JP2571602B2 - Method for producing tertiary-amylphenols - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a method for producing tertiary-amylphenols, and more specifically, by reacting 3-methyl-1-butene with phenols in a catalytic manner. 2,4, which is especially useful as a raw material for color developing color developing agents, UV absorbers, resin additives
It is possible to easily and efficiently obtain tertiary-amylphenols such as p-tert-amylphenol, which are particularly useful as raw materials for di-tert-amylphenol, oil-soluble dye intermediates, rubber additives, and the like. To a process for the production of tertiary-amylphenols.

[Conventional technology]

As a method for producing tertiary-amylphenols, particularly, 2,4-di-tertiary-amylphenol and p-tert-amylphenol, which are particularly useful as described above,
Conventionally, a method is known in which phenols are alkylated with tertiary-amyl alcohol or isoamylene in the presence of an acid catalyst. Among them, a method utilizing isoamylene which is close to a crude material is industrially advantageous, and various methods based on a reaction between phenols and isoamylene have been studied.

As the reaction between the isoamylene and the phenols, to date, (i) a method using high-quality isoamylene, that is, 2-methyl-2-butene or 2-methyl-1-butene, and (ii) isoprene extraction residue C There is a method in which isoamylene (a mixture of 2-methyl-2-butene and 2-methyl-1-butene) in the _five fractions is used as a mixture.

As the method (i), for example, (ia) a method using a liquid acidic catalyst such as sulfuric acid, phosphoric acid, or benzenedisulfonic acid as a catalyst; (ib) a cation exchange resin (Amberlyst-15 or the like) as a catalyst; A method using a solid acidic catalyst such as a silica-alumina type catalyst (zeolite, mordenite, etc.) (JP-A-60-174739), and a method (iiic) using an active zeolite as a catalyst (JP-A-60-181)
042 JP) have been proposed, on the other hand, as a method for the (ii), after reacting remove residual isoprene and cyclopentadiene in (iia) isoprene extraction residue C ₅ fraction with maleic acid, an organic carboxylic acid A method of reacting phenols with sulfuric acid as a catalyst in the presence of an anhydride or the like (JP-A-50-35122), (iib) isoprene extraction residue C
A method of reacting isoamylene produced by hydrogenating the _five fractions in the presence of a transition metal hydrogenation catalyst such as palladium or nickel with phenols in the presence of an inorganic solid acid or an acidic ion exchange resin catalyst (JP Akira 60-174739 JP), (iiic) after cyclopentene isoprene extraction residue C ₅ distillate hydrogenated, a method of reacting a phenol in the presence of an inorganic solid acid catalyst (JP 62-153235 JP ) Has been proposed.

However, high quality isoamylene, ie 2-
In the above method (i) using methyl-2-butene or 2-methyl-1-butene, that is, (ia), (ib) and (ic), 2,4-di-tert-butene having relatively high purity is used. Although 3-amylphenol, p-tert-amylphenol and the like can be obtained, high-purity 2-methyl-2-butene and 2-methyl-
1-butene has a serious problem that it is expensive, whereas C ₅ distillate of isoamylene i.e. 2-methyl-2-butene and 2-methyl-1-above utilizing butene (ii) ie (iia) In the methods (iib) and (iic), isoamylene is used in the form of a mixture without isolation, so that the raw material itself is relatively inexpensive and excellent in that it can be easily obtained in large quantities, but the raw material itself is excellent. Since it is a complex mixture and requires a complicated pretreatment, even when the yield of the alkylation reaction itself is high, the concentration and purity of the target tertiary-amylphenols in the product are low. In order to obtain a target product of low purity and high purity, there was a serious problem that the whole process was complicated and was not always economically satisfactory.

[Problems to be solved by the invention]

As described above, in the conventional method for producing tertiary-amylphenols, the alkylating agent used is tertiary-amyl alcohol or so-called isoamylene (that is,
-Methyl-2-butene and 2-methyl-1-butene), which are serious in that high-grade alkylating agents themselves are expensive, or the process is complicated and high-purity production is difficult to obtain efficiently. Therefore, development of a new manufacturing method with less restrictions on such raw materials has been an issue.

The present invention has been made based on such circumstances.

