JPH07242579A - Production of alkylphenols - Google Patents

Abstract

PURPOSE:To reduce olefin polymers formed by side reaction and obtain alkylphenols useful as an oil-soluble phenol resin, etc., in high selectivity and yield by reacting phenols with olefins in the coexistence of activated clay and a specific alcohol. CONSTITUTION:This method for producing alkylphenols is to react phenols such as phenol with olefins such as ethylene in the coexistence of activated clay and a 1-8C straight-chain or branched chain alcohol such as methanol in an amount of preferably 0.1-25wt.% (based on the weight of the phenols).

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention is used as an industrial chemical such as an oil-soluble phenolic resin, various synthetic resin modifiers and surfactants, and also as a raw material for medicines, agriculture, fragrances, dyes and other organic compounds. The present invention relates to a method for producing alkylphenols used as

[0002]

2. Description of the Related Art Conventionally, as a method for producing alkylphenols, there is a method of alkylating phenols by reacting phenols with olefins, alcohols or alkyl halides. As the reaction catalyst, hydrochloric acid, sulfuric acid, phosphoric acid, polyphosphoric acid or Lewis acid (aluminum trichloride, boron trifluoride, etc.) is often used. In addition, there are examples of using mineral catalysts such as zeolite, mica, clay, and montmorillonite, but with phenols having electron-withdrawing substituents, the reaction is difficult to proceed with these mineral catalysts alone, and they are treated with a mineral acid or the like. Is being used. In addition to the above catalysts, alkylation catalysts such as hydrogen fluoride and H-type cation exchange resins are used.

[0003]

When the above-mentioned mineral acid or Lewis acid is used in the liquid phase reaction, a large amount of strong acid is contained in the reaction solution. Need to use. Further, after the reaction, there are disadvantages that the separation of the reaction solution and the catalyst requires complicated operations such as neutralization, liquid separation, and washing with water, and a large amount of phenol-containing wastewater is discharged. When using a mineral catalyst such as zeolite, mica, clay, or montmorillonite alone to improve the reaction rate, a large amount of catalyst is used, so the reaction solution and the catalyst are separated by a separation means such as simple filtration or centrifugation. This is not easy, and since the amount of catalyst for olefins is large, olefin polymerization is likely to occur and the selectivity of alkylphenols decreases. The poly α-olefin produced by this polymerization may have an unsaturated double bond in the molecule, which adversely affects the oxidative stability. Further, when it is molded into pellets and used as a gas-phase reaction catalyst, the yield of the target product is remarkably deteriorated due to the decrease in surface area. Hydrogen fluoride is expensive and
It is a catalyst that is extremely difficult to handle industrially because the materials used for the reaction are limited. The H-type cation exchange resin was developed as a catalyst that can facilitate the separation of the reaction solution and the catalyst and does not require the use of a corrosion resistant reactor. Part of the catalyst swells and becomes gelatinized. Further, the H-type cation exchange resin has a drawback that it is expensive.

[0004] As described above, the conventional manufacturing method has industrial drawbacks, and therefore, an inexpensive and high-yield manufacturing method of alkylphenols is desired.

[0005]

[Means for Solving the Problems] In order to solve the above problems, the inventors of the present invention have conducted diligent research, and as a result, when reacting phenols and olefins in the presence of activated clay, the carbon number is 1 to 8 It was found that the reaction rate is improved when the reaction is carried out in the coexistence of the linear or branched monohydric alcohol, and the present invention was completed.

That is, the present invention provides a method for producing alkylphenols in which a phenol and an olefin are subjected to a nuclear alkylation reaction in the presence of activated clay and a linear or branched monohydric alcohol having 1 to 8 carbon atoms. The present invention relates to a method for producing an alkylphenol, which is characterized in that the synthesis is carried out at.

The activated clay catalyst used in the present invention is preferably a clay mineral such as montmorillonite or halloysite treated with a mineral acid. The mineral acid is solubilized by attacking structural cations in the octahedral layer, Promotes activation of montmorillonite or halloysite. This opens up the clay structure and increases the surface area. These acid-treated clays are believed to act as strong Bronsted acids.

