JPS5838225A - Preparation of alkylphenols - Google Patents

Abstract

PURPOSE:To obtain the titled compound, economically, by the catalytic reaction of a phenolic compound having one or more hydrogen atoms on the aromatic ring with an alcohol in the presence of a catalyst containing metal oxide, wherein said catalyst is pretreated with a phenolic compound, etc. CONSTITUTION:An alkylphenol useful as a raw material of plastics, plasticizers, antioxidants, fungicides, and pesticides, can be prepared by the catalytic reaction of a phenolic compound having one or more hydrogen atoms on the aromatic ring with a 1-4C alcohol using a catalyst containing metal oxide such as aluminum oxide, magnesium oxide, manganese oxide, iron oxide, zeolite, etc. which is pretreated with a phenolic compound or a phenolic compound and a 1-4C alcohol. The catalytic properties can be improved in terms of the activity, selectively, induction period, life, etc. The phenolic compound used in the pretreatment is not necessarily the one having one or more hydrogen atoms on the aromatic ring.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a method for combining phenols and alcohols in a gaseous phase with Km
This invention relates to a method for producing alkylphenols by catalytic reaction.

In particular, the present invention provides phenols or alcohols a
A method for alkylating hydrogen atoms of phenols using a metal oxide-containing catalyst pretreated with K to produce alkylphenols having at least 7 or more alkyl groups.

Among alkylphenols, it is known that ortho-7A and -56-dimethylphenol, which is a Nell compound, are important as raw materials for the production of polyphenylene ether (PPIIII), which is a useful plastic.

Alkylphenols are resin I11 plasticizers.

It is also known that many studies have been conducted on it for its use as a raw material for antioxidants, bactericidal agents, and pharmaceuticals.

Aluminum e-oxide, magnesium oxide, manganese oxide, iron oxide, chromium oxide, zeolite, etc., and their additions with various components have already been used as catalysts for the arunelization method of phenols and alcohols. Methods of catalytic reaction are known, but when considering the overall performance of the catalyst, these methods are not sufficient in some respects such as activity 1 selectivity, induction period, lifespan, etc., and are not satisfactory catalysts. sea bream.

From this perspective, the inventors of the present invention have continued intensive research to solve these problems.

We have found that these problems can be easily improved by pre-treating the metal oxide-containing catalyst with phenols and/or alcohols before providing it to the alkaline reaction, and we have arrived at the method of the present invention. This is what I did.

That is, the present invention provides a method for producing alkylphenols by subjecting a phenol having at least 7 hydrogen atoms at an aromatic apex to a gas phase catalytic reaction with an alcohol, in which a metal oxidation agent pretreated with a phenol and/or an alcohol is used. This is a method for producing alkylphenols, characterized by using a chemical catalyst.

What are the phenols used in the method of the present invention?

A phenolic compound having an aromatic ring hK/or more hydrogen atoms, with the general formula (in the formula, R1 to R5Fi, hydrogen, a hydrogen fluoride group, a hydrosil group, or an aromatic compound such as unsubstituted or substituted phenyl or naphthyl). It is a hydrocarbon group.

At least seven or more of them are hydrogen atoms. ) It is expressed as

Examples of such compounds include phenol, cresols, xylenols, trimethylphenols, and various ethylphenols Is.

Examples include n-1180-, T@rt- butylphenols, phenylphenols, naphthylphenols, and the like.

Similarly, phenol compounds in which one or more different types of f-functional groups are transferred to the aromatic ring can also be used.

Alcohols used in the method of the present invention.

It is a lower alcohol with a prime number of 1/~q, such as methanol, ethanol, and coprobanol.

1110-propertool, n-butanol L1go -
butanol, t@rt-butanol, etc.

Catalysts that can be used in the method of the present invention include, for example, aluminum oxide-containing catalysts, magnesium oxide-containing catalysts, manganese oxide-containing catalysts, iron oxide-containing catalysts, and zeolite-containing catalysts.

In other words, as a catalyst containing ml-containing al-turfonium.

Aluminum oxide and its main ingredient.

