CS241576B1 - Method of alkylphenoles preparation - Google Patents

Abstract

The invention relates to a process for the preparation of alkylphenols by reacting the phenol with the olefin on a base allgomers of propene or butene mol. wt. 150 to 1500 using active aluminosilicate catalyst. The invention can be used in the chemical industry.

Description

The invention relates to a process for preparing alkylphenols by reacting phenol with olefins based on propene oligomers and butenes of an average molecular weight of 150 to 1500 in the presence of an active aluminosilicate catalyst.

Alkylated phenols containing hydrocarbon substituents based on propene oligomers and butenes having an average molecular weight of 150 to 1,500 have advantageous use as intermediates in the manufacture of additives for lubricating oils of the metal salt type of alkylphenol derivatives, alkylphenyldithiophosphoric acids, alkylsalicylic acids and manponic bases used as manganese bases for engine oils. They are also suitable as intermediates for the production of surfactants, synthetic resins and additives for macromolecular materials.

Alkylphenols. They are prepared most preferably by reaction of phenol with olefins, since the addition reaction does not produce unpleasant by-products requiring special processing. Of the known catalysts used in alkylation, some are sufficiently effective, but their use is associated with separation problems. alkylate.

Such catalysts include inorganic acids such as sulfuric acid (US Patent No. 2,008,017, French Patent No. 793,219), Lemis acids of the type of aluminum chloride, hydrogen fluoride, boron trifluoride (French Patent No. 805,912, US Patent No. U.S. Pat. No. 2,698,867, U.S. Pat. No. 2,398,253) or stannous, ferric and zinc chloride, or even mixtures of boron trifluoride with phosphoric acid or sulfuric acid and aluminum chloride (U.S. Pat. No. 2,789,143). treatment by neutralization and washing to produce contaminated waste water.

When using organic sulfonic acids as catalysts (U.S. Pat. No. 2,865,966, the alkylation catalyst must also be removed by washing with water to prevent dealkylation of the product in the treatment of the alkylate at elevated temperature. Neutralization of the alkylate is also required after the use of inorganic acids on porous carriers. for example, tetraphosphoric acid on active clay (U.S. Pat. No. 2,415,069, Chemical Industry 16, 533, 1966).

More preferably, in the alkylation of phenol, the catalysts are insoluble in the reaction medium. Such are cation exchangers based on high molecular weight sulfoacids (British Patent Nos. 731,270 and 953,929), activated alumina (USSR Patent No. 210181) or actively aluminosilicates (French Patent No. 1,203,604), which are readily detached from alkylate and do not leave free acids in the alkylate.

The drawbacks of cation exchange catalysts in the alkylation of phenol with higher olefins are their relatively low efficiency and higher cost. Alumina requires relatively high temperatures in the alkylation reaction.

According to the Czechoslovak invention (Ao No. 183 320), an active aluminosilicate having a specific surface area of 150 to 400 m ² / g, a structural acidity of 15 to 60 mg 'KOH / g with a free acidity content of not more than 3 mg KOH / g is used as a catalyst. g, a structural water content of 5 to 15 wt. 2 to 10 wt. %, With 1 mole of the phenol, at a temperature of 60 to 200 ³ C 0.3 to 3 mol of an olefin or a mixture otlefínov · mol. 70 to 1,000 wt. in the presence of 5 to 60 wt. % aluminosilicate per phenol.

Using such an aluminosilicate according to method AO no. 183,320, undesirable polymerization side reactions are largely suppressed, no chemically contaminated effluents are formed, and the content of mono- and dialkyl-substituted phenols in the alkylate can be controlled to a large extent, depending on the molar ratio of alkenes to phenol.

However, the alkylation of phenol with olefins based on an oligomer of propene and butenes with an average molecular weight of more than 150 showed that under the conditions of the invention number 183 320, which required a temperature of more than 130 degrees C, more remarkably dealkylation of the alkylphenols formed and partially cleaved and shortened alkyl chains. As a result, the yield is then reduced and the properties of the alkylates are varied.

