CS276819B6 - The process for the preparation of 1,1,3-trimethyl-3-phenylindane - Google Patents

Abstract

The method for producing 1,1,3-trimethyl-3-phenylindane is carried out from a raw material containing at least one of the compounds ^-methyl-styrene, dimethylphenylcarbinol, unsaturated dimers of ε-methyl-styrene and cumylphenols at a temperature of 60 to 360° C (90 to 250° C) on a stationary heterogeneous activated and formed aluminosilicate catalyst. A particularly suitable raw material is the by-products from the production of the so-called cumene phenol and acetone, containing practically all of the above components. The activation of aluminosilicates (bentonites, montmorillonite) is usually carried out before forming into particles of 0.2 to 50 mm either with an aqueous solution of mineral acids (HC1, H2SO4) or with an ammonium salt of mineral acids, from the raw product 1,1,3-trimethyl-3- -phenylindane is isolated.

Description

The invention relates to the production of 1,1,3-trimethyl-3-phenylindan from technically readily available raw materials, on acid heterogeneous bed catalysts, with high activity, the crude product already being catalyst-free and the main and by-products being easily isolated therefrom.

1,1,3-Trimethyl-3-phenylindan is an interesting organic intermediate not only for the synthesis of new biologically active substances, but also low-solids oils, special organic solvents and can itself be a plasticizer of polymethylmethacrylate (organic glass). It can be prepared by dimerization of N-methylstyrene on sulfonated polymers, but especially on aluminosilicate catalysts at a temperature of 50 ₄ to 170 ° C / Akperov NI et al .: Izv. Nauk Az. SSR, ser. phys. - technolmat. Science 1985, 6 (4), p. 97-101; CA 105, 24654d (1986);

Kawakami Yuhsuke and ini: Polym. J. (Tokyo) 13, 859 and 947 (1981);

NSR Patent 2,906,294; U.S. Patent 4,142,998 or on a Co-Mo-Al catalyst at 175-300 ° C. However, ob-methylstyrene is needed, which is obtained by dehydrogenation of cumene, dehydration of dimethylphenylcarbinol or isolation from by-products of the production of phenol and acetone, so-called cumene. In these it is even present in small amounts [Malinowska H. et al.: Chem.Anal. 19, 511 (1974) and 1,1,3-trimethyl-3-phenylindan, which can be isolated from them in an energy-intensive manner.

However, the method of production of 1,1,3-trimethyl-3-phenylindan from unsaturated dimers of methylstytene (Macho V .: Czech author's certificate 245 894) as well as from dimethylphenylcarbinol (Macho V., Jureček li .: Czech author's certificate) is interesting. 248,936), both of which can use broader fractions from the by-products of the production of cumene phenol and acetone using acidic heterogeneous or homogeneous catalysts. In the case of heterogeneous, these are suspended aluminosilicate catalysts or phosphates in the bed, both types (in the case of phosphate of phosphoric acid) to be removed from the crude product before the isolation of 1,1,3-trimethyl-3-phenylindan or at least neutralized. In the case of phosphates, it is also necessary to add trihydrogenphosphoric acid additives to the raw material. Thus, the method of the present invention takes advantage of the two methods and solves the problems.

Process for the production of 1,1,3-trimethyl-3-phenylindan from a feedstock containing at least one compound from oZ-methylstyrene, dimethylphenylcarbinol, unsaturated dimers of n-methylstyrene, 2-cumylphenol, 4-cumylphenol and tricumylphenols, on an acid catalyst at a temperature of 60 to 360 DEG C. is carried out in such a way that the raw material is fed in the gaseous and / or liquid phase to a stationary heterogeneous catalyst formed by acid activation and by forming and / or shaping the aluminosilicate. particle size 0.2 to 50 mm. 1,1,3-Trimethyl-3-phenylindan is isolated from the crude product by distillation, crystallization and recrystallization.

The advantage of the process according to the invention is the high catalytic activity and selectivity of the applied catalysts in the bed, their easy regenerability, while they do not contaminate the crude product and do not need to be isolated. Then lower energy consumption and process-free waste. In one technological step, not only dimerization of α-methylstyrene takes place, followed by isomerization to 1,1,3-trimethyl-3-phenylindane (1,1,3-trimethyl-3-phenylhydrindene;

H-indene-2,3-dihydro-1,1,3-trimethyl-3-phenyl), but also dehydration of dimethylphenylcarbinol by subsequent dimerization and isomerization, isomerization of unsaturated dimers of methylstyrene, thermal-catalytic decomposition of cumylphenols to give phenol * al, l , 3-trimethyl-3-phenylindane. Finally, the formation of valuable cumene from the by-product fractions of the phenol and acetone production is also advantageous, especially if these are fed to the catalyst in the bed at temperatures of 200 to 360 ° C.

