JP2000072703A - Production of alkylene oxide adduct of alkylcyclohexanol - Google Patents

Abstract

PROBLEM TO BE SOLVED: To efficiently produce the subject adduct useful as a surfactant by a method excellent in productivity by reacting a specific adduct with hydrogen in the presence of a hydrogenation catalyst in a saturated hydrocarbon-based solvent. SOLUTION: (A) An alkylene oxide adduct of an alkylphenol of formula I [R1 is a 6-20C alkyl; R2 is H, methyl or ethyl; (n) is >=1], (e.g. nonylphenol ethoxylate) is reacted with (B) hydrogen in the presence of (C) a hydrogenation catalyst and optionally (D) water in (E) a saturated hydrocarbon-based solvent at 30-200 deg.C under 0.5-18 MPa hydrogen pressure to provide the objective adduct of formula II. The component C is preferably a ruthenium catalyst supported by carbon or alumina. The component E is preferably a cyclic saturated hydrocarbon.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a method for producing an alkylcyclohexanol alkylene oxide adduct. More specifically, the present invention relates to a method for obtaining an alkylcyclohexanol alkylene oxide adduct by reacting an alkylphenol alkylene oxide adduct with hydrogen using a hydrogenation catalyst in the presence of a saturated hydrocarbon solvent. Alkyl cyclohexanol alkylene oxide adducts are useful as surfactants and their raw materials.

[0002]

2. Description of the Related Art Alkylcyclohexanol alkylene oxide adducts have excellent properties as nonionic surfactants. Among them, the ethylene oxide adduct has a low pour point and is easy to handle even if the number of moles of ethylene oxide added is relatively high, and is easy to handle. For example, other nonionic surfactants such as higher primary alcohol ethoxylates It can be said that it has excellent properties not found in the agent.

[0003] Several methods for producing alkylcyclohexanol ethoxylates having a higher alkyl group in the side chain of the cyclohexane ring are known as follows. For example, German Offenlegungsschrift 4417947
Discloses a method for obtaining alkylcyclohexanol by subjecting an alkylphenol to nuclear hydrogenation and then reacting with ethylene oxide in the presence of a base catalyst to obtain alkylcyclohexanol ethoxylate. However, it is generally known that when a secondary alcohol such as alkylcyclohexanol is reacted with ethylene oxide in the presence of a base catalyst, the reaction is very slow. For example,
"New Surfactant" (by Hiroshi Horiguchi, Sankyo Publishing Company, 1975)
On page 626, the reaction between alcohol and ethylene oxide by a base catalyst is described in “Generally ethylene ethylene oxide”.
Oxide reacts quickly with primary alcohols, but slower with secondary alcohols, and is abbreviated.
Therefore, when alkylcyclohexanol and ethylene oxide are reacted by a base catalyst to obtain alkylcyclohexanol ethoxylate, a small amount of alkylcyclohexanol ethoxylate (primary alcohol) generated in the early stage of the reaction and ethylene oxide are preferentially used. , And as a result, an unreacted amount of unreacted alkylcyclohexanol remains unpreferably.

[0004] In addition, H. Stache et al. Hydrogenated 1 mol of isooctylphenol ethylene oxide adduct,
Isooctylcyclohexanol ethylene oxide 1
After obtaining the molar adduct, it is reacted with ethylene oxide to obtain isooctylcyclohexanol ethoxylate (Tr.-Mezhdunar. Kongr. Pov.
erkhn. -Akt Vestishvhamm 7
th (1977) Vol. 1 378-391). However, there is no description about what kind of catalyst was used and under what conditions for the hydrogenation reaction of 1 mol of isooctylphenol ethylene oxide adduct.