This deficiency has been shown to be substantially eliminated by the process of preparing alkylphenoils by reacting phenol with olefins based on propene oligomers or butenes of an average molecular weight of 150 to 1500 in the presence of 3 to 10 wt. % active structural acid aluminosilicate 15 to 60 mg KOH / g, with a specific surface area of 50 to 400 cm ² / g, containing 5 to 15 wt. % structurally bound water, 2 to 10 wt. % sorbed water and with a free acidity of at most 4 mg KOH / g as a catalyst according to the invention.

SUMMARY OF THE INVENTION The phenol is mixed with the active aluminosilicate to raise the temperature to 130-170 ° C to distill the sorbed water from the catalyst, after which the olefin is added in an amount of 0.2-0.5 mol per 1 mol of phenol. , the mixture was maintained with stirring at 150-180 C ^and not more than 3 hours, the separation of the catalyst the phenol is distilled off nezreagovianými olefins to be used in the following preparation.

It has also been found to be advantageous if the active aluminosilicate has a specific surface area of 100 to 150 m ² / g.

In the process according to the invention, the heating of the phenol with active aluminosilicate increases the effect of the catalyst by distilling off the sorbed water, which results in a reduction in its amount to about half that of the process according to the invention. AO č. 183,320, and also when using the recited 241576 phenol from the previous reaction, it allows the olefins present there to react with less reactive unsaturated bonds. In this way, good conversion of long-chain and branched alkenes is also achieved, which forms a substantial proportion in propene oligomers and mole butenes. with a weight of 150 to 1500 and thus a reduction in the amount of olefins in the alkylphenols formed.

After addition of the olefin to the phenol-active aluminum mixture, the alkylation reaction at 150-180 ° C has a rapid course and the equilibrium is reached in less than 3 hours, which is approximately half the value required for the reaction to proceed. podfa čs. AO 183 320, thus allowing a good utilization of the reaction space.

Alkylphenols are also present in minor quantities in the recirculated phenol and are thus used to contribute to a good yield.

Active aluminosilicates suitable as catalysts of the invention are obtained by treating bentonite-type natural soils with an appropriate amount of minerals, in particular, hydrochloric and sulfuric acids, at elevated temperature and subsequently removing excess acid by washing with water.

The characteristic physical properties of the active aluminosilicate depend on the composition and purity of the feedstock and the conditions of mineral acid activation. The requirements for active aluminosilicate catalyst of the present invention are also met by some commercial active clays with a higher H-montmorillonite content, which are used in industry in the sorption refining of minerals, new oils and edible fats and oils.

The process for the preparation of the alkylphenols of the invention is advantageously applied for the alkylation of phenol with higher boiling olefins with a broader molar distribution. % by weight, such as viscous oligomers of propene and butenes, obtained industrially by reacting Friedel-Crafts catalysts on these olefins. Such oligomers are, for example, propylene oils having an average molecular weight of 400 to 00 and the distillates obtained therefrom having an average molecular weight of 200 to 400 (distillate) and 600 to 1000 (distillation residue). Mixtures of alkenes with alkanes or small-reactive hydrocarbons may also be used for the alkylation, which is desirable in the alkylation of phenol with higher molecular weight viscous alkenes.

The catalyst used in the preparation of the alkylphenol is as described above. of the invention separates from the alkylate by filtration or centrifugation, the residues of the alkylphenols and reactants preferably being obtained from the solid by washing or extraction, for example with hydrocarbons, and then returning to the reaction mixture. Examples

The active aluminosilicates ¹ used in the examples had the following physical properties:

Vfastnosť Dimensions specific surface area m ² / g structural acid mg KOH / g free acid mg KOH / g structural water wt. % sorbed water wt. %

Active aluminosilicate

A B 112.0 161.0 49.7 50.2 0.38 0.26 0.1 5.9 8.5 7.2

Example 1

In a four-necked flask equipped with stirrer, thermometer, condensers and dropping funnel, 7 g of active aluminosilicate A is added to 94 g (1 mole) of phenol and stirred while distilling water by raising the temperature to 150 ° C. 78 g (0.25 mol) of propylene polymer of average molecular weight 310 are added over 30 minutes and the temperature is raised to 170 ° C, maintaining the mixture for 2 hours.

