CS245895B1 - Method of arylalkylation of phenol - Google Patents

Abstract

The increase in the selectivity of the arylalkylation of phenol with α-methylstyrene dimers as well as α-methylstyrene compared to known processes by 20 to 30% to cumylphenols is achieved by suppressing the simultaneous irreversible isomerization of unsaturated α-methylstyrene dimers to saturated ones (1,1,3-trimethyl-3-phenylindane). The tryalkylation is carried out under the catalytic effect of an arylalkylation or alkylation catalyst at 60 to 240 °C so that α-methylstyrene dimers or α-methylstyrene are semi-continuously or continuously added to an excess of phenol in the presence of a catalyst (activated clay, polyphosphorates, zeolites), or a reaction mixture with a mol. ratio of olefinically unsaturated α-methylstyrene dimers:phenol = 1:2 to 10. Unconverted phenol and optionally α-methylstyrene dimers are separated and recycled, preferably after separation of at least 30% of the 1,1,3-trimethyl-3-phenylindane present.

Description

245835

BACKGROUND OF THE INVENTION The present invention relates to a method for increasing the selectivity of arylalkylation of phenolipiphylene styrene and / or α-methylstyrene to orcylphenylphenol, and in particular p-kuipylphenol to provide simultaneous isoipetization of unsaturated dimers of .alpha.-methylstyrene. unlike the unsaturated ones, under the arylalkylation conditions, the arylalkylating intermediate phenol is not a precursor of the intermediate α-methylstyrene.

It is known to obtain o-cumylphenol and p-cumylphenol from so-called phenolic spherical distillation (U.S. Pat. No. 2,769,844; V. Brit. Pat. No. 1,235,415; Romanian Pat. No. 57,169) by distillation of film-based evaporators (MS). , the author's certificate 195 254), by crystallization and, in particular, by extralctive crystallization of the n-alkanes C6 to C12 (Dutch Patent 722,524; CA 68, 95,512). However, these raw materials are considerably limited. Therefore, the importance of arylalkylation of phenol or alkylphenol with α-methylsyrene under the catalytic action of Lewis and bromobenzoic acids, such as trihydroxyphosphoric acid and zeolites [Kurashev, is of increasing importance. and others: Nefteehmija 8,842 (1969) 7, 507 (1977)]; U.S. Pat. 2,247,402; polish pat. In this connection, α-methylstyrene led other prodrugs, such as phenol, acetophenone and cumene, by thermocatalytic decomposition of phenol resins on aluminosilicates, most zeolites (automotive certification USSR 583 996; U.S. Pat. No. 2,217,175; Nos. 4,339,605 and 4,358,618; U.S. Pat. Nos. 118,409 and 121,796; V. Brit.

Such production of α-methylstyrene is relatively energy-intensive and does not allow for other technically important components of phenolic compounds to be obtained. In addition, the arylalkylation of phenol by α-methylstyrene by known processes does not allow high selectivity and yield of phenyl phenol. This is because, on the active arylalkylation catalysts, the dimerization of the α-methylstyrene unsaturated dimers, which is also selectively isomerized to the saturated dimers, is also effected by the catalytic catalysts, in particular 1,1,3-tri-methyl-3- phenylindane, the formation of which is practically irreversible.

It is also of interest to disclose a method of arylalkylating phenol to cumylphenols such as dimethylphenylcarbolol and dimers of α-methylstyrene. However, in the case of the use of α-methylstyrene dimers, the low conversion of α-methylstyrene dimers, or low cumylphenium yields, is typically below 65%. Similarly, even with the arylalkylation of dimethylphenylcarbinol, the fact that its own arylalkylating agent intermediates it by dehydration to form α-methylstyrene results in a markedly higher selectivity than in the use of pure-produced pure α-methylstyrene. however, the method of the invention.