An object of the present invention is to prepare high-purity 2,4-di-tert-amylphenol, p-tert-amine from a phenol and an alkylating agent.
It is an object of the present invention to provide a practically advantageous method for producing tertiary-amylphenols which can easily and efficiently obtain tertiary-amylphenols having a high utility value such as amylphenol.

[Means for solving the problem]

The present inventors have conducted intensive studies in order to solve the above-mentioned problems, and as a result, phenols were used in the presence of a specific acidic catalyst by using a specific alkylating agent, that is, a mixture of 3-methyl-1-butene and isoamylene. Depending on the method
The raw material is not limited to isoamylene as in the past, and high-purity 2,4-di-tert-amylphenol, p-
They have found that tertiary-amylphenol and the like can be obtained easily and efficiently, and have completed the present invention based on this finding.

That is, the present invention provides a process for producing tertiary-amylphenols, which comprises reacting a mixture of 3-methyl-1-butene and isoamylene with phenols in the presence of a cation exchange resin catalyst. Things.

You may get isoamylenes by hydrotreating a C ₅ fraction containing isoprene or isoprene, but in the process, usually 3-methyl-1-butene by-product. In the present invention, 3-methyl-2-butene can be used, which is industrially extremely advantageous. The composition of the alkylating agent of the present invention comprises isoamylene (2-methyl-2-butene and 2-methyl-2-butene).
(Methyl-1-butene) is 98% to 2% by weight, and 3-methyl-1-butene is 2% to 98% by weight. It is industrially preferable that the ratio of 3-methyl-1-butene to the alkylating agent is 10% by weight or more.

Also, a mixture containing other inert hydrocarbons and impurities may be used as long as the object of the present invention is not hindered.

In the present invention, the phenols used as one of the reaction raw materials include those used for the synthesis of known tertiary-amylphenols, and more generally, have at least one phenolic hydroxyl group, and At least one
Compounds having a hydrogen atom on an aromatic ring which can be substituted with a tertiary-amyl group, and usually, for example, the following general formula: (However, n in the formula is 1 or 2, preferably n = 1
And m represents an integer of 0 to 2, preferably 0 or 1, provided that n + m represents an integer of 4 or less, preferably 2 or less. R ¹ represents an inert substituent such as an alkyl group having about 1 to 18 carbon atoms and a cycloalkylalkyl group. The compound represented by the formula (1) can be preferably used.

Specific examples of R ^{1 in} the above formula [I] include, for example, methyl group, ethyl group, n-propyl group, n-butyl group, n
-Pentyl group, n-hexyl group, n-octyl group, n-
N-alkyl groups such as nonyl group, n-decyl group, n-dodecyl group, n-hexadecyl group and n-octadecyl group;
-Methyl-1-propyl group, 2-methyl-1-butyl group, 3-methyl-1-butyl group, 2,2-dimethyl-1-
Propyl group, 2-methyl-1-pentyl group, 3-methyl-1-pentyl group, 4-methyl-1-pentyl group, 3,3
-A branched primary alkyl group such as dimethyl-1-butyl group, 2-methyl-1-hexyl group, 2-methyl-1-heptyl group, 2-methyl-1-octyl group, isopropyl group, sec- Butyl group, 1-ethyl-1-propyl group, 1,3
-Dimethyl-1-propyl group, 1-methyl-1-pentyl group, 1,3,3-trimethyl-1-propyl group, 1-methyl-1-hexyl group, 1-methyl-1-heptyl group, 1
A sec-alkyl group such as -methyl-1-nonyl group, tert
-Butyl group, tert-amyl group (tertiary-amyl group), tert
-Hexyl group, tert-heptyl group, tert-octyl group,
Various alkyl groups such as tert-alkyl groups such as tert-decyl group, cyclopentyl group, methylcyclopentyl group,
Examples thereof include a cycloalkyl group such as a cyclohexyl group, a methylcyclohexyl group, an ethylcyclohexyl group, and a cyclooctyl group, and a cycloalkylalkyl group such as a cyclopentylmethyl group, a cyclohexylmethyl group, and a cyclohexylethyl group.

Among these various groups, an alkyl group having about 1 to 10 carbon atoms is preferable. Representative examples are tert-amyl group, te
There are rt-butyl group, tert-octyl group and the like.