For example, catalysts containing silicon oxide and magnesium oxide include magnesium oxide alone and magnesium oxide as a main component, such as manganese oxide, steel oxide, boron oxide, and silicon oxide.

It contains one or more types of /W14b<Fi selected from iron oxides and the like.

In addition, the manganese oxide-containing catalyst may include manganese monoxide alone or manganese monoxide as a main component, and in addition to this, for example, 7 selected from magnesium oxide, silicon oxide, iron oxide, alkali metals, alkaline earth metal S, and sulfuric acid. Examples of iron oxide-containing catalysts include iron oxide alone or iron oxide as a main component, such as silicon oxide, chromium dioxide, zinc oxide, and manganese oxide.

It contains seven or more selected from alkali metals and alkaline earth metals.

As a zeolite-containing catalyst in f,! Protons, lanthanum, nickel, steel, manganese, chromium, cobalt, boron, zinc, cadmium, alkali metals, and alkaline earth metals are present in the central anion cavity of each type of zeolite, such as Y-type and Y-type.
These include those containing zeolite with cation exchange of 8 or more.

Each ml used for these catalysts! As raw materials for the chlorides, conventional compounds are used.

The catalyst can be prepared by combining various raw materials, adding a small amount of water, and kneading them in a kneader, mixer, etc., or by adding a basic component to an aqueous solution of various raw materials and co-precipitating as an insoluble precipitate. Depending on the quality of the product, filtration, washing and drying,
Ordinary preparation methods such as firing and molding methods can be used as they are. For catalysts containing nine zeolites, ordinary ion exchange methods can be applied.

The metal oxide-containing catalyst used in the method of the present invention may be treated with phenols and alcohols by the following method, but any method may be used.

tA) A method in which the catalyst is pretreated by contacting the catalyst with a gas or liquid containing phenols and/or alcohols before being charged into the reactor; (B) A method in which the catalyst is pretreated by contacting the catalyst with a gas or liquid containing phenols and/or alcohols before being charged into the reactor. The phenols used for catalyst pretreatment are generally the same as the compounds listed above. There is no need for at least/side of 2R1 to R5 to be a hydrogen atom.

In addition, when treating with these phenols, the phenol may be a single type, or a mixture with -f4 or higher types.

It may also be diluted with a suitable gas (inert rare gas, nitrogen gas, reducing gas, etc.).

The treatment with the phenols is carried out at a temperature ranging from room temperature to 10[theta]C for 1[sigma] minutes to oz.

(9) The alcohol used in the pretreatment of the catalyst is a lower alcohol with a carbon atom number/~q, but if the subsequent reaction is methylation, methanol is used, and if ethylation is carried out, ethanol is used. It is preferable that the alcohol used in the reaction is the same as the alcohol used in the reaction, but this is not necessarily the case.

This treatment with alcohols is carried out at a temperature range of % room temperature to 6°C for /θ minutes to -q hours.

In addition, when treating with a mixture of phenols and alcohols (even if the treatment is carried out in the temperature range of room temperature to 4θθ℃ for 70 minutes to Q1
Time is done.

The catalyst used in the reaction, whose activity has decreased, is activated with oxygen and water vapor, and then pretreated with phenol sI and alcohols again.

Although the theoretical interpretation of the effects of pretreatment with alcohols on phenol II and t9 in the method of the present invention is not necessarily clear, phenols and alcohols are adsorbed onto the catalyst surface by treatment with phenol 1liii and/or alcohols. It is believed that the presence of phenolates and alcoholades in the catalyst provides a favorable field for activity and selectivity when the alkylating agent and the alkylated agent are brought into close proximity during one reaction.

It is also believed that the shortening of the induction period is due to the fact that a sufficient number of active sites are generated at the start of the reaction.

Furthermore, the effect on the lifespan is thought to be that the alkylating agent decomposes and the active sites that would carbonize are inactivated by the adsorption of phenols and/or alcohols, thereby preventing carbonization.

When carrying out the method of the present invention, the molar ratio of phenols and alcohols to be supplied is appropriate: /~l:/σ, and 3
:/~/:l is more preferable.

