CS241576B1 - A method of preparing alkylphenols - Google Patents

Abstract

The invention relates to a method for preparing alkylphenols by reacting phenol with olefins based on propene or butene oligomers with a molecular weight of 150 to 1500 using an active aluminosilicate as a catalyst. The invention can be used in the chemical industry.

Description

The present invention is concerned with the preparation of alkyl phenols by reacting phenol with olefins on a base of propene base and butenes having an average molecular weight of 150 to 1500 with the presence of an active aluminosilicate as catalyst.

Alkylated phenols containing hydrocarbon substituents based on propene and butene oligomers having an average molecular weight of 150 to 1500 have preferred uses as intermediates in the preparation of lubricating oil additives of the metal salts of alkylphenols, alkylphenylthiophosphoric acids, alkylsalicylic acids and base bases used as polar dispersants in motor oils. They are also suitable as intermediates for the production of surfactants, synthetic resins and additives for macromolecular materials.

Alkylphenols. they are prepared by the most preferred phenol-olefin treatment, since unsuitable byproducts requiring a special treatment are not produced in addition to the known catalysts. The known catalysts used in prialkylation are sufficiently effective, but the applications are associated with alkylate separation problems. Such catalysts include inorganic acids such as sulfuric acid (US Patent No. 2,008,017, French Patent No. 793,219), Lemis acids of aluminum chloride type 1, hydrogen fluoride, boron trifluoride (French Patent No. 805,912, US Patent No. 2,698 867, U.S. Pat. No. 2,398,253] or stannous, ferric and zinc chloride or mixtures of boron trifluoride with phosphoric acid or sulfuric acid and aluminum chloride (U.S. Patent No. 2,789,143). these catalysts require treatment by neutralization and washing to produce contaminated waste water.

When using organic sulphonic acids as catalysts (U.S. Pat. No. 2,865,966), the alkylation catalyst must also be removed by washing with water if dealkylation of the product during elevated temperature alkylate processing is prevented. acids on porous carriers such as tetrafosphoric 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. cation-exchange ion exchangers provide high molecular weight sulfoacids (British Patent No. 731,270 and 953,929), activated alumina (U.S. Pat. No. 2,101,881, or actively aluminosilicates (French Patent No. 1,203,604), which are easy to remove from the alkylate and do not leave in the al- acid free acid.

The disadvantages of cation exchange catalysts in the alkylation of phenol by higher olefins are their relatively low efficiency and higher cost. Aluminum oxide requires relatively high temperatures in the alkylation reaction.

According to the Czechoslovak invention (No. 183,320), for the preparation of alkyl substituted phenols, aluminosilicate with a specific surface area of 150 to 400 m 2 / g, a structural acid of 15 to 60 mg / KOH / g at the content of high acidity is used as catalyst. not more than 3 mg KOH / g, a structural water content of 5 to 15 wt. % / O and sorbated water 2 to 10 wt. %, wherein at 0.3 to 3 moles of olefin or a mixture of moles of moles are applied per mole of phenol at 60 to 200 ° C. weight 70 to 1000 in the presence of 5 to 60 wt. % aluminosilicate to phenol.

Using such an aluminosilicate by the method of AO No. 183 320, undesirable polymerization reactions are noticeably suppressed, chemically impure waste water is not produced, and the content of mono- and di-alkyl substituted phenols in the alkylate is regulated to a considerable extent according to the molar ratio of alkenes to phenol.

However, the alkylation of phenol with olefins based on propylene oligomer and butenes of average molecular weight above 150 has shown that under the conditions of the invention number 183 320, which requires a temperature of more than 130 degrees C, there is a more remarkable de-alkylation of the resulting alkylphenols and partly to cleavage and shortening of alkyl chains. As a result, the yield and the properties of the alkylates are reduced.

It has been found that this drawback is substantially eliminated by the process of preparyalkylphenols by the reaction of phenol with olefins in the presence of propene or butene average molecular weight oligomers of 150 to 1500 in the presence of 3 to 10 wt. % of active aluminosilicate of structural acidity of 15 to 60 mg KOH / g, with a specific surface area of 50 to 400 cm 2 / g, with a content of 5 to 15 wt. % Of structurally bound water, 2 to 10 wt. % of sorbed water and with free acidity more than 4 mg KOH / g as catalyst, according to the invention.