Specific examples of the compound represented by the formula [I] include, for example, phenol, o-cresol, m-cresol,
Xylenol such as p-cresol and 2,6-dimethylphenol, 2-ethylphenol, 4-ethylphenol, 2,6-diethylphenol, 2-propylphenol, 4-propylphenol, 2-isopropylphenol, 4-isopropylphenol , 2-butylphenol, 2-sec-butylphenol, 4-sec-butylphenol, 2-tert-butylphenol, 4-tert-butylphenol, 2,6-di-tert-butylphenol,
2-pentylphenol, 4-pentylphenol, 2
-(1-methylbutyl) phenol, 4- (1-methylbutyl) phenol, 2- (1-ethylpropyl) phenol, 2- (1,3-dimethylpropyl) phenol,
2- (2-methylbutyl) phenol, 4- (2-methylbutyl) phenol, 2-tert-amylphenol,
Tert-amylphenol such as 4-tert-amylphenol, 2-hexylphenol, 4-hexylphenol, hexylphenol such as 2-tert-hexylphenol, heptylphenol such as 2-heptylphenol, 2-octylphenol, 2- tert-octylphenol, octylphenol such as 4-tert-octylphenol, decylphenol such as 2-decylphenol, 2-cyclohexylphenol, hydroquinone,
Resorcin, catechol and the like can be mentioned.

These phenols may be used alone or in a combination of two or more.

In the present invention, as the cation exchange resin catalyst, for example, a sulfonic acid type cation exchange resin, a sulfonic acid type cation exchange resin having a huge network structure (porous structure), and the like can be used. A sulfonic acid type cation exchange resin having a network structure can be suitably used.

Specific examples of the cation exchange resin include, for example, “Amberlyst-15” (both manufactured by Rohm and Haas) “Diaion HPK25”, “Diaion HPK40”
(All manufactured by Mitsubishi Kasei Kogyo Co., Ltd.).

The cation exchange resin catalyst used in the present invention is characterized in that neutralization treatment of the used catalyst is unnecessary, ease of separation from a product, etc., 4-tert-amylphenol, 2,4-di- Excellent in yield and selectivity of 3-amylphenol and the like.

In the present invention, a mixture of 3-methyl-1-butene and isoamylene is reacted with at least one phenol in the presence of the acidic catalyst to produce a desired tertiary-amylphenol.

At this time, the desired tertiary-amylphenol can be produced by appropriately selecting and adjusting the reaction conditions such as the type of the phenol used and the ratio of the reaction raw materials used.

For example, when the purpose is to produce particularly highly useful 4-tert-amylphenol, phenol is used as the phenol to produce 2,4-di-tert-amylphenol. In such a case, the phenols include phenol, 2-tert-amylphenol,
Use 4-tert-amylphenol or a mixture thereof.

The reaction of a mixture of phenol, 3-methyl-1-butene and isoamylene usually results in 2,4-di-tert-amylphenol, 4-tert-amylphenol and a small amount of 2-tert-amylphenol. A mixture such as phenol can be obtained.

In the present invention, the ratio of the mixture of 3-methyl-1-butene and isoamylene and the phenols used in the reaction is not particularly limited,
Tert- introduced per molecule of phenols normally used
It is desirable to adjust to various ratios according to the number of amyl groups.

That is, for example, the purpose is to obtain a mono-tert-amylphenol such as 4-tert-amylphenol from a mixture of phenol, 3-methyl-1-butene and isoamylene, and one phenol compound per molecule is used. When introducing a tertiary-amyl group, it is preferable to use about 1 mol of the above mixture per 1 mol of the phenols used, and to synthesize 2,4-di-tert-amylphenol. When two tertiary-amyl groups are introduced per phenol molecule, for example, for the purpose of carrying out the reaction, it is preferable to use about 2 mol of the mixture per mol of phenol used.

The reaction can be carried out in the absence of a solvent or, if desired, in a solvent.

As the solvent, usually, various inert organic solvents having a small aprotic polarity can be suitably used,
Specific examples include saturated hydrocarbons such as pentane, hexane, heptane, octane, nonane, and decane, and alicyclic hydrocarbons such as cyclohexane. If desired, a low-reactive protic solvent such as methanol or ethanol can be used.

These solvents may be used alone or in a combination of two or more.

The reaction temperature varies depending on other conditions such as the type and composition of the reaction raw materials and cannot be uniformly specified.
The temperature is preferably in the range of about to 120 ° C.

