CS257813B1 - Method of phenol and/or alkylphenol arylalkylation - Google Patents

Abstract

Arylalkylase of phenol and / or alkylphenol is carried out in a liquid phase with the suspension suspended acid catalyst or scrubber catalyst bed (active bleaching earth, activated zeolites P2 ° 5 on the support) the arylalkylating agent is a fraction from the distillation residue from the production of phenol and acetone catalyzed decomposition of cumene hydroperoxide, obtained distillation or rectification under reduced pressure (0.1 to 15 kPa) containing a mixture of dimethylphenylcarbinol, acetophenone, phenol and c0-methylstyrene, in a total amount of 75 to 100%. Dimethylphenylcarbinol / phenol molar ratio or alkylphenol is used from 0.4 to 2.5 (0.7 to 1.3).

Description

The invention relates to the arylalkylation of phenol and / or alkylphenol by a non-traditional arylalkylating agent® based on a by-product from the production of phenol and acetone, so-called. cumene.

Arylalkylphenols are known antioxidants for fuels, oils and polymers, but also as intermediates for even more effective stabilizers, pharmacological agents, herbicides, plant and animal growth regulators (U.S. Pat. No. 3,012,879; Tropathy H. et al., Arg. Biol. Chem. India 37, 1375 (1973), CA 79, 101 522 h (1973), Belgian patent 612 832, CA 58, 11 901 (1963);

NSR pat. 1,198,831).

In the last period is also appreciated their high disinfectant, respectively. bactericidal and fungicidal effect. Some of them, such as cumylphenols are isolated from so-called. phenolic pitch by fractional distillation (U.S. Pat. No. 2,769,844, Romanian Pat. No. 57,169 and V. Brit. Pat. No. 1,235,415) or by crystallization with n-pentane or n-heptane (Dutch Pat. 722,524; C.A.

68, 95,512 j).

However, these resources are very limited. Therefore, the arylalkylarium of phenol or alkylphenol of alpha-methylstyrene is increasingly becoming increasingly important under the catalytic action of lewis and bronsted acids (Kurashev et al; Neftechimija 9, 842 (1969); 7,507 (1967); US Pat. 2,247,402; and Polish Pat. 100). 643). Alpha-methylstyrene, in addition to products other than phenol, acetophenone and cumene, is produced by thermocatalytic decomposition of so-called. phenolic pitch on aluminosilicates, in particular zeolites (USSR author's certificate 583 996; US Pat. 2 217 175, 4 339 605 and 4,358,618; Czechoslovak Author's certificate 118 409 and 121 796; V. Brit. Pat.

169 291).

Such production of alpha-methylstyrene is relatively energy intensive and, in addition to phenol, does not make it possible to obtain other technically important components from phenol pitches. Moreover, the arylalkylation of phenol-methylstyrene by known methods does not achieve high selectivity, only low yields of o- and β-cumylphenol are obtained. This is due to the simultaneous dimerization of alpha-methylstyrene to unsaturated dimers, which is also isomerized to saturated dimers by the action of acid catalysts such as alkylation and arylalkylation catalysts, in particular 1,1,3-trimethyl-3-phenylindane, whose formation is virtually irreversible. Also known is an interesting method of arylalkylation of phenol and / or alkylphenol according to U.S. Pat. Copyright O3vedčenia AO 250 861, which is carried out in the liquid and / or vapor phase at a temperature of 70-260 ^U C, catalyzed by the at least one brůnstedovskej and / or a Lewis acid, or of Compound of aluminum in the liquid and / or solid form, wherein the arylalkylating agent is, inter alia, dimethylphenylcarbinol and dimethylphenylcarbinol with alpha-methylstyrene; However, it is technically less desirable to use a too varied mixture of the above-mentioned components in an arylalkylating agent and to separate acetophenone from near boiling components.

