CS251952B1 - Process for preparing an arylalkylating agent - Google Patents

Abstract

The preparation of an arylalkylating agent containing methylphenylcarbinol in an amount of 40 to 100 % and usually other components such as styrene, ethylbenzene, acetophenone, propylene glycol, styrene oligomers, C6 to C11 hydrocarbons is carried out by rectifying the methylphenylcarbinol and/or acetophenone fraction from the crude products of epoxidation of alkenes with ethylbenzene hydroperoxide, in which acetophenone is usually further selectively hydrogenated to methylphenylcarbinol. The hydrogenation of the fraction is carried out in the liquid or vapor phase at a temperature of 70 to 210 °C on a catalyst containing at least one metal or compound of metals of groups I.b, II.b, VI.b and VIII of the periodic system.

Description

251952

BACKGROUND OF THE INVENTION The present invention relates to the preparation or recovery of an arylalkylating agent containing homethylphenylcarbinol and optionally other components particularly suitable for the production of 1-phenyl-1 (2-hydroxyphenyl) ethane, 1-phenyl-1- (4-hydroxyphenyl) ethane and optionally also 1-phenoxy-1-phenylethane as a mixture of benzylmethylphenol and di- (benzylmethyl) phenol isomers as a starting material of the by-product from the epoxidation of alkenes with ethylbenzene hydroperoxide.

Arylalkylation of phenol by styrene has been known for a long time under the catalytic action of aluminum chloride, hydrogen chloride, trihydrogenphosphoric acid, polyphosphoric acid and oxalic acid [U.S. Pat. 2,247,402 Chem. Abstr. 35, 62, 676 [1941]; Kurashev M. V. and others: Neftechimija 9, 428 (1969); Pau-kin J.M. and others: Neftechimija 9, 842 (1969), Kumok S. S., et al. Vsesojuz. Chim. Obšč.17, 460 (1972)], as well as the detailed result of the formation of individual components under the catalytic effect of p-toluenesulfonic acid [Lukasik L. et al., Przem. Chemicz. 26, 10, 530 (1977)].

However, it requires relatively pure starting monomers - styrene and phenol. It is well known in the prior art that in the so-called phenolic salts, mainly in the anterior fraction, there are mainly dimethylphenylcarbinol and acetophenone, as well as byproducts of epoxidation of alkenes, with organic hydroperoxides, especially ethylbenzene hydroperoxide - methylphenylcarbinol and acetophenone. which are technically and economically more valuable. Such possibilities for the technical treatment and evaluation of the main presence of acetophenone, methylphenylcarbinol and phenol, without the more demanding separation of the side components, are possible according to the invention.

A process for the preparation of an arylalkylating agent containing methylphenylcarbinol of 40 to 100%, furthermore styrene binders of 0 to 50% and 0 to 30% of other components such as ethylbenzene, acetophenone, propylene glycol, styrene oligomers and hydrocarbons to C 1 -C 8, is carried out by crosslinking the epoxidation products of the alkene or alkenes with ethylbenzene hydroperoxide, preferably from the epoxidation product of propene by ethylbenzene hydroperoxide to methyloxirane, by rectifying the fraction containing camphenylphenylcarbinol and / or acetophenone and / or further selectively hydrogenating it in liquid and / or or in a vapor phase at a temperature of 70 to 210 ° C on a hydrogenation catalyst or catalysts containing at least one metal and / or a metal compound Ib, ILb, VI. b and VIII. groups of the periodic system, preferred honey and silver on carriers and ske-flight honey. The advantage of the production method according to this invention is the raw material availability, while the other economically and economically valuable products from the epoxidation of alkali alkali metal oxides, especially propylene to propylene oxide by epoxidation with ethylbenzene hydroperoxide. Also advantageous is the fact that it is not necessary to isolate pure acetophenone or methylphenylcarbinol and other components from the starting material, nor to separate the phenol ethylbenzene, propylene glycol and the like, prior to dosing for selective hydrogenation. In a non-final series of methods, it complements a set of procedures by which it is possible to extend the number of technically available arylalkylation agents and the use of by-products from peemicemic manufacturing.

