CS257813B1 - A method of arylalkylating phenol and / or alkylphenol - Google Patents

Abstract

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

Description

257813

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

Arylalkylphenols are known antioxidants for spirits, oils and polymers, but also intermediates for even more effective stabilizers, pharmacological preparations, herbicides, plant and animal growth regulators (U.S. Pat. No. 3,012,879; Tropathy H. and others: Arg. Biol. Chem. India, 37, 1375 (1973), CA 79, 101, 522 h (1973), Belgian Pat., 612, 832; CA 58, 11, 901 (1963); In recent years, their high disinfectant, resp. bactericidal and fungicidal effect. Some of them, such as cumylphenols, are isolated from so-called phenolic pitches by fractional distillation (U.S. Pat. No. 2,769,844, Romanian Pat. No. 57,169 and V. Brit. Pat. No. 1,235,415) but by recrystallization with n-pentane or n-heptane (Dutch Pat. No. 722,524; CA 68, 95,512).

However, these raw materials are very limited. Accordingly, the phenol or alkylphenol of alpha-methylstyreneen is important in the catalytic action of Lewis and bronsted acids (Kurashev et al .; Neftechimija 9, 842 (1969); 7 507 (1967); U.S. Pat. No. 2,247,402; and Polish Pat. 100,643). At the same time, alpha-methylstyrene led other products, acophenol, acetophenone and cumene, by thermocatalytic decomposition of so-called phenolic pitches of aluminosilicates, especially zeolites (USSR 583 996; US Pat. No. 2,217,175.4,339,605 and 4,358,618; 118 409 and 121 796; V. Brit.

Such production of alpha-methylstyrene is relatively energy-intensive and apart from phenol, it does not allow other technically important components to be obtained from phenolic resins. In addition, arylalkylation with phenol-methylstyrene by known procedures does not achieve high selectivity, only low yields and p-cumylphenol are obtained. This is due to the simultaneous dimerization of alpha-methylstyrene to unsaturated dimers, which are also due to acid catalysts, such as alkylation catalysts and arylalkyls, being saturated to saturated dimers, especially 1,1,3-trimethyl-3-phenylindane, whose formation is practically irreversible. An interesting method of arylalkylation of phenol and / or alkylphenol-substituted MS is also known. AO 250 861, which is carried out in a liquid and / or vapor phase at a temperature of 70-260 UC, with the catalytic action of at least one bromosulfonic acid and / or lewisic acid or aluminum compound in liquid and / or solid form, in which the arylakylating agent except others are also dimethylphenylcarbinol and dimethylphenylcarbinol with alpha-methylstyrene, the aromatic alkylating agent may also be a fraction from the distillation residue of phenol and acetone production catalyzed by the decomposition of cumene hydroperoxide, with the advantage of separating at least a substantial portion of acetophenone and cumylphenol. However, it is technically less desirable to use too bright a mixture of higher boiling components in an arylalkylating agent and to separate acetophenone from components with close boiling points.

According to the present invention, the arylalkylation of phenol and / or alkylphenol is contemplated. AO 250 861 implements that arylalkylation takes place in a liquid phase with suspended acid catalyst or catalyst scrubber, preferably with active bleaching earth, wherein the arylalkylating agent is a fraction from the distillation residue of phenol and acetone production by catalytic decomposition of cumene hydroperoxide, obtained by distillation or rectification under reduced pressure, preferably at a pressure of 0.1 to 15 kPa, containing a mixture of dimethylphenylcarbinol, acetophenone, phenol and optionally alpha-methylstyrene, in a total amount of 75-100%, using a total molar ratio of dimethylphenylcarbinol / phenol and / or alkyl -phenol 0.4 to 2.5, preferably 0.7 to 1.3. The advantage of the process according to the invention, in addition to the advantages mentioned in the basic author's certificate, is the technically simpler and less energy-demanding separation of the arylalkylate, the need for a separation of the acetophenone from the fraction obtained from the phenol pitch by the arylaiclation due to the presence of dimethylphenylcarbinol. energy-intensive dehydration of dimethylphenylcarbinol to alpha-methylstyrene, and no difficult recovery of phenol from the anterior fraction of the so-called phenol pitches.Thereby, 2 arylalkylate is technically easy, even by differential distillation, to separate acetone phenone (tv 202 ° C / 101 kPa) from o-cumylphenol (tv 160 And p-cumylphenol (tv 187 C / 1.3 kPa), then the distillation residue containing cumylphenols can be easily separated or, as such, without further isolation, can be used as an intermediate in the processes of utilizing cumene phenols .

Especially dimethylphenylcarbinol, acetophenone and phenol are preferably separated from the so-called phenolic mixtures under reduced pressure by rectification, eventually alpha-methylstyrene is present. The presence of alpha-methylstyrene depends on the thermal stress of the distillation residue from the 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 the phenolic compounds. The minimization of alpha-methylstyrene is needed both for reasons of energy savings and cumylphenol yield because arylalkylation of phenol or alkylphenol is more selective with dimethylphenylcarbinol 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 bentonites (montmorillonite, clinoptilolite, and the like) are suitable. Further details of the method of the invention as well as other advantages are apparent from the examples.