The alcohols to be coexisted when the phenols and the olefins are reacted are linear or branched monohydric alcohols having 1 to 8 carbon atoms, and particularly preferably,
It is one kind or a mixture of 2 to 4 kinds selected from methanol, ethanol, 1-propanol and 2-propanol, and the mixing ratio is not particularly limited, but it is desirable to select one kind in consideration of recovery and the like. . The addition amount of alcohols is preferably 0.1 to 25% by weight with respect to the weight of phenols, when the addition amount is less than 0.1% by weight, the effect of improving the reaction rate is poor, and when the addition amount exceeds 25% by weight,
The latent heat of vaporization of alcohols makes it difficult to raise the temperature in the reactor, resulting in a decrease in the reaction rate.

The phenols used are not particularly limited, and examples thereof include phenol and substituted phenols. The substituent of the substituted phenols is not particularly limited, but is, for example, an alkyl group having 1 to 6 carbon atoms [eg, methyl group, isopropyl group, isobutyl group, isoamyl group, etc. (including dialkyl group and trialkyl group)] ], A substituted alkyl group (the alkyl portion has the same meaning as described above, and the substituent includes a phenyl group, an amino group, an alkoxy group, a carbonyl group, a carboxyl group (including its alkyl ester), etc.), carbon Number 1-6
An alkoxy group (for example, a methoxy group, an ethoxy group,
Propoxy group etc.), halogen atom (eg chlorine, fluorine, bromine etc.), lower alkylthio group (eg methylthio group, isopropylthio group etc.), acyl group having 1 to 7 carbon atoms (eg acetyl group, phenylcarbonyl group etc.) ),
An amino group, a carboxyl group (including its alkyl ester), a cycloalkyl group (having 4 to 7 carbon atoms) and the like are included.

The olefins to be reacted with the phenols are not particularly limited, and examples thereof include olefins having 1 to 28 carbon atoms (eg ethylene, isobutylene, octadecene, etc.), substituted olefins having 1 to 28 carbon atoms, and the like. . Examples of the substituent of the substituted olefin include a phenyl group, a halogen atom (for example, chlorine, fluorine, bromine, etc.), a nitro group, an amino group, a carbonyl group, an alkoxy group having 1 to 6 carbon atoms (for example, a methoxy group, Ethoxy group, propoxy group, etc.), lower alkylthio group (for example, methylthio group, isopropylthio group, etc.), C1-C1
7 acyl group (for example, acetyl group, phenylcarbonyl group, etc.), amino group, carboxyl group (including its alkyl ester), cycloalkyl group (having 4 to 7 carbon atoms) and the like.

The mode, form, etc. of reacting phenols and olefins are not particularly limited. For example, a batch system or a continuous system may be used, regardless of liquid phase reaction or gas phase reaction.
The amount of the reactant used is not particularly limited, but either the phenols or the olefins may be used in excess, and the reaction is performed at the amount used to maximize the reaction rate and the unreacted raw material is recovered. The reaction is carried out in a convenient amount. The method of charging phenols, olefins, alcohols and catalysts includes a method of charging all at once at the start of the reaction and a method of sequential charging, and is not particularly limited, but considering reduction of olefin polymer as a by-product, olefin is considered. It is preferable to use a method of sequentially preparing the kinds.

As the solvent, a solvent inert to the reaction, for example, saturated hydrocarbons, higher aliphatic alcohols such as benzene, toluene, chlorobenzene and the like can be used depending on the reaction temperature. However, it is not always necessary to use a solvent because the reaction proceeds sufficiently even without solvent.
The amount of the catalyst used varies depending on the reaction mode, the acid strength of the catalyst, and the like. When a large amount of the catalyst is used, the filtration efficiency is reduced and a large amount of an olefin polymer, which is a by-product, is produced, which is not preferable. As an example of the amount of catalyst used, when used in a suspension bed, it is 0.1 to 25 relative to the weight of phenols.
It is used in the range of about wt%. Preferably 0.5 to 15% by weight
Is.

The reaction temperature varies depending on the reaction mode, the amount of catalyst, and the kind of the reaction substance, but usually in the liquid phase reaction, the temperature at which the alcohols to be coexisted are refluxed, that is, 30 to 22.
The temperature is 0 ° C, preferably 60 to 200 ° C, and in the gas phase reaction is 200 to 500 ° C, preferably 220 to 500 ° C.