Increase Method. the selectivity of arylalkylaphenol by α-methylstyrene and / or α-methylstyrene dimers to cumylphenols by suppressing the ultimate isomerization of unsaturated α-methylstyrene dimers to saturated, such as 1,1,3-trimethyl-3-phenylindane, under the catalytic action of arylalkylation and / or alkali The catalyst is carried out in such a way that the dimers of [alpha] -methylsyrene and / or [alpha] -ethylstyrene are added continually or continuously to the excess of phenol in the presence of a catalyst and / or continuously and / or a semi-continually contacting catalyst with a reaction molar memory of an unsaturated dimer of α-methylstyrene: phenol-1: 2 to 10, wherein the nonconverted phenol and optionally unconverted α-mlylstyrene diameters are separated, in the case of dimers of α-methylstyrene mainly after isolation of at least 30% of the present 1,3,3-trimethyl-3-phenylindane. An advantage of this invention is the high yields of cumylpheniums and the possibility of utilizing for the arylalkylation of dimers of " methylstyrene " from so-called phenolic mixtures with the addition of other compounds such as o-cumyl phenol, phenol, α-methylstyrene and acetophenene. Last but not least, it is possible to utilize the pareelocration of unsaturated dimers of .alpha.-methylstyrene and to suppress the formation of virtually unreactive 1,1,3-trimethyl-3-phenylindane. In the case of the use of α-methylstyrene, the acaryl alkylating agent can be obtained by comparison with, or even greater than, that of dimethylphenylcarbinol. α-Methylstyrene, under the catalytic effect of strong acids, dimerizes mainly by the equilibrium reaction to unsaturated dimers of α-methyl-styrene, in particular 2,4-diphenyl-4-methyl-1-pentene (I) and trans- and cis-2 4-diphenyl-2-pentene (II.). (i) 243895 5

(ιι) (III) with unsaturated dimers of I and II. with the catalytic effect of the acid catalyst of elevated temperature, both decompose to --methylstyrene and, on the other hand, are skeletally, almost irreversibly isomerized to 1,1,3-trimethyl-3-phenylindane (III.).

According to the present invention, the arylalkylation conditions of phenoludimers of α-methylstyrene as well as of α-methylstyrene to cumylphenols are formed in order to essentially undergo only the decomposition of unsaturated dimers and aarylalkylation and fail to undergo skeletal isomerization of unsaturated dimer-methylstyrene to practically unreactive 1,1,3-trimethyl-3-phenylindane.

Arylalkylation and alkylation catalysts also typically catalyze the decomposition of dimer-methylstyrene, especially unsaturated dimers, into α-methylstyrene, but also skeletal isomerization.

The arylalkylation catalysts are essentially identical to the alkylation catalysts. Most preferred are trihydrogenphosphoric acid, phosphorus pentoxide, polyphosphoric acids either as such but most often on carriers, i.e. as beterogenic catalysts. Then alumina, activated by aluminosilicates, especially synthetic but also naturally zeolites, also activated bentonites, especially so called. active or bleaching earth, especially bleaching clay with polyphosphates, then bleaching earth with phosphorus pentoxide. Sulfuric acid is less suitable as a low molecular weight organic sulfocyanate. Suitable catalysts are also cationic resins, especially sulfonated polymers such as sulfonated styrene-divinylbosene co-polymer resin, sulfonated polystyrene, sulfonated polypropylene, sulfonated condensed phenylene ketone resins, sulfonated polyphenylene oxide resins, and the like.

The catalysts of the present invention are mainly applied as dispersed in arylalkylation medium in bed or bed. Less suitable but also homogeneous catalysts are also useful.

In order to avoid virtually non-viral skeletal isomerization of unsaturated dimer-methylstyrene, the aryl-alkylation is to be a constant excess of phenol. It is advantageous to dispense α-methylstyrene dimers into the present phenol with the catalyst. In the case of semi-continuous or continuous arylalkylation on the catalyst in the bed, a high molar excess of phenol is also required in the feed of the raw materials, the more that 2 moles of α-methylstyrene float over 1 mole of unsaturated dimers.