The invention is based on the fact that safenol is mixed with the active aluminosilicate to raise the temperature to 130-170 ° C by distillation of the sorbed water from the catalyst, after which an olefin in the amount of 0.2 to 0.5 mol is added to the mixture. per mole of phenol, the mixture is then kept under stirring at 150 to 180 [deg.] C. for a maximum of 3 hours, and after separation of the catalyst, the phenol is distilled off with the unreacted olefins used for 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 for the heating of phenol with an active aluminum silicate, the effect of the catalyst is increased by distillation of the sorbed water, which results in a reduction in its amount to about half the value as in the method of AO no. using the phenol from the intermediate reaction, it allows olefins present therein to react with less reactive unsaturated bonds. Tactose achieves good conversion of both long-chain and branched alkenes, which form an essential part of the oligomer of the ipropene of the abutene moles. the weight of 150 to 1500 and the decrease in the amount of olefins in the resulting alkylphenols.

After the addition of the olefin to the phenol-active aluminosilicate mixture, the alkylation reaction at 150-180 ° C has a rapid equilibrium state of less than 3 hours, which is approximately half the time value required to perform the reaction. . AO 183 320, thereby allowing a good use of the reaction space. In a recirculated phenol, alkylphenols are also present in lesser amounts, and thus they are used and contribute to good yield.

The actively aluminosilicates suitable for the catalysts of the present invention are obtained by treating the natural soils of a bentonite phtotype with an appropriate amount of mineral acids, especially hydrochloric acid, and sulfuric acid, at elevated temperature and subsequent removal of excess acid by washing with water.

The characteristic physical properties of the active aluminosilicate depend on the composition and purity of the feedstock and on the mineral acid activation condition. The desired active aluminosilicate catalysts according to the invention also include some commercially active higher H-montmorillonite clays which are used in industry for the sorption refining of mineral oils and edible fats and oils.

The process for preparing alkylphenols according to the invention is advantageous for the alkylation of phenol by higher boiling olefins with a wider distribution of moles. masses, such as the propylene glycol viscols and the butenes obtained by the propylene glycol catalysts for these olefins. Such oligomers are, for example, propylene oils having an average molecular weight of 400 and < RTI ID = 0.0 > 00 < / RTI > and an average molecular weight of 2.00 to 400 (distillate) and 600 to 1000 (distillation residue). For alkylation, isomers of alkenes with alkanes or small-reactive carbon atoms can be used, which is the prialkylation of phenol by viscous alkenes of higher molecular weight.

The catalyst used in the preparation of the alkylphenol according to the invention is separated from the alkylate by filtration or centrifugation, whereby the residues of the alkylphenol and the reactants are desirably recovered from the solids by washing or extraction with, for example, hydrocarbons and then returned to the reaction mixture.

The actively aluminosilicates used in the examples are characterized by characteristic physical properties:

Property Size specific surface m2 / g structural acidity mg KOH / g free acidity mg KOH / g structural water wt. % sorbed water wt. %

Active Aluminosilicate AB 112.0 161.0 49.7 50.2 0.38 0.26 6.1 5.9 8.5 7.2 Example 1 In a four necked flask equipped with a stirrer, thermometer, condenser, and dropping funnel g (1 mol) of phenol adds 7-active aluminosilicate A and mixes by distilling the water by raising the temperature to 150 ° C. 78 g (0.25 mol) of propylene polymer of an average molecular weight of 310 are added over a period of 30 minutes and the temperature is raised to 170 ° C while maintaining the mixture for 2 hours.

The catalyst is removed by filtration and the excess phenol containing 8% of hydrocarbons and 1.5% of alkylphenols is distilled off by filtration at a pH of 1.3. The phenol to olefin molar ratio is 4 and the catalyst content is 4.1 wt. ° / o. 92 g of alkylphenol having an average molecular weight of 381 with a p-isomer content of 53.1%, o-isomers of 33.0%, and 13.9% of a cinematic viscosity of 8.7 mm 2 s are obtained. "1 at 100 ° C. The alkylphenol yield is 81.5% per naphthalene. Example. 2 In an apparatus as in Example 1, a quantity of 14.1 g was added to 188 g (2 mol) of phenol and successively heated to 140 ° C with stirring. 136 g of isobutylene polymer are added to the mixture. mass 232 (0.67 mol), while the temperature increased to 160 ° C, where the mixture was maintained for 2 hours. The catalyst was removed by filtration and excess phenol was distilled off from the filtrate to give 200 g of an alkylphenol of average molecular weight 326, a kinematic viscosity of 9.2 .mu.m2 s @ 1 at 100 DEG C., containing 10 .mu.m. % hydrocarbons. Molar ratio of olefin phenol in the reaction! is 3: 1 and responsive

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