Carrying out one reaction by mixing water into the reaction raw materials has the effect of extending the life of the catalyst, increasing Kg, and suppressing unnecessary decomposition of alcohols.

In the method of the present invention, the 13 reaction degree is 40θ~j70℃
, preferably in the range of J/17 to jJ0°C.

If the reaction temperature is lower than this range, the conversion rate will be insufficient in the usual reaction format and it is not practical, and if the reaction temperature is set higher than this range, the selectivity of the reaction tends to decrease.

The reaction can be carried out in liquid phase, gas phase, under pressure or under reduced pressure, and the reaction format can be fixed bed or moving bed.

Although any type of fluidized bed is possible, a fixed bed is generally used.

Hereinafter, the present invention will be specifically explained with reference to Examples, but the present invention is not limited to the contents of these Examples.

The catalyst performance in Examples/~IIK is the conversion rate.

-11-tei is indicated by the silenol selectivity, and is defined by the following formula.

Conversion rate (mono) Conversion rate of phenol (mole capsule) -
, Ruxyleno-1-Kumii-shaku (Feno-J et al. 1)-1
6-Xi-Tsu l-Gobakuken (Methanol Reijun) Example 3
-4 catalyst performance Fi conversion rate of raw material phenols,
It is indicated by the selectivity of the target product, each defined corresponding to the above formula.

sJ! EXAMPLE/The reaction system used for alkylation consists of a feed pump for phenol and methanol, a vaporizer for the raw liquid, one quartz glass reaction charge, and a product vapor condensation section.

The central part of a quartz glass reactor was filled with a catalyst of 7θ to σ messi and installed at an internal pressure in an electric furnace.

The catalyst was commercially available magnesium oxide, and after it was installed in the above-mentioned apparatus, the catalyst layer temperature was set to SOO°C, and only phenol was supplied at /θm//hr for 3 hours for treatment.

NextKli [space velocity/, 4j hr tear engineering/-
methanol and water (supplied molar ratio i:s
: /, 7) Ceramics, Comparative Example / The results are shown when the reaction was carried out in exactly the same manner as Fi, Example /, except that the pretreatment of the catalyst with phenol was not carried out.

Example - The catalyst used was manganese dioxide, and the reaction temperature and catalyst treatment temperature were 30°C and liquid nitrogen temperature.

Comparative Example - Reaction example 3 was carried out in exactly the same manner except that the pretreatment of the catalyst with phenol was not carried out. Magnesium oxide was used as the catalyst, and /λa''CK was held in advance in a medium rod, and 9 ortho-cresol was reacted with 2 After soaking for an hour, place it in the reactor.

Comparison f.
The catalyst used was ferric oxide as lJ, the reaction temperature and catalyst treatment temperature were 37θ℃, and only phenol was t/θd/h.
The kernels were supplied and treated with r for 3 hours, and the liquid-pneumatic transmission
The procedure was the same as in Example 1, except that the molar ratio of phenol, methanol, and water C feed, /:3:/, l) was fed at a rate of /II hr''.

Comparative Example q: The reaction was carried out exactly as in Example 1, except that no pretreatment of the catalyst with phenol was carried out. It consists of an ethanol supply pump, a raw material liquid vaporizer, a reactor, a product vapor condensation section, and a receiver.

Prior to the ethylation reaction, the catalyst was pretreated by supplying only ethanol to the magnesium oxide catalyst layer at 3jθ°C for KJ hours, and then the molar ratio of phenol and ethanol was adjusted to /:! On the other hand, as Comparative Example S, the results are shown when the reaction was carried out in exactly the same manner as with the catalyst using ethanol.

Orthoethyl phenol and diethylphenol contained Example 6 Reaction value fji #-i used for alkylation, metacresol and methanol feed pump.

It consists of a reactor unit for vaporizing the raw material liquid, a condensing vessel for the product vapor, and a receiver.

Prior to the methylation reaction, only metacresol was converted to 4Iλθ
After treating the catalyst by supplying a mag-wood catalyst layer K for j,j hours at °C, the reaction temperature was increased to /7j.
The molar ratio of metacresol and methanol (6 molar ratio) is shown in the table as δ°C.