Further, George E. et al. Tille
octylphenol ethoxylate, a kind of alkylphenol ethoxylate (trade name: Trit)
onX-100) in an ethanol solvent in the presence of a rhodium carbon catalyst to obtain octylcyclohexanol ethoxylate (ANALYTICALBI).
OCHEMISTRY 141, 262-266 (19
84)). However, in this method, the reaction rate is extremely slow, and a long reaction time is required to obtain an alkylcyclohexanolalkylene oxide adduct having a sufficiently high conversion, which is disadvantageous in that the productivity is inferior. A method for producing a novel alkylcyclohexanolalkylene oxide adduct that has solved these problems has been desired.

[0006]

An object of the present invention is to provide a novel method for producing an alkylcyclohexanolalkylene oxide adduct useful as a surfactant, which is efficient and excellent in productivity.

[0007]

Means for Solving the Problems The inventors of the present invention have made intensive studies to achieve the above object, and as a result, an alkylphenol alkylene oxide adduct and hydrogen were converted to a saturated hydrocarbon solvent using a hydrogenation catalyst. When reacted in the presence of, compared with the case of using a conventionally used solvent,
The present inventors have found that an alkylcyclohexanolalkylene oxide adduct can be produced more efficiently and with high productivity, and have completed the present invention.

That is, the present invention provides the following equation (1)

Embedded image (Wherein, R ¹ represents an alkyl group having 6 to 20 carbon atoms;
² represents a hydrogen atom, a methyl group or an ethyl group;
Wherein an alkylphenol alkylene oxide adduct represented by the above formula (1) and hydrogen are reacted with a hydrogenation catalyst in the presence of a saturated hydrocarbon solvent.

Embedded image (Wherein, R ¹ represents an alkyl group having 6 to 20 carbon atoms;
² represents a hydrogen atom, a methyl group or an ethyl group;
Which represents the above integer).

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION In the alkylphenol alkylene oxide adduct represented by the formula (1), which is a raw material in the method of the present invention, R ¹ represents an alkyl group having 6 to 20 carbon atoms. The structure of R ¹ is not particularly limited, and may be a straight-chain structure or a branched structure, and may have any structure of a structural isomer that an alkyl group can take. Further, the bonding position of R ¹ is determined by an alkoxylate group (—O
(CH ₂ CHR ² O) _n H group)
Any of the third and fourth positions may be used. Further, R ² in the oxyalkylene unit (—CH ₂ CHR ² O—unit) represents a hydrogen atom, a methyl group or an ethyl group. Specifically, the oxyalkylene unit is an oxyethylene unit (—CH ₂ CH _2).
O-unit), oxypropylene unit (-CH ₂ CH (C
H ₃ ) O-unit) or oxybutylene unit (—CH ₂ C)
H (CH ₂ CH ₃ ) O-unit). n is an integer of 1 or more. When n is 2 or more, the repeating unit may have only one of an oxyethylene unit, an oxypropylene unit, or an oxybutylene unit, or may have two or more types. It may have an oxyalkylene unit. When it has two or more types of oxyalkylene units, it may be added randomly or in blocks.

The range of n is not limited, but is usually in the range of 1 to 50. Structural isomers of R ¹ to alkylphenol alkylene oxide adduct represented by the formula (1), R ¹
And the compounds having different types and numbers of the oxyalkylene units and the positional isomers of the alkoxylate groups, and these compounds can be used alone, but are usually a mixture of two or more types. Further, a mixture of two or more alkylphenol alkylene oxide adducts represented by the formula (1) having different numbers of carbon atoms in the alkyl group R ¹ may be used.