The reaction pressure is not particularly limited and the reaction can be carried out under normal pressure to pressurization.However, usually, the reaction system's own pressure ~ 20 kg / cm ² G
It is preferable to be within the range.

The reaction system is not particularly limited, and may be any system such as a batch system, a semi-batch system, a continuous system, and a semi-continuous system.

There is no particular limitation on the method of using the catalyst. For example, a fixed bed or a suspension bed can be suitably used.
If desired, a moving bed, a distribution bed, or the like can be used.

There is no particular limitation on the order and method of addition when the phenols and the mixture are introduced into the reaction system.For example, the phenols and the mixture may be mixed in advance and introduced into the reaction system, or Separately or stepwise may be introduced into the reaction system separately, and when using a batch system or a semi-batch system, either one, preferably, phenols is introduced into the reaction system in advance, and an acidic catalyst and optionally In the presence of a solvent, a method of introducing the other one of the reaction raw materials, preferably the above-mentioned mixture, may be used.

When the reaction is carried out batchwise or semi-batchwise in a non-continuous manner, the ratio of the acidic catalyst used is uniformly defined because it varies depending on other conditions such as the type of phenols, the content of impurities and the reaction temperature. Although it is not possible, it is generally preferable to be within a range of about 0.1 to 100 parts by weight, preferably about 1 to 10 parts by weight, based on 100 parts by weight of the phenols used. And composition,
The reaction temperature or the number of the tertiary-amyl groups to be introduced may vary depending on other conditions such as the number of the tertiary-amyl groups, and thus cannot be uniformly defined. Is preferred. In addition, 3-methyl-1-
When the reaction is carried out by dropping a mixture of butene and isoamylene into the reaction system, it is usually desirable to continue the reaction for about 0.5 to 5 hours after completion of the dropping.

When the reaction is performed continuously, the amount of the catalyst used is not particularly limited, and by appropriately adjusting the space velocity,
Although the conversion and selectivity to the desired tertiary-amylphenol can be adjusted, the specific size of the normally used space velocity can be calculated from the above-mentioned catalyst usage rate and reaction time. Can be.

In addition, when the solid acidic catalyst contains water, it is desirable to use an appropriate activation treatment prior to the above reaction. As an activation method, for example,
In a temperature range of 100 to 150 ° C, in an inert gas stream or in an inert atmosphere such as under reduced pressure, the water content is 1% by weight.
A method in which the drying treatment is carried out until the temperature becomes equal to or less than about is suitably used.

Further, when the activity of the catalyst is reduced, the catalyst may be subjected to an appropriate regeneration treatment and used repeatedly.

Tertiary compounds such as 2,4-di-tert-amylphenol and 4-tert-amylphenol synthesized as described above
Amylphenols can be separated from the reaction mixture by a known post-treatment method, purified to a desired purity, and recovered. Further, the obtained intermediate tertiary-amylphenols can be further alkylated with the above mixture, if desired.

In this way, various tertiary-amylphenols such as 2,4-di-tertiary-amylphenol and 4-tertiary-amylphenol, which are particularly useful, can be obtained easily, efficiently and economically. be able to.

In the present invention, the introduction position of the tertiary-amyl group is preferentially para to the phenolic hydroxyl group of the phenol in the case of mono-substitution, and in the case of di-substitution. Is preferentially in the 2,4-position, and when phenol is used, 4-tert-amylphenol or 2,4
-Di-tert-amylphenol can be obtained with high selectivity.

[Action]

In the present invention, 3-methyl-
A mixture of 1-butene and isoamylene is used,
Methyl-1-butene is a known isoamylene, i.e., 2-
Methyl-2-butene and 2-methyl-1-butene differ from each other in the relative position of the double bond and the side chain methyl group.
When -methyl-1-butene is used as an alkylating agent,
Common sense predicts that an isopentyl group other than the tertiary-amyl group is substituted into the aromatic ring of the phenol, but surprisingly, 3-methyl-1-butene is used as an alkylating agent. In this case, it was found that a tertiary-amyl group can be selectively introduced as in the case of isoamylene.

It is presumed that these phenomena are probably due to the combined catalytic action of the isomerization reaction and the alkylation reaction using an acidic catalyst such as a cation exchange resin.