As Comparative Example 4, the reaction was carried out in exactly the same manner as in Example 6 except that the pretreatment of the catalyst with metacresol was not carried out. ) October 1980, Japan Patent Office Commissioner Shima 1) Spring m Indication of the case 1982 %' Patent Application No. 13, No. 557 2, Name of the invention Process for producing alkylphenols 8, Person making the amendment, Case Relationship with Patent applicant address 5-15 Kitahama, Higashi-ku, Osaka Name (
209) Sumitomo Chemical Co., Ltd. - Representative name: Sat
Takeshi 5, ? fti +E O) Contents of additions to the Claims column and Detailed Description of the Invention column 6 of the ZJ Specification 1) The scope of the claim will be corrected according to the terms and conditions.

2) Delete the entire text "under gas phase" on page 1, line 14 of the specification.

3) Lines 16 to 18 of the same line “In particular, the present invention is F!/-*
at* means...(omitted)...The hydrogen atom of phenol is replaced by "j". It is pretreated and used to remove the hydrogen atoms of phenols.

4) Page 8, lines 3 to 4, page 7, line 8, page 7, line 7, page 7, lines 11 to 12, negative line 8, line 19, , on page 9, lines 1 to 2 and page 9, line 3, line 24, correct the words "with phenols and or alcohols" to "with phenols or phenols and alcohols". .

5) Delete "gas phase" in the 8th negative 9th line.

6) On page 8, lines 10 to 12, the phrase "characterized by the use of phenols...(omitted)..." was replaced with "the metal oxide-containing catalyst was pre-contained with phenols... (omitted)..."
Or, it must be used after being pretreated with phenols and alcohols.''

7) All “tert-butylphenols” on page 4, line 9 of the same
-butylphenols”.

8) On page 6, lines 4 and 5, the statement ``proton in the central anion gap'' is corrected to read ``one central cation is a proton''.

9) In the 1st and 2nd lines of page 8, the statement [May be diluted with gas (... (omitted)...)] has been replaced with "gas (inert rare gas, water vapor, nitrogen gas). , reducing gas, etc.) may be accompanied.''

10) On page 8, lines 12 and 13, [This alcohol...(omitted)...is carried out. ”
Delete the entire text.

11) Page 8, line 18 It says "water vapor" [Water vapor-containing gas]”

12) On page 9, lines 5 to 8, the phrase "phenols...(omitted)...therefore, during the reaction" has been replaced with "phenols or alcohols are adsorbed on the catalyst surface and during the reaction." I am corrected.

13) Page 10, line 10 It says "pressurize, depressurize" Correct it to "pressurization,'ygF!r:,,depressurization."

14) In the 8th to 9th lines from just below No. 11, see [Conversion rate of phenols in Examples 5 to 6...(omitted)].1 The catalyst performance in Example 5 is based on the raw material meta. "Conversion rate of cresol" is corrected.

15) Page 18, line 5 It says, "The results are shown in Table 2." "I let him do it. The result is as per the second sentence," he corrected.

16) Page 15, line 12 from the bottom - 11j, line 1 from the bottom
The entire text of Example 5 on the first line is deleted.

17) On page 17, lines 1 and 2, and page 17, line 7, "Table 6" is corrected to "Table 5."

18) "Example 6" in Table 5 on page 17, line 10 from the bottom of page 16, lines 4 to 5 on page 17, is corrected to "Example 5."

19) On page 17, line 8, in table 5, page 17, the phrase “Comparative Example 6” has been replaced with the claim “phenols having at least one hydrogen atom in an aromatic ring together with alcohols” A method for producing alkylphenols by catalytic reaction."

Claims (1)

[Claims] In the method of producing alkylphenols by subjecting phenols having at least one/even hydrogen atom to an aromatic loam in a vapor phase catalytic reaction with alcohols, metal oxides that have been pre-processed with phenols and/or alcohols. A method for producing alkylphenols, characterized by using a catalyst.