DE1593786B1 - Process for isomerizing o- and / or p-alkylphenols - Google Patents

Description

3 4

With regard to the better results that are achieved with the method according to the invention, about 0.5: 1 and is preferably between 0.5 and. Earth 3: 1. The clay should generally be about 5 to 40 alkali metal cations, such as calcium, magnesium, weight percent, preferably 7 to 25 percent by weight, rium and strontium ions, in particular calcium, based on the alkylphenol present,
or magnesium ions, take up the bulk of the 5 The overall reaction mixture quickly takes up one of the base exchangers. Other ions, such as alkali temperature between about 125 ° C and the decomposition metal ions or transition metal ions, can heat the reactants to a temperature. One keeps taking smaller part of the seats. The presence of the temperature between about 140 and 200 ° C, in front of more than about 1.4 weight percent alkali metal, preferably at the reflux temperature of the mixture (based on dry weight), can cause poor results (180 to 190 ° C). The reaction can in itself both produce results in the isomerization. Natural clays performed with underpressures as well as with overpressures can be used for the purposes of the present; advantageously one works at Atmosphä-invention to be used; because of their high back pressure or under autogenous pressure. Under diehaltes sen of alkali metal cations in the Basenaus- conditions, the equilibrium of the exchanger places must be i5 isomerization reaction in about ¹ J \ to about 4 hours treated with alkaline earth metal cations, such. B. ion exchange resins or generally between about V ₂ and 2 hours. At the end of this period, the clay is filtered off; to replace metal ions. the filtrate is subjected to fractional distillation, taking examples of naturally occurring aluminum throws.

Silicattones which meet the requirements of the invention. The o- and / or p-alkylphenols with alkyl requirements Sufficient are, for example, those under the groups with at least 5 carbon atoms, in all trade names "Bentolite L", "GelwhiteL" and mean about 5 to 30 carbon atoms on the "Clarolite T-60" known clays that have a crystal lattice are used by the method according to the invention from an aluminum oxide octahedron layer between should, for example, the o- and / or or p-iso are two Silicon oxide tetrahedral layers with a mesh of amylphenol, hexylphenol, heptylphenol, distance in direction 001 between 10 and 20 Å octylphenol, nonylphenol, decylphenol, dodecyl and a cationic base exchange capacity between phenol, hexadecylphenol, octadecylphenol, eicosyl about 80 and 120 milliequivalents per 100 g of phenol, docosylphenol, tricosylphenol and Mi-clay have, d. H. Montmorillonites (cf. Ki rk- mixtures of these compounds. Preferably acts O t h m e r, Encylopedia of Chemical Technology, 30 these alkylphenols are secondary alkyl vol. 4, pp. 28 to 30, 1st edition 1949, second print phenols.

1954), which is also less than about 1.4 weight- The o- and or or p-alkylphenols can by

percent iron and in their crystal lattice the alkylation of phenols with olefins in the presence Base exchange places mainly from alkaline earth an alkylation catalyst, such as a strong acid metal ions are occupied. 35 or an acid activated clay.

These special clays are activated with acids, a particularly suitable starting material for the

generally with mineral acids, such as sulfuric acid, processes according to the invention can be prepared, and phosphoric acid, preferably sulfuric acid. By using phenol with straight-chain 1-alkenes agreed organic acids, such as toluenesulfonic acid, at least 5 carbon atoms in the presence of the can also be used. 40 acid-activated tones, which are also used for the iso-

The clay can be activated with acid before it is used for merization. Best used to add to the isomerization mixture. The clay one for the implementation of a 1-alkene, which so pure can also be activated in situ. With an activation as is possible. In order to produce secondary o- and p-alkylphenols in this way, the clay is first heated to a water content of about 5 to 8 percent by weight. The 1-alkene is counter-dried with an excess of phenol. Care must be taken to ensure that the temperature of the clay and acid is kept at a temperature between about 40 and HO ⁰ C long enough to avoid overdrying of the clay, so that an alkylation of the occurs because this results in partial deactivation. Phenol takes place. Lower temperatures at the In general, a satisfactory alkylation is achieved, favor the formation of o-alkylphe drying at 100 to 120 ° C. in 2 to 3 hours. According to 5 ° nols and / or alkylphenyl ethers. It is assumed that the clay along with about 0.02% of drying will constitute an intermediate sample of 0.1 g of acid per gram of clay in the reaction product of the reaction. They are also brought out as a mingling. starting materials for the inventive

If the tone is activated beforehand, it can be brought into the position of m-alkylphenols,
an anhydrous acid solution, e.g. B. with a solution 55 The following examples serve to further illustrate sulfuric acid in ether together. The suspension of the present invention,
The mixture is filtered and washed several times with the solvent to remove excess acid. After a short drying time, the clay represents an example 1
good isomerization catalyst, without 60

further addition of acid. 24.6 g of a mixture of o- and p-sec-amylphenol

The acid and the clay or acid treated were added to 9.4 g of phenol in a suitable vessel Clay are added to the reaction mixture, which is added. This amylphenol-phenol mixture was the 0- and / or p-alkylphenol with alkyl groups with 6.4 g of »Bentolite L« (26 percent by weight, based on with at least 5 carbon atoms as well as phenol 65 on amylphenol), a natural clay with a contains. The presence of phenol favors the montmorillonite crystal lattice in which each Formation of m-monoalkylphenols. The Molver- a layer of aluminum oxide octahedra between two ratio of phenol to alkylphenols is at least layers of silicon oxide tetrahedra, and 0.4 g

concentrated H ₂ SO ₄ added. The analysis of the clay in percent by weight (based on dry weight) gave the following values:

SiO ₃ 74.2

Al ₂ O ₃ ........ 18.6

MgO 4.67

CaO 1.89

Fe ₂ O ₃ 0.34

Na ₂ O 0.22

K ₂ O 0.046

TiO ₂ 0.17

This reaction mixture was heated under reflux (180 to 19O ⁰ C). Equilibrium of conversion was reached in 2 hours (~ 65 to 70% m-isomer in the mixture of amylphenol isomers). A sample was taken from the reaction mixture for analysis; the solution was filtered off from the clay; the filtrate was examined with the aid of gas-liquid chromatography. The reproducibility was about ± 2%.

For comparison, a second test was carried out under identical conditions, with the The proportions were the same, but instead of "BentoliteL" a commercially available clay, namely "Retrol" (clay of the Möntmorillonite type) was used. "Retrol" showed in the analysis, based on the dry weight, the following values:

SiO ₂ 70.9

Al ₂ O ₃ 17.0

MgO 3.2

CaO 1.6

Fe ₂ O ₃ 3.9

Na ₂ OK ₂ O 1.0

TiO ₂ 0.6

After 2 hours, the isomerization in the comparative experiment was only about 42% of equilibrium achieved. Even after a reaction time of 14 hours, only 54% of equilibrium was reached.

Example 2

The isomerization experiment and the comparative experiment according to Example 1 were repeated, however with the modification that an o- and p-sec-octylphenol mixture is used instead of amylphenol ίο was.

After one hour, the isomerization with “Bentolite L” had reached equilibrium. In the comparison experiment four times as long was required to reach equilibrium.

Example 3

The isomerization experiment and the comparative experiment according to Example 1 were repeated, but with

ao the modification that an o- and p-sec-dodecylphenol mixture was used instead of amylphenol. After one hour, the isomerization with “Bentolite L” had reached equilibrium. In the comparison experiment 83% of equilibrium were only reached after one hour. After 4 hours were at the comparison test reached 94% of equilibrium.

To the great activity of the clays according to the invention and those with the aid of the method according to the invention To explain further improvements to be achieved, isomerization and corresponding Comparative tests carried out according to Example 1, using different o- and p-alkylphenols together with only 10 percent by weight of clay, based on alkylphenol, were used. The results of these tests are summarized below: B = »Bentolite L «, R =» Retrol «.

example Alkylphenol volume Effective
Time (hours) wheel
% Balance 4th sec-octylphenol
sec-octylphenol B.
R. 1/100
1/38 10/95 5 sec-dodecylphenol
sec-dodecylphenol B.
R. 1/100
1/54 4/62 ** 6 sec-tridecylphenol
sec-tridecylphenol B *
R * 4/96
4/31 **8th sec-hexadecylphenol
sec-hexadecylphenol
sec-eicosylphenol
sec-eicosylphenol B.
R.
B.
R. 1/85
l / to ver
negligent
4/77
7 / ~ 10 4/100
7 / -10

* 9.44 weight percent clay based on tridecylphenol. ** Infrared analysis.

Example 9

The isomerization according to Example 1 was repeated again, but using “Gelwhite L”, a natural one Clay was applied with a montmorillonite crystal lattice. This clay had, on dry weight, related, following composition:

SiO ₂ .
Al ₂ O ₃ .
MgO.
CaO ..

65.1 Fe ₂ O ₃ 25.3 Na ₂ O 4.15 K ₂ O 2.66 TiO ₂

. 1.04 1.35 0.04 0.26 After 3 hours the isomerization was 96% des Equilibrium reached.

Other aluminosilicate clays that have been used in known processes have been used in the Method according to example 1 used; it turned out that they are ineffective. A montmorillonite with the composition given below (in percent by weight, based on the dry weight) had not caused isomerization even after heating for 4 hours.

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SiO ₂ 72.3 Fe ₂ O ₃ .. 0.3 to 1.1 was un-

Al ₂ O ₃ 16.5 Na ₂ O 5.93 effective.