〔Example〕

(Example 1) Into a 2 liter autoclave equipped with a stirrer, 589 g of phenol and 50 g of a cation exchange resin (Amberlyst-15) as a catalyst were charged and heated to 90 ° C. Then set the temperature to 9
The mixture of 3-methyl-1-butene and isoamylene (2-methyl-2-butene and 2-methyl-2-butene) [3-methyl-1-butene 24 wt% , 2-methyl-2-butene 15% by weight, 2
-Methyl-2-butene 61% by weight] was added over 3 hours. After the addition was completed, the reaction was continued at the same temperature for another 2 hours. After completion of the reaction, the yield of the reaction solution after removing the catalyst by filtration was 980 g. This reaction solution was distilled under reduced pressure using a 50φ, 25-stage Oldershaw distillation apparatus at an overhead pressure of 20 mmHg to separate 363 g of an initial fraction, 450 g of a tertiary-amylphenol fraction, and 157 g of a bottom.

The composition of these fractions was analyzed by gas chromatography.

The results are shown in Table 1. The percentages shown are all percentages by weight.

Identification of Main Product The structure of the tertiary-amylphenol obtained in Example 1 was determined by gas chromatography fractionation and then identified by NMR analysis.

Table 2 shows the results of the NMR analysis. As shown in Table 2, it was confirmed that the introduced alkyl group had a methyl group adjacent to the tertiary carbon and was a tertiary-amyl group. The NMR chart of this product shows that phenol and isoamylene (2-methyl-2-butene,
-Methyl-1-butene).
This was consistent with that of amyl phenol, which also confirmed that it was tertiary-amyl phenol.

Example 2 Phenol was placed in a 2 liter autoclave equipped with a stirrer.
380 g and 50 g of a cation exchange resin (Amberlyst-15) as a catalyst were charged and heated to 50 ° C.

While stirring, a mixture of 3-methyl-1-butene and isoamylene [3-methyl-1-butene 53% by weight,
8% by weight of 2-methyl-1-butene, 2-methyl-2-
Butene 39% by weight] 620 g was added over 5 hours, during which the reaction time was kept at 50 ° C.

After the addition was completed, the reaction was continued at the same temperature for another 2 hours. The yield of the reaction solution after filtering the catalyst was 980 g.

The pressure at the top of the column is increased by a 50φ 25-stage Oldershaw still.
Perform vacuum distillation at 20 mmHg, first fraction 59 g, middle fraction 251 g, 2,4
430 g of a di-tert-amylphenol fraction and 230 g of a bottom were obtained.

The composition of these fractions and the residue was analyzed by gas chromatography.

 The results are shown in Table 3.

Example 3 A 2-liter autoclave equipped with a stirrer was charged with 810 g of p-tert-octylphenol and 50 g of a cation exchange resin (Amberlyst-15) as a catalyst, and heated to 90 ° C.

While stirring, a mixture of 3-methyl-1-butene and isoamylene [3-methyl-1-butene 53% by weight,
8% by weight of 2-methyl-1-butene, 2-methyl-2-
Butene 39% by weight] 190 g was added over 3 hours, during which the reaction time was kept at 90 ° C.

After the addition was completed, the reaction was continued at the same temperature for another 2 hours. The yield of the reaction solution after filtering the catalyst was 980 g.

This was subjected to distillation under reduced pressure at a column pressure of 20 mmHg in a 50φ, 25-stage Oldershaw still, and 435 g of an initial fraction, 363 g of a 2-tert-amyl-4-tert-octylphenol fraction, and 172 g of a bottom 172 g.
I got

The composition of these fractions and the residue was analyzed by gas chromatography.

 The results are shown in Table 4.

According to the present invention, 3-methyl-1 is used as an alkylating agent.
Tert-amylphenols such as 4-tert-amylphenol and 2,4-di-tert-amylphenol using butene mixed with isoamylene and using a cation exchange resin as a catalyst, Easy and efficient with high purity,
In addition, a process for producing tertiary-amylphenols which can be obtained economically and which is extremely advantageous in practice can be provided, and the industrial value thereof is extremely large.

Claims (1)

(57) [Claims] 1. A process for producing tertiary-amylphenols, which comprises reacting a mixture of 3-methyl-1-butene and isoamylene with phenols in the presence of a cation exchange resin catalyst.