The selective hydrogenation of acetophenone with methylphenylcarbinol can be carried out at a pressure of 0.09 to 45 MPa, which can be carried out not only in liquid but also in vapor phase, e.g. on a scrubbed catalyst. In addition to the aceto-phenone, methylphenylcarbinol, ethylbenzene, styrene, dimethylphenylcarbinol, propylene glycol, other components may be present in the feedstock to be hydrogenated, but at least dimethylphenylcarboline and alpha-methylstyrene are preferably removed therefrom, especially if the other production goal is In the course of hydrogenation, dimethylphenylcarbinol can be partially dehydrogenated and optionally dehydrated or hydrogenolyzed to naisopropylbenzene. Due to its high selectivity, it is suitable to carry out the hydrogenation at higher temperatures, preferably in the range 100-150 ° C. At a temperature below 70 ° C, the hydrogenation clarity is already very low and at temperatures above 210 ° C with respect to the bonding of the hydroxyl group with the secondary carbon of other influences, the chemical equilibrium is particularly low. to hydrogen displaced predominantly to the dehydrogenation side and more easily hydrogenation of methylphenylcarbinol occurs when hydrated.

Suitable selective catalysts for the hydrogenation of acetophenone to methyl phenylcarboline are catalysts based on the media and its compounds (Raney honey, skeletal honey, oxides of the media, oxides of the media on carriers, copper-chromium and copper-chromite-calcium, such as copper-chromite-barium) catalysts), furthermore silver, less suitable are zinc and chromium (poorly effective).

However, combined, mixed and mixed catalysts based on Cu-Zn, Cu-Zn-Cr, Cu-Zn-Fe and the like, whether in the form of alloys, oxides, metals or oxides on carriers, are suitable.

Metal-based catalysts VIII. the group can only be applied to the lowest temperature range, possibly after preliminary partial digestion, e.g., sulfur compounds. Metal Based Catalysts VIII. although the groups possess the most potent hydrogenation catalysts, but due to their high efficiency in the C = C double bonds, they are less suitable because they catalyze the hydrogenation of the aromatic ring. C-H and C-C bonds are completely hydrogenolyzed at higher temperatures. The hydrogenation catalysts are either in the bed reactor, in the flare or dispersed in the hydrogenation medium.

Hydrogenation can also be accomplished by the presence of solvents, and other components of aceto-phenone fractions can also fulfill this function. In the case of the use of selective catalysts during the hydrogenation of the acetophenone, without any alteration, propylene glycol, phenol, optionally styrene, is present, so that the hydrogenate, without the need for additional phenol, can be directly led to arylalkylation.

The process of the present invention may be carried out continuously, semi-continuously or discontinuously. Further details of the invention as well as other advantages are apparent from the examples. EXAMPLE 1 From the so-called phenolic pitch, consisting essentially of a distillation residue from the production of phenol and acetone by catalytic decomposition of cumene hydroperoxide, a fraction of the boiling point of 27 DEG to 160 DEG C./6 .7 kPa is distilled off by differential pressure distillation. % 6 wt. phenol has this composition (in% by weight): acetophenone = 36.9; dimethyl phenylcarbinol = 22.4; phenol-20.9; cumylphenols - · 2.6 and alpha-methylstyrene = 0.7.

This multicomponent mixture is conducted in a continuous arylalkylation, carried out on a phosphate catalyst on a carrier medium (beads of 5 millimeters in diameter, containing 22.6 wt% phosphorus and an acid number of 298 mg KOH / g), in nitrogen at 160 ° C. And pulling the catalyst up to 0.4 g. An aryl alkylate of this composition (in% by weight) is obtained: aceto-phenone = 46.2; dimethylphenylcarbinol = 0.4, phenol = 4.6 and cumylphenols = 32. After separation of the cumylphenols via cumylphenates, the sodium distilled acetophenone fraction contains 72% by weight. acetophenone, and the other, and more specifically non-identified, byproducts. This fraction leads to hydrogenation both in the liquid phase and on the scrubbed catalyst or the catalyst. in the steam phase.