Specific examples of the alkylphenol alkylene oxide adduct represented by the formula (1) include hexylphenol ethoxylate, heptylphenol ethoxylate, octylphenol ethoxylate, nonylphenol ethoxylate, decylphenol ethoxylate, and undecylphenol ethoxylate. Alkyl phenols such as tridecylphenol ethoxylate, tetradecylphenol ethoxylate, pentadecylphenol ethoxylate, hexadecylphenol ethoxylate, heptadecylphenol ethoxylate, octadecylphenol ethoxylate, nonadecylphenol ethoxylate, eicosylphenol ethoxylate Ethoxylates, such as hexylphenol propoxylate , Heptyl phenol propoxylate, octyl phenol propoxylate, nonyl phenol propoxylate, decyl phenol propoxylate, undecyl phenol propoxylate, tridecyl phenol propoxylate, tetradecyl phenol propoxylate, pentadecyl phenol propoxylate, hexadecyl phenol propoxylate, hepta Alkyl phenol propoxylates such as decyl phenol propoxylate, octadecyl phenol propoxylate, nonadecyl phenol propoxylate, and eicosyl phenol propoxylate;
For example, hexylphenol butoxylate, heptylphenol butoxylate, octylphenol butoxylate, nonylphenol butoxylate, decylphenol butoxylate, undecylphenol butoxylate, tridecylphenol butoxylate, tetradecylphenol butoxylate, pentadecylphenol butoxylate, hexadecyl Alkylphenol butoxylates such as phenolbutoxylate, heptadecylphenolbutoxylate, octadecylphenolbutoxylate, nonadecylphenolbutoxylate, and eicosylphenolbutoxylate, for example, octylphenol (ethylene oxide / propylene oxide) random copolymer, octylphenol (ethylene oxide) (Butylene oxide) random copolymer, octylphenol (propylene oxide / butylene oxide) random copolymer, nonylphenol (ethylene oxide / propylene oxide) random copolymer, nonylphenol (ethylene oxide / butylene oxide) random copolymer, nonylphenol (propylene) Oxide / butylene oxide)
Alkylphenol alkylene oxide random copolymers such as random copolymers, for example, octylphenol (ethylene oxide / propylene oxide) block copolymer, octylphenol (ethylene oxide / butylene oxide) block copolymer, octylphenol (propylene oxide / butylene oxide) block Copolymer, nonylphenol (ethylene oxide / propylene oxide) block copolymer,
Examples include alkylphenol alkylene oxide block copolymers such as nonylphenol (ethylene oxide / butylene oxide) block copolymer and nonylphenol (propylene oxide / butylene oxide) block copolymer.

The hydrogenation catalyst used in the method of the present invention is a catalyst having the ability to hydrogenate the aromatic ring of the phenolalkylene oxide adduct represented by the formula (1) with hydrogen to form a cyclohexane ring. Any catalyst may be used. Specific examples of such a catalyst include a supported catalyst of ruthenium, rhodium, palladium or platinum, a complex catalyst of these metals, Raney nickel, Raney cobalt and the like. Specifically, the supported catalyst of ruthenium, rhodium, palladium or platinum is, for example, ruthenium carbon, rhodium carbon, palladium carbon, a carbon-supported catalyst of these metals such as platinum carbon, such as ruthenium alumina, rhodium alumina, etc. Metal-alumina-supported catalysts, such as palladium-silica-alumina, silica-alumina-supported catalysts of these metals such as platinum-silica-alumina, for example, palladium-silica-magnesia, etc. Catalysts include, for example, barium sulfate supported catalysts of these metals such as barium palladium sulfate, for example, titania supported catalysts of these metals such as ruthenium titania. Further, a material carrying two or more kinds of metals simultaneously at an arbitrary ratio may be used. Specific examples thereof include catalysts supported on carbon such as ruthenium-rhodium carbon and palladium-platinum carbon, and catalysts supported on alumina such as ruthenium-rhodium alumina and palladium-platinum alumina. These supported catalysts may be used alone or as a mixture of two or more at an arbitrary ratio. The amount of metal carried is not particularly limited,
Usually, it is in the range of 0.01 to 20% by weight. These catalysts may be in the form of powder or crushed, or may be formed into pellets or spheres. Further, generally available hydrous products of these catalysts can also be used.