To a three-necked flask of 250 cm @ 3 tempered with an oil bath equipped with a stirrer, a thermometer and a water-cooled condenser, weigh 60 g of the I. fraction obtained by distillation. phenol mixtures from the production of phenol and acetone by catalytic decomposition of cumene hydroperoxide. The fraction I obtained at 30 DEG-165 DEG C./2.67 kPa has the following composition (in% by weight): .alpha.-methylstyrene = 0.3; alpha-methylstyrene dimers = 4.2 (of which unidentified = 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.

While not stirring, the first fraction is heated until the desired reaction temperature is reached. Then 12 g (i.e. 20% by weight of the first fraction) of the active bleaching earth prepared by the activation of bentonite are punched and are in the composition (in% by weight): S102 = 54.7; A12C3 = 18.6;

MgO = 3.9; CaO = 2.2; Fe 2 O 3 »2.6; K2O = 0.2; TiO 2 = 0.2; Na2O = 0.05; loss on ignition = = 17.4% (powder, sieve residue sitek 0.2 mm = 3.7%; bulk density = 491 kg.m ^).

The reaction temperature is maintained at an accuracy of 12 ° C over the entire reaction time of 4 hours, while the reaction water (from the dehydration of dimethylphenylcarbinol) is continuously removed.

The results are summarized in Table 1. 257813

Table 1

Analysis of arylalkylate (% by weight)

Conversion <%>

Selectivity (%)

Dimers of alpha-methylstyrene u 0 1—1 Ό) O o q o q í q Φ Φ p p U XU Λ X -Q>. <0 δ SX C 1 dd - 4d> p (0 1 t | rtj i — 1 Φ Φ o Φ (Ω o Ai xr cm>> 1 a: a X iM «—4 rt i — l 1 | | OP i — 1 1-1 φ rd Cb> 1 O 0 rd rd r Ai> q> 4> (<W> iP φ C cq> 4>,>, H 2 'Φ q CH q <up V * Φ Φ q q d q φ ř m m m m m m bi bi bi bi bi bi bi bi bi bi bi bi bi bi bi bi bi bi bi bi bi bi bi C> 1 Ψί> N b • H i C> 1 rd Ss 3> iAi SdP> OP 0 rS § 6 Ό Q) Ό Ό> u>. P rd P 1 P -4 Φ P 0 3 3 1 SX 'C C J 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 Φ Φ Φ Φ Φ Φ Φ 1 1 1 1 1 1 1 p • d 0 0 • d Ϊ ní ní 05 O O 05 1 1 05 05 05 05 05 τ τ τ 0,0 0,0 0,0 0,0 0,0 0,0 0,0 , 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 ..

To a three-necked flask of 1 dm @ 2, equipped with a thermometer, stirrer, and condenser, condensate the distilled low-boiling portions, tempered with an oil bath, rinse 500 g of the I. fraction of the phenol pitch specified in Example 1, and add 100 g of active ingredient while stirring at 150 ° C. The bleaching earth is also specified in Example 1. Water is then continuously distilled from the three-necked flask and the granulated clay in a total amount of 9.5 g is lowered for 5 h. After 5 h, the reaction product is cooled, filtered, the separated bleaching clay is carefully used for arylalkylation and crude the reaction product is analyzed and separated by rectification.

The crude reaction product consists (in% by weight) of 45.9 acetone, 1,5-o-cumylphenol, 38,8p-cumylphenol, 3,5 phenol and 7.5 dimers of alpha-methylstyrene. Phenol is recirculated after separation, the dimers of alpha-methylstyrene are either recirculated or used as a fuel component and the acetophenone is isolated as pure. Also pure p-cumylphenol is isolated, optionally together with o-cumylphenol or with admixtures of acetophenone and dimers of alpha-methylstyrene. Example 3

Rectification of the distillation residue from phenol production by "cumene-so-called phenolic salt" is rectified under reduced pressure (2.67 kPa) on a 3-theoretical efficiency column and a 2: 1 reflux ratio to give I. fraction boiling 92.5 to 95 ° C / 2.67 kPa of this composition (in% by weight): acetophenone = 52.9, dimethylphenylcarbinol = 24.3, phenol - 20.7, alpha-methylstyrene - 1.7, dimers of alpha-methylstyrene -0.3 o-cumylphenol / 0.05 and p-cumylphenol / 0.05 This I fraction was weighed at 500 g into a three-necked flask, as specified in Example 2, heated to 130 ° C with stirring and 26 ml added. g of the active bleaching clay specified in Example 1. Arylalkylation takes place over 3.5 while distilling off 15.5 g of the low-boiling fraction (water and alpha-methylstyrene) .The arylalkylate after separation of the catalyst has the composition (% by weight): acetophenone = 52.8, dimethylphenylcarbinol = 0.0, phenol = 4.2, alpha-methylstyrene = 0.1, dimers of alpha-methylstyrene = 4.5 o-cumylphenol = 0.5 and p-cumylphenol = 37.3 Conversion of methylphenylcarbinol = 100% and selectivity of conversion of dimethylphenylcarbinol to p-cumylphenol = 91.4%; selectivity of phenol to p-cumylphenol conversion = 100%. 4

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.