The catalyst was removed by filtration and excess phenol containing 8% hydrocarbons and 1.5% alkylphenols was distilled off from the filtrate under reduced pressure (50 mbar). The molar ratio of phenol to olefin is 4 and the catalyst content in the mixture is 4.1 wt. ° / o. 92 g of an average molecular weight of 381 having an β-isomer content of 53.1% / o, an o-isomer of 33.0% and a hydrocarbon content of 13.9%, a kinematic viscosity of 8.7 mm ² s ^-1 at 100 ° C are obtained. The yield of alkylphenols is 81.5% of the olefin loaded.

Example. 2

In the apparatus of Example 1, 14.1 g of phenol (188 g, 2 mol) was added with stirring, and the mixture was gradually heated to 140 ° C. 136 g of isotoutylene mol polymer are added. weight 232 (0.67 mol) while raising the temperature to 160 ° C, maintaining the mixture for 2 hours. Filtration removed the catalyst and the filtrate was distilled off under reduced pressure, excess phenol to obtain 200 g of alkyl phenol of average molecular weight 326, kinematic viscosity of 9.2 mm ² · s at ^_1 100, containing 10.2 wt. % of hydrocarbons. The molar ratio of phenol to olefin in the reaction is 3: 1 to reactive

24157G component is 4.1 wt. % catalyst. The alkylphenol yield is 82% based on the olefin used.

EXAMPLE 1 a d 3

In the apparatus of Example 1, a mixture of 94 grams of phenol (1 mole) and 7 grams of aluminosilicate B is heated to 170 ° C with stirring while water is distilled off. 89 g (0.28 mol) of propylene polymer of molecular weight 310 are added and the temperature is maintained at 170 DEG C. for 90 minutes. The catalyst is separated from the mixture by filtration and excess olefin-containing phenol is distilled off under reduced pressure to give 106 g of an average molecular weight of 400, containing 54.7% of the .beta.-isomers, 33.1% of the o-isomers and 12%. , 2% hydrocarbons. The molar ratio of the reactants was 3.5 and the catalyst content was 4 wt. % in the reaction mixture. The alkylphenol yield is 80.7% on the olefin employed.

Example 1 4

In the apparatus of Example 1, 94 g (1 mol) of phenol and 18.8 g of aluminosilicate B are mixed at 80 ° C and the mixture is heated to 170 ° C with stirring, distilling off the water. 106 g (0.2 mol) of propylene polymer of average molecular weight 830 are added and the mixture is stirred for 3 hours at 1185 ° C. The catalyst is then filtered off and excess phenol is distilled off at a pressure of 50 mbar.

The distillation residue in an amount of 167 g is an alkylphenol with an average molecular weight of 910, containing 39% of hydrocarbons. Reaction at a molar ratio of phenol to olefin of 5: 1 containing 7.2 wt. % of the catalyst in the mixture provides 56% conversion of olefins to alkylphenols.

EXAMPLE 5

In a 4-neck 6,000 cm ³ flask equipped with a stirrer, thermometer, condenser, and dropping funnel, 145 g of aluminosilicate A was added with stirring to 1940 g of phenol (20.63 moles) and the temperature was raised to 150 ° C with distillation. water from the catalyst. 1600 g (5.16 mol) of propylene polymer of average molecular weight 310 were added gradually over 60 minutes, after which the temperature was raised to 170 ° C, keeping it under stirring for 120 minutes.

The catalyst is separated by filtration and the olefin containing olefin and alkylphenols is distilled off from the filtrate by distillation under a reduced pressure of 50 mbar. The distillation residue is alkylphenol as the reaction product. The reaction mixture contained 4.1% catalyst and the molar ratio of phenol to olefin was 4. This process was repeated in three similarly performed syntheses, in which the distilled phenol was introduced into the reaction, containing the olefin from the previous alkylphenol preparation, supplemented with fresh phenol. to a total amount of 20.6 moles of phenol. Similarly, propylene polymer was used in an amount such that the total feed was 5.16 mol.

A total of 3183 g (33.8 mol) of phenol, 6257 g (20.2 mol) of propylene polymer and 580 g of aluminosilicate A were used for 4 syntheses. A total of 8 240 g of alkylphenol (average molecular weight 395, kinematic) viscosity of 8.5 was obtained. ² mm with the IP ^_1 DEG C., containing 15.6% uihlovodíkov NA 1 435 g of the phenol alcohol containing 85 ° / o phenol (12.9 moles] and the olefin of 12.5%. the yield of alkyl phenol to olefin is calculated 88.1 %.