The raw material is mainly ob-methylstyrene itself, but mainly mixtures of unsaturated dimers of α-methylstyrene, such as 2,4-diphenyl-4-methyl-1-pentene, cis- and trans-2,4-diphenyl-4-methyl-2-pentenes, hereinafter mixtures thereof with -methylstyrene, optionally also dimethylphenylcarbinol as well as cumylphenols. Then mixtures of α-methylstyrene with cumylphenols, most often 2-cumylphenol and acetophenone, then dimethylphenylcarbinol with acetophenone, cumylphenols and dimers of α-methylstyrene and the like, most often in the form of fractions! from by-products of phenol and acetone production so-called cumene method, usually isolated from the so-called phenolic resins. The raw material can also be phenolic resins without pre-treatment.

Of the temperatures in the range of 60 to 360 ° C for the selectivity mainly to 1,1,3-trimethyl-3-phenylindane, the range of 120 to 240 ° C is most suitable. With higher temperature, the selectivity to 1,1,3-trimethyl-3-phenylindane decreases and increases to cumene.

The acidic heterogeneous catalyst is formed or shaped by extrusion, resp. extrusion, pressing, etc. Acid activation of the starting synthetic aluminosilicate, but natural aluminosilicate is particularly suitable, is carried out with dilute mineral acid, such as dilute acid, such as dilute hydrochloric acid, dilute sulfuric acid, dilute nitric acid or trihydrogenphosphoric acid or aqueous ammonium salts, ammonium nitrate ammonium sulphate and the like

Of the aluminosilicates, bentonites as well as montmorillonite itself are particularly suitable.

Thus, from a mineralogical point of view, suitable natural aluminosilicates - bentonites usually consist of 70 to 85% of montmorillonite, 13 to 27% of a glassy phase and 2 to 5% of quartz. From a chemical point of view, they represent 60 to 80% by weight of silica, 9 to 22% by weight of alumina, 0.5 to 3% by weight of iron oxide, 1 to 4% of magnesium oxide, 0.1 to 2% by weight of calcium oxide , 0.1 to 1.5% by weight of potassium oxide and sodium oxide.

According to the invention, the acidic activation of the stationary catalyst can also be carried out directly in the catalyst bed, usually after a decrease in activity and removal of organic deposits, in particular by firing. Such acidic activation can be carried out not only by the action of aqueous solutions of mineral acids but also by the action of halogens and especially hydrogen halides, especially hydrogen chloride and hydrogen fluoride,

The process according to the invention can be carried out mainly continuously, but also semi-continuously and intermittently.

Additional implementation data apparent from the examples.

as well as other data are

Example 1

By rectification of the by-product from the production of phenol and acetone, the so-called by the cumene method of phenolic resins, a fraction of t is obtained on a column with an efficiency of 20 theoretical degrees and a reflux ratio of 5: 1, at a pressure of 2.67 kPa. in. 160-190 ° C / 2.67 kPa of the following composition (in% by weight): phenol = 0.5; 1,1,3-trimethyl-3-phenylindane = 2.2; 2,4-diphenyl-4-methyl-1-pentene = 59.6; trans-2,4-diphenyl-4-methyl-2-pentene = 12.1; 2-cumylphenol = 17.7 and 4-cumylphenol = 5.9. This mixture is mixed with aqueous sodium hydroxide solution and at a concentration of 40% by weight, in an amount corresponding to the need to convert phenol, 2- and 4-cumylphenol to phenolate and sodium cumylphenolates at 100 DEG C. and after distilling off water under reduced pressure (2.67 kPa ) and a temperature of 170-185 ° C, a mixture of mainly unsaturated β-methylstyrene dimers of the following composition is obtained (in% by weight): 1,1,3-trimethyl-3-phenylindan = 1,2; 2,4-diphenyl-4-methyl-1-pentene = 79.2; trans-2,4-diphenyl-4-methyl-2-pentene = 14.9; 2-cumylphenol = 0.2; 4-cumylphenol <0.01. The distillation residue consists of sodium phenolate and sodium cumylphenolates.

This mixture of unsaturated dimers of α-methylstyrene, at a concentration of 94.1% by weight, is fed in a stream of nitrogen to an acidic aluminosilicate heterogeneous catalyst in a bed - in the form of extruded rollers measuring 2.5 x 5 to 6 mm, in an amount of 0.2 cm ³ . cm ^ au · ^41-1 at a temperature of 150 + 2 ° C.