The complex catalysts of ruthenium, rhodium, palladium or platinum are specifically, for example, halides of these metals such as ruthenium chloride, rhodium chloride and palladium bromide, such as palladium acetate and rhodium propionate. Acetylacetonato complexes of these metals such as ruthenium acetylacetonate, palladium acetylacetonate, etc., for example, dichlorotris (triphenylphosphine) ruthenium, chlorotris (triphenylphosphine) rhodium, dichlorobis (triphenyl) Examples thereof include phosphine complexes of these metals such as (phosphine) palladium and dichlorobis (triphenylphosphine) platinum. These complex catalysts may be used alone or as a mixture of two or more kinds at an arbitrary ratio. Among these hydrogenation catalysts, a catalyst supported on ruthenium carbon or alumina is preferred because of its excellent catalytic activity and selectivity.

The process of the present invention is carried out in the presence of a saturated hydrocarbon solvent. The structure of the saturated hydrocarbon solvent to be used is not particularly limited, and may have a linear structure, a branched structure or a cyclic structure. The starting material is an alkylphenolalkylene oxide adduct represented by the formula (1) and a formula (2). Any product can be dissolved or dispersed as long as it can not be hydrogenated by itself. Specifically, for example, n-pentane, n
Linear saturated hydrocarbons such as -hexane, n-heptane, n-octane and n-dodecane, for example, 2-methylbutane;
2-methylhexane, 2-methylpentane, 2-methylheptane, 3-methylpentane, 3-ethylpentane,
3-methylhexane, 3-ethylhexane, 3-methylheptane, 2,2-dimethylpropane, 2,2-dimethylhexane, 2,2-dimethylbutane, 2,2-dimethylhexane, 3-methyl-3-ethyl Pentane, 2,
Examples include branched saturated hydrocarbons such as 2,3-trimethylbutane, and cyclic saturated hydrocarbons such as cyclopentane, cyclohexane, decalin, methylcyclopentane, methylcyclohexane, and p-menthane. These solvents may be used alone or as a mixture of two or more. Among these saturated hydrocarbon solvents, cyclic saturated hydrocarbons are particularly preferable from the viewpoint of reactivity and selectivity. The amount of the saturated hydrocarbon solvent to be used is not particularly limited, but the concentration of the alkylphenol alkylene oxide adduct represented by the formula (1) usually used as a raw material is 5 to 80% by weight, preferably 20 to 60% by weight. Use in range.

In the method of the present invention, it is preferable to carry out the reaction in the presence of water since the reaction rate can be further improved without impairing the selectivity. When used, water is previously dissolved in an alkylphenol alkylene oxide adduct represented by the formula (1), a catalyst and a solvent used as a raw material,
It may be dispersed or impregnated, or may be charged separately from these raw materials and the like into the reaction system. The amount of water to be used is not particularly limited, but is in the range of 0.1 to 50% by weight, preferably 1 to 4% by weight, based on the alkylphenol alkylene oxide adduct represented by the formula (1) usually used as a raw material.
The range is 0% by weight.

The reaction of the present invention is usually carried out at a hydrogen pressure of 0.5 to 1
The reaction is carried out at 8 MPa and a reaction temperature of 30 to 200 ° C. The more preferable hydrogen pressure and reaction temperature differ depending on the kind and amount of the catalyst used, the number of oxyethylene units in the alkylphenol alkylene oxide adduct represented by the formula (1), and are not uniform, but are appropriately selected. The method of conducting the reaction in the present invention is not particularly limited,
Any of a batch system, a semi-batch system and a continuous flow system can be used. When the reaction is performed in a batch or semi-batch system,
The amount of the catalyst used is not particularly limited, but is usually in the range of 0.5 to 50% by weight based on the alkylphenol alkylene oxide adduct represented by the formula (1) usually used as a raw material. ~ 50 hours. When the reaction is carried out in a continuous flow system, the reaction conditions vary depending on the type of the catalyst to be used and the like.
SV) is in the range of 0.01 to 50 hr ^-1 .

