058]

[Table 1]

[0059]

[Table 2]

[0060]

[Table 3]

[0061]

[Table 4]

[0062]

[Table 5]

[0063]

[Table 6]

[0064]

[Table 7]

[0065]

[Table 8]

[0066]

[Table 9]

[0067]

[Table 10]

[0068]

According to the present invention, a solid catalyst having an acid amount of 0.06 mmol or more per gram of catalyst and a saturated adsorption amount of normal propanol as an index of hydrophobicity of 0.6 mmol or more per gram of catalyst is used as the catalyst. By the synthesis of higher alcohols with long-chain olefins and water,
In each reaction of the synthesis of a (poly) alkylene glycol higher alkyl ether using a long-chain olefin and a (poly) alkylene glycol, the reaction rate is high, side reactions can be suppressed, the selectivity is high, and each target product can be efficiently produced.

Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI C07C 43/11 C07C 43/11 // C07B 61/00 300 C07B 61/00 300 (72) Inventor Yukio Sumino Chidoricho, Kawasaki-ku, Kawasaki-shi, Kanagawa 14-1 Inside Nippon Shokubai Co., Ltd.

Claims (6)

[Claims] 1. A method for producing a higher alcohol by reacting a long-chain olefin with water in the presence of a catalyst, wherein the amount of acid is 0.06 mmol per gram of catalyst.
A method for producing a higher alcohol, comprising using a solid catalyst having a saturated adsorption amount of normal propanol of 0.6 mmol or more per gram of catalyst. 2. The method according to claim 1, wherein the long-chain olefin is at least one selected from the group consisting of olefins having 8 to 30 carbon atoms. 3. A solid catalyst used for producing a higher alcohol by reacting a long-chain olefin with water, wherein the amount of acid is 0.06 mmol or more per gram of catalyst,
And a catalyst having a saturated adsorption amount of normal propanol of 0.6 mmol or more per gram of the catalyst. 4. A method for producing a (poly) alkylene glycol higher alkyl ether by reacting a long-chain olefin with a (poly) alkylene glycol in the presence of a catalyst, wherein the catalyst has an acid amount per gram of catalyst. 0.0
A method for producing a (poly) alkylene glycol higher alkyl ether, comprising using a solid catalyst having a mmol of 6 mmol or more and a saturated adsorption amount of normal propanol of 0.6 mmol or more per gram of the catalyst. 5. The method according to claim 4, wherein the long-chain olefin is at least one selected from the group consisting of olefins having 8 to 30 carbon atoms. 6. A solid catalyst used in producing a (poly) alkylene glycol higher alkyl ether by reacting a long-chain olefin with a (poly) alkylene glycol, wherein the acid amount is 0.06 mmol per gram of the catalyst.
The catalyst as described above, wherein the saturated adsorption amount of normal propanol is 0.6 mmol or more per gram of the catalyst.