Acid heterogeneous aluminosilicate catalyst prepared from concretite, consisting of 75 montmorillonite, 22.3 glassy phase and 2.7% quartz. This bentonite had a loss on ignition (annealing) of 8% by weight, and its analysis is as follows (in% by weight): SiO ₂ = 69.55; A1 ₂ O ₃ = 16.89; Fe ₂ O ₃ = 1.95; TiO ₂ = 0.19; MgO = 2.85; CaO = 0.20; Na ₂ 0 = 0.15; K ₂ 0 = 0.22.

The bentonite suspension in sand-free water by hydrodynamic separation is activated in three steps by extraction with hydrochloric acid with a total concentration of 2 M at 97 ° C for 8 h. After cooling and filtering the suspension and washing with deminerilized water, the wet filter cake of the suspension is compacted by means of an extruder. The extrudates obtained are dried at a temperature of 60 + 5 ° C and dried at a temperature of 105 + 5 ° C to a constant moisture content of 1 to 2% of water. The rolls of the extrudate thus produced are an efficient acidic heterogeneous catalyst.

From the reactor containing said acidic heterogeneous catalyst, vapors and liquid are passed through a condenser to a separator into the crude product. The crude product has the following composition (in% by weight): 1,1,3-trimethyl-3-phenylindane = 94.5; 2,4-diphenyl-4-methyl-1-pentene = 1,5, trans-2,4-diphenyl-4-methyl-2-pentene = 1,1.The residue consists of unidentified substances, in particular other dimers and trimers o / - methylstyrene. After distilling off under reduced pressure (2.67 kPa) with impurities of unsaturated dimers of .alpha.-methylstyrene, 1,1,3-trimethyl-3-phenylindane is obtained by recrystallization twice by purity from 99.5 to 99.9%.

Example 2

The procedure is similar to Example 1, except that the conversion temperature of the dimethylstyrene dimers on said acid-shaped aluminosilicate is 200 + 3 ° C. The crude product obtained has the following composition (in% by weight): 1,1,3-trimethyl-3-phenylindane = 96.1%; 2,4-diphenyl-4-methyl-1-pentene = 0.1; trans-2,4-diphenyl-4-methyl-2-pentene = 0.06; cumene = 2.1%. Distillation of the more volatile fractions and recrystallization twice from toluene gave 1,1,3-trimethyl-3-phenylindane of 99.8% purity.

Example 3 '

In the heterogeneous acidic aluminosilicate catalyst is characterized in Example 1, temperature-controlled at 230 + 5 ° C was injected in an amount of 0.25 cm ^ _at. .h ¹ fraction obtained from "phenolic resins", having the following composition (in% by mass): water = 0,1; dimethylphenylcarbinol = 38.7; acetophenone = 55.6; oL · -methylstyrene = 0.4; 2,4-diphenyl-4-methyl-1-pentene = 0.5; 2,4-diphenyl-4-methyl-2-pentenes = 0.5; 1,1,3-trimethyl-3-phenylindan = 0.3; 2-cumylphenol = 2.8 and phenol = 0.8. The conversion of dimethylphenylcarbinol is complete. The composition of the crude reaction product is as follows (in% by weight): 1,1,3-trimethyl-3-phenylindane = 37.3; oC-methylstyrene <0.02; phenol = 0.5; 2,4-diphenyl-4-methyl-1-pentene = 0.3; 2,4-diphenyl-4-methyl-2-pentene = 1.4; cumene = 7.2; acetophenone = 46.2; unidentified components = 7.1. Distillation of the low-boiling fractions and recrystallization three times from benzene gave 1,1,3-trimethyl-3-phenylindane of 99.2% purity.

Example 4 ·

The procedure is similar to Example 1, except that oi is used instead of the dimer fraction. -methylstyrene with a concentration of 94% by weight, with additives of 0.8% by weight. 1,1,3-trimethyl-3-phenylindane, 0.4% by weight, acetone, 1.8% by weight, mixtures of 2- and 4-cumylphenols, 1.4% by weight. 2,4-diphenyl-4-methyl-1-pentene, the remainder being unidentified components. This is passed to the heterogeneous acidic aluminosilicate catalyst at 0.2 cm ³ .cm'.h ^"1 in a nitrogen stream at a rate of 18 cm ³ _{of n} cm h. The conversion of 1-methylstyrene is 99% and the selectivity to 1,1,3-trimethyl-3-phenylindane is 85.9%. Selectivity to 2,4-diphenyl-4-methyl-1-pentene = 8.4% and trans-2,4-diphenyl-4-methyl-2-pentene = 5.7%.

Under otherwise similar conditions, but at a temperature of 150 + 3 ° C, the conversion of oC-methylstyrene is 99.8% selectivity to 1,1,3-trimethyl-3-phenylindane 94.0% 2,4-diphenyl-4-methyl- 1-pentene 3.6% and trans-2,4-diphenyl-4-methyl-2-pentene 2.4%.