In the method for removing the hydrogenation catalyst from the reaction mixture obtained by the method of the present invention, when a metal-supported catalyst is used, separation is carried out by a usual solid-liquid separation method. When a metal complex catalyst is used, separation can be performed by distillation or the like. Further, if necessary, a dehydration operation by distillation or the like and an operation of desolvation are carried out, so that an alkylcyclohexanol represented by the formula (2) corresponding to the alkylphenol alkylene oxide represented by the formula (1) used as the target raw material An alkylene oxide adduct can be obtained. In some cases, a purification operation such as removal of by-products may be performed by an operation such as distillation.

[0018]

Next, the present invention will be described in more detail by way of examples. Reference Example 1 (Synthesis of alkylphenol alkylene oxide adduct) In a 1000 ml autoclave equipped with an ethylene oxide introduction tube, 220 g of nonylphenol (nonyl group is a mixture having a branched structure, and the ortho / para ratio is 1/9) was used.
98 mol) and 40% aqueous sodium hydroxide solution 0.1.
55 g (5.5 mmol of sodium hydroxide) were charged. After replacing the inside of the system with nitrogen, the temperature was raised to 120 ° C., and then the inside of the system was reduced to 50 mmHg and dehydrated under reduced pressure for 1 hour. After completion of the dehydration under reduced pressure, the inside of the system was returned to normal pressure with nitrogen, and the temperature was raised to 150 ° C. Then, 220 g (4.99 mol) of ethylene oxide was gauged at a gauge pressure of 0.2 to 0.
The mixture was fed into the reaction system under a pressure of 4 MPa for 5 hours to perform an ethoxylation reaction of nonylphenol. After feeding ethylene oxide, aged at the same temperature for 1 hour.
After cooling, the mixture was neutralized with 0.35 g (5.8 mmol) of acetic acid to obtain 440 g of nonylphenol ethoxylate. The resulting nonylphenol ethoxylate has an average addition mole number of ethylene oxide to nonylphenol (hereinafter simply referred to as ethylene oxide addition mole number) of 5.0. In the same manner as in this reference example, alkylphenol alkylene oxide adducts having an arbitrary number of moles of alkylene oxide added were synthesized by changing the types and ratios of the alkylphenol and alkylene oxide to be reacted.

Example 1 In a 70 ml autoclave, 20 g of nonylphenol ethoxylate having a molar number of ethylene oxide of 5.0 (4 g) was added.
5.5 mmol (the number of moles of the nonylphenoxy skeleton, the same applies hereinafter)), 2.0 g of a powdery dried 5 wt% ruthenium carbon product, and 20 g of cyclohexane were charged. After the inside of the system was replaced with nitrogen and then with hydrogen, the temperature was raised to 60 ° C.
The hydrogen pressure was adjusted to a gauge pressure of 6.0 MPa, and a nuclear hydrogenation reaction was performed at the same temperature for 3 hours while continuously supplying hydrogen so as to maintain the same pressure. After completion of the reaction, the catalyst was filtered under pressure at 50 ° C. while hot, and the solvent was removed by distillation to obtain a colorless liquid fraction. ^{When 1} H and ¹³ C-NMR, elemental analysis, mass spectrometry and infrared spectrum were measured, this liquid was found to have an average addition mole number of ethylene oxide to nonylcyclohexanol (hereinafter simply referred to as ethylene oxide addition mole number). Was identified as 5.0 nonylcyclohexanol ethoxylate. The amount of hydrogen consumed during the reaction was 136.1 mmol, which was 3.00 mol times with respect to the charged nonylphenol ethoxylate.
When nonylphenol ethoxylate remaining in nonylcyclohexanol ethoxylate was quantified by liquid chromatography, the amount was 60 weight pp.
m. Further, nonylcyclohexane produced by the hydrogenolysis reaction was quantified by gas chromatography to find that the amount was 90 ppm by weight.