Hydrogenation of the acetophenone fraction in the liquid phase is carried out on an oxido-monomerochromite catalyst (Akdinsovatalyst) used in an amount of 10% by weight. at a temperature of 150 ± 3 ° C and a hydrogen pressure of 18 to 15 MPa, using a stainless steel rotary knob provided with heating accessories and temperature regulators. After 4 h, the hydrogenate is obtained with a content of 69% by weight. methylphenylcarbinol and 1.2% acetophenone.

The second portion of the fraction is hydrogenated continuously on a scraped skeletal copper (Raney-med) catalyst of 1-3 mm, at 110 ± 2 ° C, mol. the ratio of acetophenone: hydrogen = 1: 7 and the pressure close to atmospheric, when the catalyst was pulled with an acetophenone fraction of 0.28 g / ml. The conversion of acetophenone reaches 95% and selectivity to methylphenylcarbinol 93%.

The third part of the fraction is hydrogenated under similar conditions as the second part, only the skeletal diluent is used in a silica gel for bulk (bulk density - = 1.080 kg / day 3; CuO = 64.5% by weight; 5% by weight, R2O3 - 0.5% by weight, loss on ignition - 3% by weight) pre-treated reduced in nitrogen hydrogen at 120-180 ° C.

The hydrogenation is carried out at 140 ° C, with the conversion of acetophenone to 65% and selectivity to methylphenylcarbine 95%. Example 2

For the liquid phase hydrogenation, the acetophenone fraction from the so-called phenolic salts is taken after isolating the dimethylphenylcarbinol of this composition (in% by weight): acetophenone = 44, phenol = 34; dimethylphenylcarbinol - 0.5; α-methylstyrene = 1.8; alpha-methylstyrene dimers = 0.8 and other, unidentified products.

300 g of the aceto-phenone fraction and 30 g of copper-chromium-calcium catalyst (Adkins catalyst) are taken for hydrogenation.

The hydrogenation is carried out at a temperature of 100 ± 1 ° C and a pressure of 10 MPa. The obtained hydrogenate contains (in% by weight): 0.6 alpha-methylstyrene; 34.3 methylphenylcarbinol; 6.4 alpha-cetophenone; 0.9 dimethylphenylcarbinol; 33phenol; 0.5 dimers of alpha-methylstyrene and 4,91-phenyl-1- (hydroxyphenyl) ethane.

The conversion of acetophenone to 85.4% for 5 h and selectivity to methylphenylcarboline 91.3%. This hydrogenate is conducted by naarylalkylation, carried out at a temperature of 152 + 3 ° C on phosphate catalyst (4x4 mm grain, trihydrogenphosphoric acid and polyphosphoric acid, phosphorus content = 22.6% by weight) at 0 ° C. 3 g.cm-3h -1, with selectivity to 1-phenyl-1 (hydroxyphenyl) -ethanes being 59% and 1-phenylxy-1-phenylethane 27%. In a further variant, the hydrogenation of the acetophenone fraction is carried out under otherwise similar conditions, but at a temperature of 140 ° C-2 degrees Celsius acetophenone and a selectivity of methylphenylcarbinol of 88%. Example 3

Weigh 90 g of ethylbenzene solution of ethylbenzene hydroperoxide in a rotary autoclave of 1 dm 3 of stainless steel with a concentration of 40.7% by weight, 4.8% <251952% by weight, acetophenone and 3.5% by weight. methylphenylcarbinol. Next, 35 g of ethylbenzene and 4.0 g of molybdenum diphenylate containing 4.1% by weight of molybdenum. After closure of the autoclave and removal of air, 40 g of propylene (molar excess = 3.65) are produced, and the autoclave content is rapidly heated to 110 ° C with constant rotation. The total pressure in the auto-key reaches 2.6 MPa. At this temperature, with an accuracy of + 2 ° C, epoxidation is carried out with constant rejection. Experiment sapo 60 min. the product is discharged through the condenser, weighed, the propropylene and propylene oxide are distilled off. The total conversion of ethylbenzene hydroperoxide reaches 99.6%, the selectivity to propylene oxide 53.6%, and methylphenylcarbinol 40.5% and the selectivity of propylene to propylene oxide 94.3%. The distillation residue mainly contains methylphenylcarbinol (30.3% by weight), acetophenone (9.2% by weight), ethylbenzene (60.3%), propylene glycol, catalyst and ethylbenzene hydroperoxide. Example 4