Example 5

The procedure is similar to Example 1, except that the acid activation of the bentonite instead of the hydrochloric acid extraction is made with a 1 M aqueous sulfuric acid solution at 97 DEG C. for 10 hours.

The crude product has this composition (in% by weight);

1,1,3-trimethyl-3-phenylindane = 94.1; 2,4-diphenyl-4-methyl-1-pentene = 1.5; trans-2,4-diphenyl-4-methyl-2-pentene = 1.4.

Example 6

The procedure is similar to Example 1, but the acid activation of the bentonite is done with an aqueous solution of ammonium chloride with a concentration of 2.5 M.

A product of similar composition as in Example 5 is obtained.

Example 7 ·

In addition, phenol is added to the fraction of predominantly unsaturated dimers of α-methylstyrene obtained by distillation of phenolic resins, so that the molar ratio of phenol-β dimers of methylstyrene is 3.5: 1. The composition of the raw material is then (in% by weight): cumene = 0.3; α-methylstyrene = 1.2; acetophenone = 2.8; phenol = 53.2; 1,1,3-trimethyl-3-phenylindan = 1.9; 2,4-diphenyl-4-methyl-1-pentene = 13.0; trans-2,4-diphenyl-4-methyl-2-pentene = 4.2; 2-cumyl-phenol = 6.6; 4-cumylphenol = 14.2.

a heterogeneous catalyst is used in the stationary bed of the reactor, the preparation and characteristics of which are given in Example 1.

To the activated aluminosilicate molded catalyst is the raw material it zaúaž ^ gg ^ _at 0.2 h ^-1, while the nitrogen flow rate of 12 cm ³ .cmjA ^. .h ¹ shall carry out the reaction komponentov.Výsledky achieved conversion of the unsaturated dimers j and C methylstyrene and phenol, and the selectivity of converted to 1,1,3-trimethyl-3-phenylindan kumylfenoly a function of temperature are summarized in the Table 1 below.

Table 1

Temperature (° C) Load. catalytic converter /^*^kat.’^ / Conversion (%) Selectivity (%): dimers of α-methylstyrene phenol unsaturated. methylstyrene dimer ^ to the 1,1,3-trine 1-3- _f phenylindan dimers of oC-methylstyrene to cumylphenols phenol to cumylphenols 91 0.2 16.6 7.1 38.9 100 100 100 0.2 34.6 11.3 39.3 100 100 120 0.2 40.8 10.7 45.7 93.8 100 142 0.2 24.2 8.8 57.1 100 87.7 155 ~ 0.2 · 12.8 0.0 67.0 10.1

Claims (4)

PATENT CLAIMS A process for the preparation of 1,1,3-trimethyl-3-phenylindan from a feedstock containing at least one compound from o-methylstyrene, dimethylphenylcarbinol, unsaturated dimers of .epsilon.-methylstyrene, 2-coumylphenol, 4-cumylphenol and tricumylphenols, on an acid catalyst at 60 to 360 ° C, characterized in that the feedstock is fed in the gaseous and / or liquid phase to a stationary heterogeneous catalyst formed by acid activation and formation and / or shaping of an aluminosilicate to a particle size of 0 2 mm to 50 mm, the crude product being 1,1,3-Trimethyl-3-phenylindan is isolated, for example, by distillation, crystallization and recrystallization. 2. The process according to item 1, characterized in that the heterogeneous catalyst is formed by acid activation and molding and / or shaping of a natural aluminosilicate, preferably montmorillonite and / or bentonite, acid activation, preferably mineral acid, followed by molding and / or shaping and optionally heat treatment to contain 60 to 80% by weight of silica, 9 to 22% by weight of alumina, 0.5 to 3% by weight of iron oxide, 1 to 4% by weight of magnesium oxide, 0.1 up to 2% by weight of calcium oxide, 0.1 to 1.5% by weight of potassium oxide and sodium oxide and the remainder up to 100% is water and filler. . 3. The process according to items 1 and 2, characterized in that the acid activation is carried out with dilute mineral acid, preferably hydrochloric acid and / or a dilute aqueous solution of ammonium salt of mineral acid, preferably ammonium nitrate or ammonium sulphate. 4. The process according to items 1 and 2, characterized in that the raw material is a by-product of a phenolic resin from the production of phenol and acetone by a so-called cumene process, preferably a fraction obtained from phenolic resins containing methylstyrene, unsaturated dimers -methylstyrene, dimethylphenylcarbinol, dimethylphenylcarbinol, and optionally phenol and acetophenone. End of document