Comparative Example 1 The reaction, filtration and solvent removal were carried out in the same manner as in Example 1 except that ethanol was used instead of cyclohexane to obtain nonylcyclohexanol ethoxylate. The amount of hydrogen consumed during the reaction was 54.4 mmol, which was 1.19 mol times based on the charged nonylphenol ethoxylate. When nonylphenol ethoxylate remaining in nonylcyclohexanol ethoxylate was quantified by liquid chromatography, the amount was 60.2% by weight. Further, nonylcyclohexane produced by the hydrogenolysis reaction was quantified by gas chromatography to find that the amount was 140 ppm by weight. As is apparent from the results, when the reaction was carried out using a solvent other than the saturated hydrocarbon system, the reaction was very slow and a sufficient conversion could not be obtained.

Example 2 Powdered 5% by weight ruthenium carbon hydrated product was changed to 2.0 g of powdered 5% by weight ruthenium carbon dried product.
The reaction, filtration, dehydration and desolvation were carried out in the same manner as in Example 1 except that 0 g (water content: 50% by weight) was used to obtain nonylcyclohexanol ethoxylate. The amount of hydrogen consumed was 136.1 mmol, which was 3.00 mol times the used nonylphenol ethoxylate, the amount of residual nonylphenol ethoxylate was 30 ppm by weight, and the amount of nonylcyclohexane was 55 ppm by weight.

Examples 3 to 7 Nonylphenol ethoxylates having the number of moles of ethylene oxide added shown in Table 1 (Table 1) and Table 2 (Table 2) were used. The reaction, filtration, dehydration and desolvation were carried out in the same manner as in Example 2 except that the time was changed to the time shown in Table 2 (Table 2) to obtain nonylcyclohexanol ethoxylate having a different number of moles of ethylene oxide added. The amounts of hydrogen consumed, the amount of residual nonylphenol ethoxylate and the amount of nonylcyclohexane are shown in Table 1 (Table 1) and Table 2 (Table 2) together with the results of Example 2. As is clear from the results of Table 1 (Table 1) and Table 2 (Table 2), the use of a saturated hydrocarbon solvent almost completes the reaction in 1.5 hours at any ethylene oxide addition mole number. This results in a very fast reaction rate.

[0023]

[Table 1]

[0024]

[Table 2]

Example 8 The reaction, filtration and desolvation were carried out in the same manner as in Example 1 except that n-heptane was used instead of cyclohexane.
Nonylcyclohexanol ethoxylate was obtained. The amount of hydrogen consumed was 136.6 mmol, which was 3.01 mol times the nonylphenol ethoxylate used, the amount of residual nonylphenol ethoxylate was 120 ppm by weight, and the amount of nonylcyclohexane was 95 ppm by weight.

[0026]

According to the present invention, an alkylcyclohexanolalkylene oxide adduct useful as a surfactant, which is more efficient and more productive than a conventional solvent, is produced. Method is provided,
It is extremely useful industrially.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Kyoko Ono 1-6-6 Takasago, Takaishi-shi, Osaka Mitsui Chemicals, Inc. (72) Inventor Kyokichi 1-6-6 Takasago, Takaishi-shi, Osaka Mitsui Chemicals, Inc. F Term (reference) 4H006 AA02 AC11 BA23 BA55 BB11 BE20 GP02 GP10 4H039 CA40 CB10

Claims (4)

[Claims] (1) Formula (1) (Formula 1) (Wherein, R ¹ represents an alkyl group having 6 to 20 carbon atoms;
² represents a hydrogen atom, a methyl group or an ethyl group;
Wherein the alkylphenol alkylene oxide adduct represented by the above integer is reacted with hydrogen using a hydrogenation catalyst in the presence of a saturated hydrocarbon solvent. ] (Wherein, R ¹ , R ² and n represent the above-mentioned meanings). 2. The method for producing an alkylcyclohexanolalkylene oxide adduct according to claim 1, wherein the saturated hydrocarbon solvent is a cyclic saturated hydrocarbon. 3. The method for producing an alkylcyclohexanolalkylene oxide adduct according to claim 1, wherein the reaction is carried out in the presence of water. 4. The method for producing an alkylcyclohexanolalkylene oxide adduct according to claim 1, wherein the hydrogenation catalyst is a ruthenium carbon or alumina supported catalyst.