Claims (2)

24157G of component is 4.1 wt. % catalysts. The yield of alkylphenols is 82% on seeded olefin. EXAMPLE 3 A mixture of 94 g of phenol (1 mol) and 7 g of aluminosilicate B under stirring was heated to 170 [deg.] C. while distilling off water. 89 g (0.28 mol) / propylene polymer of 310 molecular weight are added and the temperature is maintained at 170 ° C for 90 minutes. The catalyst is separated from the catalyst by filtration and excess olefin containing olefin is distilled off under reduced pressure to give 106 g of an alkyl phenol having an average molecular weight of 400, containing 54.7% of p-isomer, 33.1% by weight. -isomer and 12.2% hydrocarbons. The molar ratio of the reactants is 3.5 and the catalyst content is 4 wt. The yield of alkylphenols is 80.7% on seed oil. Example 4 In an apparatus such as Example 1, 80 g of 94 g (1 mol) of phenol and 18.8 g of aluminosilicate B are mixed and the mixture is heated to 170 ° C with stirring while distilling off the water. 106 g (0.2 mole) of polymeric propylene of an average molecular weight of 830 are added to the mixture and the mixture is stirred for 3 hours at 1185 ° C. The catalyst is then filtered off and excess phenol is distilled off from the filtrate at a pressure of 1.3 kPa. The distillation residue was 167 g of an alkylphenol having an average molecular weight of 910, containing 39% of hydrocarbons. Realization at a molar ratio of phenol to olefin of 5: 1 containing 7.2 wt. % catalyst in the mixture provides 56% conversion of olefins to alkylphenols. EXAMPLE 5 Mixing to 1940 g of phenol (20.63 mol) 145 g of aluminosilicate A is added in a four-necked 6,000-cm3 flask equipped with a stirrer, thermometer, cooler and dropping funnel and the temperature is increased 150 ° C while distilling off the water from the catalyst. 1600 g (5.16 mol) of propylene polymer of average molecular weight 310 are added successively over 60 ml, whereupon the temperature is raised to 170 ° C for 120 minutes while mixing. The catalyst is separated by filtration and the olefin containing alkyl phenols is distilled off from the filtrate by distillation under reduced pressure (1.3 kPa). The distillation residue is an alkylphenol and reaction product. The reaction mixture contained 4.1% of catalyst and the molar ratio of phenol olefin was 4. This procedure was repeated in three equally performed syntheses in which the distilled phenol containing olefin from the preparation of alkylphenol (which was fed into with phenol to a total amount of 20.6 moles of phenol, similarly, polymers of propylene were added in an amount of 5.16 moles in total to 3183 g (33.8 moles) of phenol, 6257 g (20%). 2 moles of propylene polymer and 580 g of aluminosilicate A. A total of 8,240 g of an alkylphenol of an average molecular weight of 395, a kinetic viscosity of 8.5 mm 2 s -1 at 10 ° C with a content of 15.6% hydrocarbons were obtained. of 435 gphenol-distillate containing 85% of phenol (12.9 mol) and 12.5% of olefins, the extract of alkylphenol calculated on olefin being 88.1%. CLAIMS 1. A process for the preparation of alkylphenols by reacting phenol with olefins based on propene or butene oligomers having an average molecular weight of 150 to 1500 in the presence of 3 to 10 wt. % Aluminosilicate structural acidity of 15 to 60 mg KOH / g, specific surface area of 150 to 400 m 2 / g, containing 5 to 15 µm / g. % structurally bonded, 2 to 10 wt. % sorbated water and free acid up to 4 mg KOH / g acocatalyst, characterized in that the phenol is premixed with the active aluminosilicate to increase the temperature to 130 to 170 degrees C with distillation of the sorbed water from the catalyst, . the olefin is added to the mixture in an amount of 0.2 to 0.5 mole per mole of phenol, the mixture is then kept under stirring at a temperature of 1/50 to 180 ° C for not more than 3 hours after the catalyst has been separated off and the unreacted olefins are distilled off. following preparation. 2. A process according to claim 1, wherein the active aluminosilicate has a specific surface area of 50 to 150 m @ 2 / g. Severografia, n. P., Závod 7, Most price 2,40 Kcs