According to the present invention, a process for arylalkylating phenol and / or alkylphenol according to U.S. Pat. AO 250 861 is carried out in such a way that the arylalkylation is carried out in the liquid phase with a suspended acid catalyst or a scrubbed catalyst bed, preferably with an active bleaching clay, the arylalkylating agent being a distillate fraction from phenol and acetone production by catalytic hydroperoxide distillation or rectification under reduced pressure, preferably 0.1 to 15 kPa, containing a mixture of dimethylphenylcarbinol, acetophenone, phenol and optionally alpha-methylstyrene, in a total amount of 75 to 100%, using a total dimethylphenylcarbinol / phenol and / or molar ratio of or alkylphenol 0.4 to 2.5, preferably 0.7 to 1.3.

The advantage of the method according to the invention, in addition to the advantages stated in the basic copyright certificate, is technically simpler and less energy-consuming separation of the aryl acid, eliminating the need for arylalkylation due to the presence of dimethylphenylcarbinol eliminates the demanding separation of acetophenone. phenolic pitch. The energy-intensive dehydration of dimethylphenylcarbinol to alpha-methylstyrene is enriched and there is no need for the intensive isolation of phenol from the front fraction of so-called. phenolic pitch.

In this process, acetonphenone (t 202 ° C / 101 kPa) is easily separated from the arylalkylate, even by differential distillation, from o-cumylphenol (t 160 ° C / 1.3 kPa) and p-cumylphenol (t 187 C / 1.3 kPa) . Thereafter, the distillation residue containing cumylphenols is readily separated or as such, without further isolation, it can be used as an intermediate in cumylphenol utilization processes.

It is suitable from the so-called. phenol pitch under reduced pressure by rectification to separate mainly dimethylphenylcarbinol, acetophenone and phenol, optionally present alpha-methylstyrene. The presence of alpha-methylstyrene depends on the thermal stress of the distillation residue from phenol distillation, the so-called. phenolic pitch or distillation temperature. To minimize its formation by dehydration of dimethylphenylcarbinol, the highest possible vacuum is needed in the distillation of phenolic pitches. Minimal formation of alpha-methylstyrene is required for both energy savings and cumylphenol yields, as the arylalkyl of phenol or alkylphenol is more selective with dimethylphenylcarbinol than with alpha-methylstyrene.

In addition to the usual acidic homogeneous and heterogeneous alkylation catalysts, also effective for arylalkylation, activated natural and synthetic aluminosilicates such as bentosilicates such as bentonites (montmorillonite, clinoptilolite, etc.) are particularly suitable.

It is desirable to remove the reaction water from the arylalkylation reaction medium, optionally together with the lower boiling components.

Further details of the method of the invention as well as other advantages are apparent from the examples.

EXAMPLE

Weigh 60 g of the first fraction obtained by distillation of so-called distillation into a three-necked flask with a capacity of 250 cu / tempered by an oil bath equipped with a stirrer, a thermometer and a water condenser. phenolic pitch from the production of phenol and acetone by catalytic decomposition of cumene hydroperoxide.

The first fraction obtained was m.p. in. 30 to 165 ° C / 2.67 kPa has the following composition (in% by weight): alpha-methylstyrene = 0.3; alpha-methylstyrene dimers = 4.2 (of which not otherwise identified = 1.0; 2,4-diphenyl-4-methyl-1-pentene = 2,2; 2,4-diphenyl-4-methyl-2-pentene = 0.6, 1,1,3-trimethyl-3-phenylindane = 0.4); dimethylphenylcarbinol = 36.5; phenol = 15.5; o-cumylphenol = 0.5; p-cumylphenol 0.5 and acetophenone · 41.6.

With constant stirring, the I fraction is heated until the desired reaction temperature is reached. 12 g (ie 20% by weight per fraction) of active bleaching clay, prepared by activating bentonite, are then added and have the following composition (in% by weight): S1O2 = 54.7; Al ₂ O ₃ = 18.6;

MgO = 3.9; CaO = 2.2; Fe ₂ O ₃ 2.6; K ₂ O = 0.2; TiO ₂ = 0.2; Na ₂ O = 0.05; Loss on ignition = 17.4% (powdered, sieve residue 0.2 mm = 3.7%; bulk density = 491 kg.m ^).

The reaction temperature was maintained to an accuracy of 12 ° C throughout the reaction time of 4 h. the reaction water (from the dehydration of dimethylphenylcarbinol) is continuously removed.