From the crude product, the unconverted phenol is mainly separated by distillation, rectification, especially under reduced pressure; less suitable, but extraction with most water is also applicable. Generally, non-terminated α-methylstyrene dimers are also separated. In the case of their separation, in particular by distillation but not by purification mainly under reduced pressure, at least a portion of the 1,1,3-trimethyl-3-phenylindane is desirably separated therefrom, since the isomer does not substantially give it in a removable amount in recirculation. the intermediate α-methylstyrene and thus practically do not participate in the alkylation reaction. Further details and other advantages of the invention are evident from the examples. 245895 Example 1

Rectification of the so-called phenolic spheres with a pressure of 2.67, kPa on a coil with a rate of 20 degrees and a reflux ratio of 4: 1 gives a fraction of α-methyl-styrene dimers consisting of four isomers, a part of o-cumylphenol and poid 0, 1 ° p-cumyl phenol. Of the isomers in the highest concentration is 2,4-diphenyl-4-methyl-1-pentene, to more active co-concentration is toans-2,4-diphenyl-4-methyl-2-pentene, in negligible concentration cis -2,4-diphenyl-4-yl-2-pentene and other unidentified hydrocarbons, but in a remarkable concentration, the isomer of α-methylstyrene dimer is saturated with 1,1,3-trimethyil-3-phenylindan. To this fraction is added pure phenol to a weight ratio of phenol: dimer of α-methylstyrene = 1: 1. The thus obtained mixture has a composition (in% by weight): phenol = 51.01, α-methylstyirene = 0.12, 2,4-diphenyl-4-methyl-1-pentene with trans- and cis-2,4 -diphenyl-4-methyl-2-pentenoic = 40,65,1,1,3-trimethyl-3-phenylindan = 0.03, unidentified dimers of α-methyl-styrene = 0.12, o-cumylphenol = 8 , 21 ap-cumylphenol below 0.02. From this blend, 200 g arylalkylation samples of phenol at different temperatures are collected in triple neck flasks equipped with a stirrer, heat radiator and a reflux condenser immersed in a tempered oil bath. When the desired temperature is reached, 1 wt. calculated on the cell mixture as an arylactilizing catalyst active clay, prepared by activating bentanite composition (in% / wt): SiO 2 - 54.7; A12, O3 = 18.6,

MgO ~ 3.9,

CaO = 2.2,

Fe2, O3 - 2.6, K9O = 0.2,

TiO2 = 0.2,

Na2O = 0.05%, straita. annealing = 17.4% (powder, sieve residue 0 k 0.2 m / m); bulk density = 491 kg.m ~ 3).

The temperature is. The reaction time is 2 h. The results of arylalkylation of phenol depending on the in situ temperature produced by α-methylstyrene decomposition of the olefinically unsaturated α-methylstyrene dimer (the arylalkylation catalyst also catalyses the decomposition of olefins). the unsaturated dimers of α-methylstyrene na-methylstyrene, also the isomerization of o-cumylphenol to p-cumylphenol) are included in Table 1. 1 shows that in the range of 110-150 ° C, the conversion of phenol from 17.7 up to 36.2% and dimer-methylstyrene is 80.6-97.6%, but selectivity of arylalkylation of dimers of α-methylstyrene p-cumene. lphenol 48.0 to 55.3% and the yield of c-cumylphenol from dimers of α-methylstyrene lencd 38.6 to 54%. The remainder of the selectivity of α-methylstyrene dimers up to 100% is the selectivity of olefinically unsaturated dimers to saturated 1,1,3-triroethyl-3-phenylindane, which in practice does not substantially alkylate phenol cumylphenols. In some cases, the selectivity of phenol to p-cumylphenol is greater than 100% relative to the isomerization of p-cumylphenol from the starting material.

Similar results, with only greater reaction rates, are obtained a) when applying an acocatalyst of bleaching earth with polyphosphoric acid. Example 2

In contrast to Example 1 s, the fraction of the predominant α-methylstyrene dimer is continuously fed into the phenol with the catalyst (active clay, specified in Example 1) heated to the desired reaction temperature with stirring. The fraction of α-methylstyrene dimers from the so-called phenol pitch is continuously fed into the heated phenol / active clay mixture (2% by weight of the complete reaction mixture calculated after addition of all α-methylstyrene dimers) over a period of 1-3 hours. % m / m): 2,4-diphenyl-4-methyl-1-pentene = 56.1, trans-2,4-diphenyl-4-methyl-2-pentene = = 11.4.1.1, 3-Trimethyl-3-phenylindane - 1.8, o-cumylphenol = 16.5 ap-cumylphenol = 8.6.