3,671 kg are injected into the continuously operating epoxidation reactor. h &apos; 1 of the succession (in% by weight): propylene = 45.0, ethylbenzene - 32.7, acetophenone = 2.3, methylphenylcarbinol - 2.8, ethylbenzene hydroperoxide = 17.1 and an epoxidizing catalyst = 0.1, from the epoxidation reactor, the resulting reaction mixture in an amount of 3.671 kg.h -1 is fed to a regenerative ("degassing") column, from which 1,491 kg.h -1 of the converted propylene is discharged. thereafter returning to the raw materials and the epoxidation reactor and at the bottom a "crude" reaction product in an amount of 2.180 kg.h -1 of this coating (in% by weight): propylene oxide δ = 8.6; ethylbenzene = 55.1; acetophenone = 7.62, methylphenylcarbinol = 25.81; ethylbenzene hydrobromide = 1.42; propylene glycol - 1.90 Acatalyst - 0.15. The crude reaction product is fed to a second rectification column from which 0.1875 kg is removed. h "1-propylene oxide and 1.922 kg.h" of column bottom 1% yield intermediate (% by weight): ethylbenzene - 60.3; methyl phenylcarbinol = 28.1; acetophenone - 7.7; ethylbenzene hydroperoxide = 1.6; propylene glycol = 2.1 and catalyst = 0.2.

This is fed to the 3rd rectification column, from which the topside leaves 1.201 kg.h "1 ethylbenzene and bottom at 0.791 kg.h" 1 side oxygen organic product of this yield (in% by weight): acephenone - 19 , 3; methylphenylcarbinol - 71.1, ethylbenzene hydroperoxide - 4.0; propylene glycol - 5.2 and catalyst = 0.4.

The secondary oxygenation product of the 3rd rectification column is then destroyed by the effective ammonium hydroxide extraction, which is then recovered or the next oxygenated organic product in the amount of 0.791 kg.h -1 is fed to the 4th rectification column, the head of which is 0.613 kg.h -1 leaves the acetophenone-methylcarbinol fraction (% w / w): acetophenone = 19.9; methylphenylcarbinol = 73.4; propylene glycol and dimethyl phenylcarbinol = 6.7. The heavy distillation residue from the bottom of the 4th column at 0.178 kg / hr contains about 65% of methylphenylcarbinol, 18% of acetophenone, 1.8% of catalyst, and other unidentified, mainly acidic, organic products, for selective hydrogenation to produce arylalkylating agent. Either the oxy-organic side product is used, especially after the epoxidizing agent has been removed or regenerated, and the "top" acetophenone-methylphenylcarbinol fraction can be used even as an arylalkylating agent, as well as the heavy distillation residue, especially after the deoxidation Example 5

To a 1 dm 3 stainless steel rotary autoclave, 200 g of the other oxygen-containing organic product from the production of propylene oxide by epoxidation-propylene with ethylbenzene hydroperoxide specified in Example 4 was weighed. 20 g of a copper (Raney) copper catalyst were added thereto. the autoclave is closed, the air is removed and hydrogen is brought to 15 bar. Hydrogenation is carried out at 115 ± 2 ° C for 3.5 h to give a hydrogenate which, after filtering off the catalyst, has a composition (in% by weight): acetophenone = - 0.5; methylphenylcarbinol = 92.4; propylene glycol - 5.2; styrene = 1.6 and ethylbenzene = 0.7. This hydrogenate, even without further refining, is a suitable arylalkylating agent. Example 6

The procedure is similar to that in Example 5, except that the hydrogenation of the acetophenone-methylphenylcarbinol fraction, as specified in Example 4, is selected instead of the by-product organic product. The obtained hydrogenate has the following composition (% by weight): methyl phenylcarbinol - 93.2 ; acetophenone 0.1 apropylene glycol with additional impurities = 6.7. EXAMPLE 7 The heavy distillation residue specified in Example 4 is vacuum distilled, wherein the distillate obtained has the following composition (% by weight): acetophenone = 22.1; methylphenylcarbinol = 76.8 and styrene = 0.9.