The results obtained are summarized in Table 1.

Table 1

Analysis of arylalkylate (wt.%)

Conversion (»)

Selectivity (%)

Dimers of alpha-methylstyrene

at 0 1-t Ό) ABOUT o q about q > » JJ s C q xy • H + J C 1 • lj • lj • H u X » 0) φ XU f> Λ X -Q> 4 <0 δ SX C 1 jj Jj - * Jj jj JJ (0 1 t | FLJ rj D TJ 0 ÍTj (Λ about Ai xr cm > > ·, and: and X Ή «J i-1 i-l 1 | | ABOUT JJ and t «-J φ rj cb > 1 ABOUT 0 rj rď rj aí φ q > 4 >, MJ > 4 JJ φ C C q > 4 >,>, • lj 2 Ή3 q CH q Φ jj IN * 0 Φ Φ q q C JJ MJ ♦ Η Ό φ Φ ΪΝ Φ 6 m C MJ MJ Φ xy QJ Φ ♦ H q MJ MJ g Mj 1 vd Φ i-l rj MJ JJ MJ S JJ JJ -lj rj 3 · —1 ITJ C > 1 mj > 4 b • H C • iJ i C> 1 -J > 4 □ > 4AI > IMJ > About JJ 0 »-1 § 6 TJ Q) Ό Ό Φ u -H> 4 JJ rj + J 1 JJ -J Φ 4J 0 3 3 1 SX and TJ 'Φ - c Φ 3 0 Φ SX Φ íC ItJ e 0 q A! A5 xS · 1 XT rj • H 6 1 — t d> e h C 6 with 0) Ή 0 Φ 1 1 * I-J * <TJ φ Ή -MJ • d 0 0 • H (Ti • Η Φ 05 Q them ABOUT 04 CM 1 CM I C TJ r-t 1 ie q TJ q ie q

100 0.0 48.6 6.1 0.6 32.0 1.4 5.0 0.8 3.9 100 60.7 56.2 21.8 110 0.0 49.1 5.8 0.5 37.9 0.8 0.0 0.2 1.7 100 (62.6 66.2 - 130 0.0 46.7 3.0 0.6 43.5 0.5 0.9 0.4 2.7 100 81.6 76.5 0.3 150 0.0 45.9 3.5 1.5 38.8 0.8 0.7 1.7 4.3 100 78.5 68.2 8.3 170 0.0 32.9 7.5 3.0 21.1 0.5 2.1 5.1 26.2 100 48.4 32.0 89.5

Example 2 ..

Weigh 500 g of the I. phenol pitch fraction specified in Example 1 into a three-necked 1 dm 2 flask equipped with a thermometer, stirrer and condenser for condensing the distilled low-boiling fractions, tempered with an oil bath. 100 g of active bleaching clay also specified in Example 1. Thereafter, water from the three-necked flask was continuously distilled off and the lower-boiling fractions were broken in a quantity of 9.5 g for 5 h. After 5 h, the reaction product is cooled, filtered, the separated bleaching earth is carefully used for arylalkylation and the crude reaction product is analyzed and separated by rectification.

The crude reaction product consists (in% by weight) of 45.9 acetone, 1,5-o-cumylphenol, 38.8? -Cumylphenol, 3.5 phenol and 7.5 dimers of alpha-methylstyrene. Dimethylphenylcarbinol is absent. The phenol is recirculated after separation, the alpha-methylstyrene dimers are either recirculated or used as a fuel component and the acetophenone is isolated as pure. Pure β-cumylphenol is also isolated, optionally together with o-cumylphenol or even with admixtures of acetophenone and alpha-methylstyrene dimers.

Example 3

Rectification of distillation residue from phenol production by cumene method - so-called. the phenolic pitch is rectified under reduced pressure (2.67 kPa) on a 3-th theory column with a reflux ratio of 2: 1 to give a first fraction of boiling point 92.5-95 ° C / 2.67 kPa of this composition ( % by weight): acetophenone = 52.9; dimethylphenylcarbinol = 24.3; phenol - 20.7; alpha-methylstyrene-1,7; alpha-methylstyrene dimers -0.3; o-cumylphenol (0.05) and p-cumylphenol (0.05).