The results obtained are shown in Table 2. Compared to the results in Example 1 (Table 1), we can see a markedly lower, barely semi-saturated formation of the α-methylenetyrene dimers of 1,1,3-trimethyl-3-phenylindane and ab -solutely higher selectivity of β-cumylphenol unsaturated α-methylstyrene dimers by 30 to 45%, which amounts to 77 to 87.7% and, accordingly, higher yields of p-cumylphenoil, calculated on unsaturated dimers of α-methylstyrene. 245335

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100 cm @ 3 of a phosphate catalyst (polyphosphoric acid on silica; H3PO4) can be added to a flow-through tube reactor of 80 cm in length with an inside diameter of 3 cm-o, rubbed with a thermometer well and placed in a tempered jacket. = 20% by weight, R2O3 = 3.2%, Na2O = 0.05% by weight, SiO2 = remainder) val-shaped shape (diameter 3 mm and height 8mimimeters), bulk density 0.83 kg .. dm '3.

A reaction temperature of 16.8 m &lt; 3 > is required for this catalyst after preheating. mkat-3. h-1 dispenses the reaction mixtures prepared by mixing the α-methylstyrene dimer fraction with the phenol phenol / α-methylstyrene dimer ratio = 1.54. The results of the analysis of the raw material as well as the crude reacted pro-reactants of the arylalkylation depending on the temperature are shown in Table 3. Example 4 by ficinine in Example 3 is continuously sprayed at 150 + 2 ° C, further 160 ++ 2 ° C and 170 + 2 ° C a mixture of phenol and α-methylstyrene fractionedimers in molar ratio phenol / dimer α-methylstyrene = 3.4 and a nitrogen flow of 16.8 m 3. mkať'3 h_1.

The composition of the phenol mixture with the fraction of dimeric raw material for the production of p-cumylphenol jetakite (in% by weight): phenol = 51,4, o-cumylphenol - 8,8, p-cumylphenol = 0,02, 2,4-diphenyl-4-methyl- 1-pentene = 32,1, 2,4-diphenyl-4-methyl-2-pentene-5,0, unidentified dimers of? -methyl-styrene = 0.7?, 1,3-trimethyl-3-phenylindane = 0, 5.

The results of the preparation of p-cumylphenol, depending on the catalyst load, of the phenol-dimer-α-methylstyrene dimer and the temperature are shown in Table 4.

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Weight ratio phenol: fraction of dimers of α-methylstyrene - 1: 1; reaction time2 h. From the results of arylaikylation of phenol with α-methylstyrene dimer on bleaching earth in the presence of rude concentrations of 1,1,3-trimethyl-3-phenylindan from 0.2 to 41% by weight, calculated on arylalkylation mixture without It is evident from the catalyst that the substance at lower concentrations does not have a significant influence on the arylaikylation at a concentration of 14.2% by weight. its content has already risen in the product and the yield of p-cumylphenol has decreased.

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Claims (2)

SUBJECT A process for arylalkylating phenol with α-methylstyrene and / or α-methylstyrene dimers to cumylphenols by suppressing the simultaneous isomerization of unsaturated α-methylstyrene dimers to saturated, such as 1,1,3-trimethyl-3-phenylindane, with a catalytic effect An arylalkylation and / or -alkylation catalyst at a temperature of 60 to 240 ° C, characterized in that the dimers of α-methylstyrene - and / or α-methylstyrene are added semi-continuously or continuously in excess of phenol in the presence of the catalyst and / or The reaction mixture with a mole olefinically unsaturated α-methylstyrene dimer: phenol = 1: 2 to 10 is continuously and / or semi-continuously contacted with the catalyst, wherein the unconverted phenol and optionally the unconverted? The dimers of α-methylstyrene are separated, generally recycled, in the case of α-methylstyrene dimers, after isolation of at least 30% / oz of 1,1,3-trimethyl-3-phenylindane present. 2. Method according to claim 1, characterized in that the dimers of .alpha.-methylstyrene and / or .alpha.-methylstyrene contain in total 1 to 40% by weight. other components such as o-cumylphenol, p-cumylphenol, phenol, α-cetophenone.