RU2195444C1 - Space-hindered bis-phenol production process - Google Patents

Abstract

FIELD: industrial organic synthesis. SUBSTANCE: rubber and plastics stabilizers and curers, in particular space-hindered bis-phenols having general formula

Description

где R' - водород, или алкил С1, или бензил;
R'' и R''' - одинаковы или различны и представляют собой СН₃, С₄Н₉,
используемых в качестве эффективных, неокрашивающих, нетоксичных, малолетучих стабилизаторов для каучуков, резин, вулканизатор, пластмасс и других органических продуктов.The invention relates to the petrochemical industry, in particular to a method for producing spatially hindered bis-phenols of the general formula

where R 'is hydrogen, or alkyl C1, or benzyl;
R ″ and R ″ ″ are the same or different and are CH ₃ , C ₄ H ₉ ,
used as effective, non-staining, non-toxic, non-volatile stabilizers for rubbers, rubbers, vulcanizer, plastics and other organic products.

A known method of producing spatially hindered phenols, specifically 2,2-methylenebis- (4-methyl-6-tert-butylphenol) by alkylation of 4-methylphenol with isobutylene in the presence of an acid catalyst, followed by the isolation of 4-methyl-2-tert-butylphenol and condensation with formaldehyde. The condensation is carried out in the presence of an acid catalyst in an aqueous emulsion medium containing a surfactant and an organic solvent, at a temperature of 75-90 ^o [Pat. U.S. 2796445, (1957), S.A. 51 16539 (1957)].

Also known is a method of producing 2,2-methylene-bis- (4-methyl-6-tert-butylphenol), comprising the condensation of 4-methyl-2-tert-butylphenol with formaldehyde in the presence of sulfuric acid in an aqueous emulsion medium at 80 ^o C neutralization of the catalyst and the selection of the finished product. The yield of the target product is 85-90% [Chemical industry, 1967, p. 19-21].

A known method for producing 2,2-bis- (4,6-dialkylphenols) by dealkylation of 2,4,6-trialkylphenols in the presence of the corresponding aluminum alkyl phenolates at 150-250 ^o With the allocation of dialkylphenol and further condensation with aldehydes or ketones [A. . USSR 405665, IPC C 07 C 59/16, 1971].

 A known method for producing 2,2-methylene-bis- (4-methyl-6-tert-butylphenol), including dealkylation of 2,6-di-tert-butyl-4-methylphenol by heating on an arylsulfonic acid catalyst, followed by condensation of the reaction mixture with methylal in the presence of N, N-di-methyl- (3,5-di-tert-butyl-4-hydroxybenzyl) -amine (Mannich base) with a molar ratio of arylsulfonic acid: Mannich base 1.00: 0.01-0.50 [ RF patent 2150461, IPC С 07 С 59/16, 1995].

A known method of producing spatially-hindered bis - or polyphenols by the interaction of trialkylphenols with aldehydes in an acidic medium at 60-200 ^o C. As the catalysts use Lewis acids, Bronsted, cation exchange resins [A.S. USSR N 732232, IPC C 07 C 59/16, 1980].

 The disadvantages of the above methods for producing bis-alkyl phenols include the following: the presence of a large amount of wastewater, the need to dispose of the released olefin, and the use of spatially-hindered alkyl phenols as target products.

The closest technical solution to the claimed is a method of obtaining spatially hindered bis-phenols, in particular 2,2-methylene-bis (4-methyl-6-tert-butylphenol), including transalkylation of a mixture of ionol and p-cresol with a molar ratio of 1 0: 1.3-3.0 in the presence of an acidic catalyst at 55-65 ^{° C.} , neutralization of the alkylate, isolation of monoalkyl-paracresol by distillation and crystallization, followed by washing of the resulting product and its condensation with formaldehyde [Pat. RF 2049087, IPC C 07 C 39/16, 1995].

 As a catalyst, sulfuric acid is used in an amount of 0.5-1.0% of the reaction mass.

 The condensation of monoalkyl-paracresol is carried out in a medium of a water-hydrocarbon emulsion with a 15-20% solution of formaldehyde in water.

The specified method has the following disadvantages:
- the use as raw materials of expensive individual products - ionol and p-cresol;
- the use of sulfuric acid as a catalyst, which leads to the resinification of the source and final products, as well as severe corrosion of the equipment;
- the presence of a large amount of wastewater. At least 2100 liters of water are consumed for the production of 1 ton of antioxidant;
- additional purification of monoalkyl-paracresol by recrystallization;
- the use of an emulsifier that pollutes wastewater;
- the need for preliminary preparation of an aqueous solution of formaldehyde.