The reaction pressure is not particularly limited, and may be atmospheric reaction or pressurized reaction. In the pressure reaction, the boiling point of the reaction solution is accompanied by an increase in the boiling point, so that low boiling point alcohols are advantageous for preventing bumping. However, the reaction between the phenols and the olefins proceeds sufficiently under normal pressure and is not particularly limited.

The reaction time varies depending on the type of catalyst, the amount of catalyst, and the type of reactant, but it is usually about 1 to 100 hours.

The method for obtaining the formed alkylphenols after the reaction is not particularly limited. For example, in the case of a liquid layer reaction, alkylphenols can be obtained by operations such as filtration and removal of the catalyst after completion of the reaction, and distillation of the filtrate. When the catalyst is filtered, if the filtrate is hard to pass through, a filter aid may be used. In the case of the gas phase reaction, alkylphenols can be similarly obtained.

[0017]

EXAMPLES Examples of the present invention will be described below, but the present invention is not limited to the following examples.

Example 1 940 g of phenol (10 mol) and 50.3 g of activated clay in a 5000 ml flask equipped with a stirrer, a thermometer and a reflux cooling device.
(5.4% by weight) and 50.3 g (5.4% by weight) of ethanol were weighed and heated to 150 ° C. 2348 g (10 mol) of α-olefin, which is a mixture having 16 and 18 carbon atoms, was added dropwise over 3 hours. Then, the temperature was raised to 170 ° C. over 1 hour and the reaction was performed for 2 hours. After cooling this to 80 ° C., the activated clay was removed by filtration. At this time, filtration was performed under reduced pressure (20 mmHg) using a filter cloth having a filtration area of 19.6 cm ² , and the filtrate amount after 20 seconds was measured and found to be 300 ml. Gas chromatography (column: Megabore DB-
5, 0.53φ × 30 m × 1.5 μm, internal standard method). As a result, it was confirmed that alkylphenols having 16 and 18 carbon atoms (hereinafter abbreviated as APH) were produced at a yield of 94% (gas chromatography area ratio, relative to phenol).
In addition, polyα-olefin (hereinafter abbreviated as PAO) by the side reaction was 3.3% (gas chromatogram area ratio) with respect to APH. Then, the filtrate was distilled under reduced pressure (5 mmHg) to recover unreacted phenol and α-olefin. The amount of alkylphenol obtained was 2502 g.

Example 2 After carrying out the reaction in the same manner as in Example 1 except that the amount of activated clay was 25.1 g (2.7% by weight), quantitative analysis was performed on the filtrate of the reaction solution. As a result, APH
The production rate (gas chromatography area ratio) was 91% (to phenol). PAO due to side reaction was 4.4% (gas chromatography area ratio) relative to APH.

Example 3 After carrying out the reaction in the same manner as in Example 1 except that 2.5 g (0.27% by weight) of ethanol was used, quantitative analysis was performed on the filtrate of the reaction solution. As a result, the APH production rate (gas black area ratio) was 89% (to phenol). PAO due to side reaction is 4.3 against APH
% (Gas black area ratio).

Example 4 After carrying out the reaction in the same manner as in Example 1 except that 235 g (25% by weight) of ethanol was used,
The filtrate of the reaction solution was quantitatively analyzed. As a result, AP
Production rate of H (gas black area ratio) is 90% (to phenol)
It was. PAO due to side reaction is 2.8% of APH
(Gas black area ratio).

Example 5 1520 g (10 mol) of methyl salicylate was used in a 5000 ml flask equipped with a stirrer, a thermometer and a reflux condenser, and 30.4 g (2% by weight) of activated clay and 30.4 g of ethanol were used.
(2% by weight) was weighed and heated to 200 ° C. To this, 1960 g (10 mol) of α-olefin having 14 carbon atoms was added dropwise over 3 hours. Then, the temperature was raised to 210 ° C. over 1 hour and the reaction was performed for 2 hours. Then, in the same manner as in Example 1, the filtrate of the reaction solution was quantitatively analyzed. As a result, the production rate (gas chromatography area ratio) of methyl alkylsalicylate (hereinafter abbreviated as ASM) was 85% (to methyl salicylate). The PAO due to the side reaction was 3.6% with respect to ASM (gas chromatography area ratio).