The distillate is then hydrogenated on a scrubbed tableted copper chromium catalyst (Adkins catalyst) at a temperature of 153 + 2 ° C and molar ratio of acetophenone: hydrogen = 1: 15. However, the hydrogenation catalyst is

Claims (3)

251952 10 in a stream of hydrogen at 180-210 degrees Celsius for 6 h. The obtained hydrogenate has this composition (in% w / w): aceto-phenone <0.05; methylphenylcarbinol = 94.6; styrene - 2.8 and ethylbenzene = 2.5, Example A heavy distillation residue as specified in Example 4 is fed to hydrogenation and hydrogenated on an activated copper-chromium-calcium catalyst such that hydrogen is bubbled through the hydrogenation reactor. a tempered (to 105 + 1 ° C) distillation residue and thereby pours its steam into the reactor. Similarly, a high hydrogenation efficiency of 153 ° C is obtained without distillation + 2 ° C of Example 7 and the long service life of the hydrogenation catalyst. EXAMPLE 9 Ecetophenone-methyl-phenylcarbinol fraction isolated from the epoxidation product of 1-butene-2-butene-ethylbenzene hydroperoxime contains 18.5% acetophenone, 73.9% methylphenylcarbinol and the remainder is butylene glycols and other oxygenated organic products. 200 g and 100 g of ethylbenzene as solvent are hydrogenated in an autoclave specified in Example 5 on a Raney-med catalyst (21 g) at 140 ° C + 3 ° C for 3 h. Acetophenone is hydrogenated with a conversion of 99% and a selectivity of 84. to methylphenylcarbinol. EXAMPLE 10 A procedure similar to Example 7 was followed, except that the copper-zinc-chromium catalyst and the temperature of 160 + 2 [deg.] C. were used instead of the copper copper chromate catalyst. The hydrogenation catalyst is also activated prior to hydrogenation in a stream of hydrogen at 180-210 ° C for 6 hours. The hydrogenate obtained has this composition (in% by weight): acetophenone = 0.0; methylphenylcarbinol - 89.4; styrene-7.9 and ethylbenzene = 2.6. The hydrogenate is a high quality arylalkylating agent. EXAMPLE 11 A procedure similar to that described in Example 7 was followed, except that a scaffolding Raney-nickel and a hydrogenation temperature of 85 ++ 1 ° C were used instead of the oxide copper chromate foam. The obtained hydrogenate has this composition (in% by weight): acetophenone - 0.7; methyl phenylcarbinol - 89.9; ethylbenzene and more closely identified products - 8.7. SUBJECT A method for preparing arylalkylating agent containing methylphenylcarbinol of from 40 to 100 o / o, more typically styrene in a quantity of 0 to 50% and 0 to 30% of other ingredients such as ethylbenzene, acetophenone, propylene glycol, styrene oligomers and C6 to Cfi hydrocarbons characterized in that the cross-linked products of epoxidation of the alkene or alkenes with ethylbenzene hydroperoxide, preferably from the product of the epoxidation of propene ethylbenzene hydroperoxidium to methyloxirane, are isolated by rectification of a fraction containing methylphenylcarbinol and / or acetophenone which further selectively hydrogenates in a liquid and or vapor phase at 70 to 210 ° C on a hydrogenation catalyst or catalysts containing at least one metal and / or a metal compound Ib, II.b, v.1.b. and VIII. groups of the periodic system, preferred honey and silver · on carriers and ske-flight honey.