 The technical task of the invention is to expand the raw material base, reduce the cost of the target products, reduce wastewater, recycle waste from the production of 2,6-di-tert-butyl-4-methylphenol (ionol), which currently do not find qualified use, simplifying the process and increased utilization of raw materials.

где R' - водород, или алкил С₁, или бензил;
R'' и R''' - одинаковы или различны и представляют собой СН₃, С₄Н₉,
переалкилированием смеси алкилфенолов, в качестве которых используют отходы производства 2,6-ди-трет-бутилфенола, полученного алкилированием фенола изобутиленом, со стадии ректификации состава, мас.%:
2,6-Ди-трет-бутилфенол (2,6-ДТБФ) - 1,0 - 30,0
2,4-Ди-трет-бутилфенол (2,4-ДТБФ) - 10,0 - 15,0
Смолы - 1,5 - 4,0
2,4,6-Три-трет-бутилфенол (2,4,6-ТТБФ) - Остальное (до 100)
или отходы алкилфенолов производства 2,6-ди-трет-бутил-4-метилфенола (ионола) со стадии регенерации метанола состава, мас.%:
2,6-Ди-трет-бутилфенол (2,6-ДТБФ) - 1,0 - 10,0
4,6-Ди-трет-бутил-2-метилфенол (4,6-ДТБ-2МФ) - 0,5 - 5,0
Диметиламинометилфенол - 1,0 - 4,0
Димеры фенолов - 1,0 - 8,0
Смолы - 0,1 - 1,0
2,6-Ди-трет-бутил-4-метилфенол (ионол) - Остальное (до 100)
и орто-фракции со стадии выделения 2,6-ди-трет-бутилфенола состава, мас. %:
2-Трет-бутилфенол (2-ТБФ) - 45,0 - 60,0
2,6-Ди-трет-бутилфенол (2,6-ДТБФ) - 15,0 - 25,0
Фенол - Остальное (до 100)
в количестве 20-50 мас.% на массу алкилфенольных отходов в присутствии арилсульфокислоты в количестве 1-4 мас.% на массу алкилфенолов при температуре 120-145^oС, с последующей нейтрализацией полученного алкилата, выделением 2,4-диалкилфенола ректификацией и конденсацией его с альдегидами или их производными, выбранными из группы: формальдегид, параформ, ацетальдегид, метилаль или бензалдегид, выделением целевого бис-алкилфенола.The technical result is provided in the proposed method for obtaining spatially-hindered bisphenols of the formula

where R 'is hydrogen or C ₁ alkyl or benzyl;
R ″ and R ″ ″ are the same or different and are CH ₃ , C ₄ H ₉ ,
by transalkylation of a mixture of alkyl phenols, which are used as waste from the production of 2,6-di-tert-butylphenol obtained by alkylation of phenol with isobutylene, from the rectification stage of the composition, wt.%:
2,6-Di-tert-butylphenol (2,6-DTBP) - 1.0 - 30.0
2,4-Di-tert-butylphenol (2,4-DTBP) - 10.0 - 15.0
Resins - 1.5 - 4.0
2,4,6-Tri-tert-butylphenol (2,4,6-TTBF) - Other (up to 100)
or waste alkylphenols production of 2,6-di-tert-butyl-4-methylphenol (ionol) from the methanol recovery stage of the composition, wt.%:
2,6-Di-tert-butylphenol (2,6-DTBP) - 1.0 - 10.0
4,6-Di-tert-butyl-2-methylphenol (4,6-DTB-2MF) - 0.5 - 5.0
Dimethylaminomethylphenol - 1.0 - 4.0
Phenol Dimers - 1.0 - 8.0
Resins - 0.1 - 1.0
2,6-Di-tert-butyl-4-methylphenol (ionol) - Else (up to 100)
and ortho-fractions from the stage of separation of 2,6-di-tert-butylphenol composition, wt. %:
2-Tert-butylphenol (2-TBP) - 45.0 - 60.0
2,6-Di-tert-butylphenol (2,6-DTBP) - 15.0 - 25.0
Phenol - Else (up to 100)
in an amount of 20-50 wt.% per weight of alkyl phenol waste in the presence of arylsulfonic acid in an amount of 1-4 wt.% per weight of alkyl phenols at a temperature of 120-145 ^o C, followed by neutralization of the obtained alkylate, isolation of 2,4-dialkylphenol by distillation and condensation with aldehydes or their derivatives selected from the group: formaldehyde, paraform, acetaldehyde, methylal or benzaldehyde, isolation of the target bis-alkyl phenol.

The process of condensation of 2,4-dialkylphenol with the above aldehydes or their derivatives is carried out in a hydrocarbon solvent taken in an amount of 10-50 wt.% Per reaction mass or without solvent at a temperature of 70-140 ^o C and a molar ratio of 2,4-dialkylphenol: aldehyde equal to 2.0: 1.0-1.5.