Example 6 After the reaction was carried out in the same manner as in Example 5 except that 2-propanol was used instead of ethanol, quantitative analysis was carried out on the filtrate of the reaction solution. As a result, the production rate of ASM (gas chromatography area ratio) was 82% (to methyl salicylate). PAO due to side reaction was 3.4% (gas chromatography area ratio) with respect to ASM.

Comparative Example 1 After carrying out the reaction in the same manner as in Example 1 except that ethanol was not used, quantitative analysis was performed on the filtrate of the reaction solution. As a result, the production rate of APH (gas area ratio) was 78% (to phenol). PAO due to side reaction was 4.4% (gas chromatography area ratio) with respect to APH.

Comparative Example 2 After carrying out the reaction in the same manner as in Example 2 except that ethanol was not used, quantitative analysis was carried out on the filtrate of the reaction solution. As a result, the APH production rate (gas black area ratio) was 65% (to phenol). PAO due to side reaction was 5.5% (gas chromatography area ratio) with respect to APH.

Comparative Example 3 After carrying out the reaction in the same manner as in Example 5 except that ethanol was not used, quantitative analysis was carried out on the filtrate of the reaction solution. As a result, the production rate of ASM (gas chromatography area ratio) was 60% (to methyl salicylate).
PAO due to side reaction was 4.0% (gas chromatogram area ratio) relative to ASM.

Comparative Example 4 After carrying out the reaction in the same manner as in Example 5 except that ethanol was not used in Example 5 and the amount of activated clay was increased to 247.8 g (16.3% by weight), the filtrate of the reaction solution was used. Was quantitatively analyzed. As a result, the production rate of ASM (gas chromatography area ratio) was 70% (to methyl salicylate). The PAO due to side reaction increased to 16.4% (gas chromatography area ratio) with respect to ASM. Further, the amount of filtrate was measured in the same manner as in Example 1, and it was 60 ml, which required a filtration time of 5 times.

The alkylphenols and methyl alkylsalicylates obtained in Examples 1 to 6 and Comparative Examples 1 to 4 exhibited the properties shown in Table 1 below.

[0029]

[Table 1]

Gas chromatography area of phenol or methyl salicylate Gas chromatography area of APH or ASM Gas chromatography area of PAO

[0031]

[Equation 1]

[0032]

The present invention provides a conventional catalyst such as sulfuric acid,
Unlike hydrochloric acid, phosphoric acid and hydrogen fluoride, it is not soluble and does not require a corrosion resistant reaction vessel. Further, in the present invention, the filtration efficiency can be significantly improved by reducing the amount of the catalyst, and it becomes possible to reduce the olefin polymer by the side reaction, and as a result, the alkylphenols are highly yielded and highly selected. Can be manufactured at a rate.

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[Procedure amendment]

[Submission date] May 10, 1994

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As the solvent, a solvent inert to the reaction, for example, saturated hydrocarbons, higher aliphatic alcohols and the like can be used depending on the reaction temperature. However, it is not always necessary to use a solvent because the reaction proceeds sufficiently even without solvent. The amount of the catalyst used varies depending on the reaction mode, the acid strength of the catalyst, and the like. When a large amount of the catalyst is used, the filtration efficiency is reduced and a large amount of an olefin polymer, which is a by-product, is produced, which is not preferable. As an example of the amount of catalyst used, when used in a suspension bed, it is based on the weight of phenols.
It is used in the range of 0.1 to 25% by weight. Preferably 0.5 to
15% by weight.

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[0029]

[Table 1]

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[0031]

[Equation 1]

Claims (2)

[Claims] 1. A method for producing an alkylphenol in which a phenol and a olefin are subjected to a nuclear alkylation reaction, the synthesis is carried out in the coexistence of activated clay and a linear or branched monohydric alcohol having 1 to 8 carbon atoms. A method for producing an alkylphenol, comprising: 2. The amount of addition of the linear or branched monohydric alcohol having 1 to 8 carbon atoms is 0.1 to the weight of phenols.
The method for producing an alkylphenol according to claim 1, wherein the amount is 25% by weight.