MgO 3.8 K ₂ O 0.045 SiO ₂ 62.7 Fe ₂ O ₃ 1.02

CaO 1.2 TiO ₂ 0.17 ⁵ Al ₂ O ₃ 24.4 Na _a O 5.16

Also a montmorillonite with the following ^{Mg0 4} '° ^K * ° °' ⁰⁴

Composition (based on dry weight) CaO 2.55 TiO ₂ 0.24

Claims (1)

1 2 p-alkylphenol, especially p-tert-butylphenol, in counter- Claim: Was one of an activated fuller's earth and one inorganic acid, especially conc. Sulfuric acid, Process for isomerizing o- und.bzw. existing catalyst to a temperature of or p-alkylphenols, the alkyl groups of which are heated from 175 to 200.degree. C., preferably 175 to 185.degree Contain at least 5 carbon atoms, to the ent- and the m-alkylphenol from the reaction mixture speaking m-alkylphenols is separated by heating in. When activated fuller's earth is active of at least 0.5 moles of phenol per mole of fourth fuller's earth ("Fulcat", cf. column 1, parts 12 to 15) Alkylphenol and an acid-activated aluminum. niumsilikattones, which a crystal lattice from a io From the German Auslegeschrift 1 069 583 is an aluminum oxide octahedron layer between two processes for the production of catalysts by silicon oxide tetrahedron layers with a lattice treatment of dried powdered, bentonite spaced in the direction 001 between 10 and 20 Å known to be washed out with concentrated sulfuric acid without subsequent and a cationic base exchange capacity. According to this method, the treatment is carried out in a temperature range known per se for the ion exchange of 100 g of clay between about 80 and 120 milliequivalents per 15 with an acid at least about 125 ° C, characterized by an amount that characterizes the ion exchange capacity that the isomerization of bentonite is equal to or by a factor of 1.1 to a temperature of about 140 to 200 ° C in counter- to 1.15, based on acid-consuming consumption of less than about 1.4 percent by weight of impurities free Bentonite, is higher.
Iron (based on the dry weight) included- As seen from column 1, para. 2 of the German Auslegeden acid-activated aluminum silicate clay pre-writing 1069 583 stating be take by the Behänd- ^, in the crystal lattice of the Basenaustauscher- lung with hot acid and the alkaline earths removed "bursts mainly loaded by alkaline earth metal ions and replaced by hydrogen and aluminum,
are set. 25 In French patent 1 354 508 a process for the preparation of 3-alkylphenols described, with 2,4- or in the presence of phenol 2,6-dialkylphenols with activated bleaching earth Temperatures above 150 ° C, preferably 170 to 190 ° C, The invention relates to an improved method 30 of being heated. As active bleaching earth are included for isomerizing o- and / or p-alkylphe- generally acid-activated bentonites (p. 1, column 2, nolen whose alkyl groups are called at least 5 carbon lines 25/26). containing atoms to the corresponding m-alkylphe- The process of the invention for isomerization nolen. by heating the o- and / or p-alkyl of o- and / or p-alkylphenols, their alkylphenols contain at least 5 carbon atoms in the presence of at least 0.5 mol of phenol 35 groups per mole of alkylphenol and of an acid-activated aluminum corresponding m-alkylphenols by heating mini silicon tones. in the presence of at least 0.5 moles of phenol per mole It is well known, e.g. B. from the USA.-patent alkylphenol and an acid-activated aluminum specification 3 014 079 that ο- and / or p-alkylphenols silicate tones, which form a crystal lattice of an aluminum by heating to over about 125 ⁰ C in the presence of a 4 ° niumoxyd- Octahedron layer between two silicon-strong acid or natural or synthetic alumina tetrahedron layers with a lattice spacing in miniumsilikattone to m-alkylphenols of direction 001 between 10 and 20 Å and one can be isomerized. cationic base exchange capacity between about _Λ Clays of the montmorillonite type are 80 and 120 milliequivalents per 100 g of clay, \ proposed and specifically "Retrol" and "Tonsil®" 45 at a temperature of at least about 125 ° C is mentioned. Although the process for alkylphenols is characterized by the fact that the isomerization is simply described, it can be seen from the counterparts at a temperature of about 140 to 200 ° C. that the process only works for less than about 1.4 percent by weight Iron is suitable alkylphenols in which the alkyl (on a dry weight basis) containing acid group contains fewer than 5 carbon atoms. The 50 activated aluminum silicate tones makes, in the application of this isomerization process on o-crystal lattice the base exchange places predominantly and / or p-alkylphenols, whose alkyl groups are occupied by alkaline earth metal ions,
Contain at least 5 carbon atoms, but has by the method according to the invention can various disadvantages. First, in older processes, o- and / or p-alkylphenols, the alkyl groups to reach equilibrium of conversion 55 with at least 5 carbon atoms, rapidly a long reaction time - in some cases from to their corresponding m-alkylphenols under Er-25 up to 30 hours - required. Some keys reaching the approximate balance of the surrounding area ineffective. The older processes show some changes without significant side reactions isomal only side reactions instead of isomerization. be merized. In the one used according to the invention For example, o- and / or p-nonyl-6q acid-activated aluminum silicate clay are the base phenols split into lower alkylphenols and not exchange places predominantly of alkaline earth metals m-Nonylphenol isomerized. Are the known ions occupied; Iron lies in both the basic substance Isomerization catalysts first for alkylation (colloidal) as well as in exchangeable form (isomorphic) of phenol used with «-olefins, so are very much before. The space lattice is within the specified intensive reaction conditions necessary. 65 area stretchable. The German Auslegeschrift 1186 873 describes a low iron content, the base exchange Process for isomerizing p-alkylphenols to the capacity and specificity of the ions that make up the base ends corresponding m-alkylphenols, which occupy exchange positions, are important factors in the