This fraction I is weighed in an amount of 500 g into a three-necked flask specified in Example 2, heated to 130 ° C with stirring, and 26 g of active bleaching clay specified in Example 1 are added. Arylalkylation is carried out for 3.5 while distilling off 15.5 g of low boiling fraction (water and alpha-methylstyrene). The arylalkylate after separation of the catalyst has the following composition (wt.%): Acetophenone = 52.8; dimethylphenylcarbinol = 0.0; phenol = 4.2; alpha-methylstyrene = 0.1; alpha-methylstyrene dimers = 4.5; o-cumylphenol = 0.5 and p-cumylphenol = 37.3. Methylphenylcarbinol conversion = 100% and selectivity of conversion of dimethylphenylcarbinol to p-cumylphenol = = 91.4%; selectivity of phenol to p-cumylphenol conversion = 100%.

attaches

From the I. phenol pitch fraction specified in Example 3, it was extracted with an aqueous solution of sodium hydroxide at a concentration of 10% by weight. sodium phenolate is extracted at room temperature. Thereafter, after washing the water and removing the moisture, an almost phenylated I. fraction of the following composition (% by weight) is obtained: acetone phenone = 55.0; dimethylphenylcarbinol = 38.4; phenol = 0.8; alpha-methylstyrene = 0.4; alpha-methylstyrene dimers = 4.3; o-cumylphenol = 0.2 and p-cumylphenol <0.5.

K 100 wt. 38.1 wt. parts of o-cresol (mole ratio of dimethylphenylcarbinol) o-cresol = 0.8) in the presence of 20 wt. parts of active clay as a suspended (heterogeneous) catalyst specified in the example

1. The arylalkylation is carried out at a temperature of 130 ± 2 ° C for 4.5 hours, continuously removing a low-boiling fraction in a total amount of 5% by weight. section. The arylalkylate after separation of the catalyst contains (in wt.%): Acetophenone = 39.6; dimethylphenylcarbinol = 0.0; o-cumylphenol = 0.2; p-cumylphenol = 3.0; phenol = 0.3; o-cresol = 8.6; p-cumyl-o-cresol = 39.7; alpha-methylstyrene = 0.1 and alpha-methylstyrene dimers = 7.2.

Thus, the conversion of dimethylphenylcarbinol is 100%; selectivity of dimethylphenylcarbinol to p-cumyl-o-cresol = 85% and selectivity of o-cresol to p-cumyl-o-cresol = 100%.

Example 5

A phosphate catalyst (polyphosphates on silica, P = 22.61% by weight) of grain size x 6 mm is injected at a temperature of 160-3 ° C in an amount of 0.086 kg.m -1, s ^-1 . faction

-3 3 -3 -1 from phenolic pitches Specified in Example 3, at a nitrogen flow rate of 4.67.10 m · s, with conversion of dimethylphenylcarbinol reaching 99.7% and phenol 76% and selectivity of dimethylphenylcarbinol to o-cumylphenol (2-cumylphenol) = 8% and p-cumylphenol (4-cumylphenol) = 64%. The unconverted raw materials separated from the arylalkylate are recirculated.

Claims (2)

OBJECT OF THE INVENTION A process for the arylalkylation of phenol and / or alkylphenol according to U.S. Pat. 250 861, characterized in that the arylalkylation is carried out in liquid phase with a suspended acid catalyst or in a scrubbed catalyst bed, for example with active bleaching clay, wherein the arylalkylating agent is a fraction from the distillation residue from phenol and acetone production catalyzed by decomposition or cumene hydroperil by rectification under reduced pressure, in particular at 0.1 to 15 kPa, contain a mixture of dimethylphenylcarbinol, acetophenone, phenol and optionally alpha-methylstyrene, in a total amount of 75 to 100%, using a total dimethylphenylcarbinol / phenol molar ratio of arylalkylation and / or alkylphenol 0.4 to 2.5. 2. Method according to claim 1, characterized in that a ratio of dimethylphenylcarbinol / phenol and / or alkylphenol of 0.7 to 1.3 is used.