 Wastes from the production of ionol from the stage of separation of 2,6-di-tert-butylphenol and the stage of methanol regeneration currently do not find qualified use - they burn.

 Introduction into waste containing various alkyl-substituted phenols, ortho-fractions allows their more complete use, since along with the transalkylation reaction between 2,4,6-tri-alkylphenols and 2-tert-butylphenol, the 2,6- isomerization reaction di-tert-butylphenol to 2,4-di-tert-butylphenol and the phenyl alkylation reaction of the liberated isobutylene to 2-tert-butylphenol and 4-tert-butylphenol, which in turn enter into a transalkylation reaction, which leads to an increase yield of 2,4-dialkylphenols.

 A feature of the use of the ortho fraction is the ability to simultaneously obtain two different 2,4-alkyl phenols.

So, when using wastes from the production of ionol from the methanol recovery stage, two target products can be obtained:
2,4-di-tert-butylphenol and 2-tert-butyl-4-methylphenol, in approximately equal amounts and, without separating them, to obtain a mixture of the corresponding bis-alkylphenols on their basis.

 The separation of the catalyst by filtration, passing through calcium oxide or treatment with the main agents can dramatically reduce, or even completely avoid the formation of phenolic wastewater, as well as increase the yield of intermediate and target products, the loss of which with an aqueous layer is inevitable.

The starting reagents meet the following requirements:
- Benzenesulfonic acid - TU 6-36-0204229-25-89;
- Para-toluenesulfonic acid - TU 6-14-144-76;
- Alkylbenzenesulfonic acid - TU 2481-036-04689375-95;
- Formaldehyde - GOST 1625-89;
- Paraform - TU 6-09-3208-78;
- Paraldehyde - TU 6-09-1682-77;
- Acetaldehyde - GOST 9585-77;
- Methal - TU 6-09-4227-75;
- Benzaldehyde - GOST 157-78;
- Gasoline solvent - GOST 443-76;
- N-pentane or pentane-isopentane fraction TU 6-09-3661-74; TU 38.30366-88;
- Hexane - TU 6-09-3375-78;
- Nefras (White Spirit) - GOST 3134-78;
- Absorbent - TU 38.103349-76 and TU 2411-418-05742686-98.

 The process is carried out as follows.

 Ionol production waste, the ortho fraction from the 2,6-DTBP separation unit and arylsulfonic acid (benzene, alkyl or p-toluenesulfonic acid) are loaded into an autoclave with a stirrer, a thermocouple, a heating jacket. The amount of the ortho fraction is 20-50 wt.% Of the mass of the loaded waste, and the amount of catalyst is 1-4 wt.% Of the mass of the loaded alkyl phenols.

The resulting mixture is heated with stirring to 120-145 ^o C, maintained at this temperature for 3-6 hours, and the pressure in the autoclave rises to 2.0-3.5 atm. At the end of the process, the pressure decreases to almost atmospheric. Then the autoclave is cooled, the catalyst is separated (passed through calcium oxide, treated with alkaline agents) and the resulting transalkylate is sent for distillation.

 The isolated 2,4-di-alkyl-phenol is used to produce bis-alkyl-phenols, for which it is loaded into a reactor equipped with a stirrer, a thermometer and a reflux condenser. Arylsulfonic acid in the amount of 1-4.0 wt.% On loaded 2,4-di-tert-butylphenol is added there.

The mixture is heated to 55-70 ^o C until complete melting, then the mixer is turned on and the claimed aldehyde or its derivative is dosed in an amount of 1.0-1.5 moles per mole of alkyl phenol within 1.0-2.0 hours. At the end of dosing, stirring of the reaction mixture is continued for 2-6 hours at a temperature of 70-140 ^o C. In the case of obtaining bis-phenols with a melting point above the reaction temperature (which makes the stirrer difficult to work), at the end of dosing of the aldehyde, an organic solvent in an amount of 10-50 wt.% per reaction mass (gasoline, nefras, n-pentane, hexane). At the end of the reaction, the catalyst is separated (for example, by filtration) and bis-alkyl phenols are isolated from the above solvents.

 The yield of the target products on the loaded 2,4-dialkylphenol is 92-98 wt.% From theoretical.

 The essence of the method is confirmed by the following examples.

 Example 1

1000 g of ionol production waste (from the methanol recovery stage) of the composition are loaded into the autoclave, wt.%: 2,6-di-tert-butylphenol (2,6-DTBF) - 2.2; di-methyl-aminomethylphenol (DMAMF) - 1.20; 4,6-di-tert-butyl-2-methylphenol (4,6-DTB-2-MF) 0.80; phenol dimers - 3.9; resins - 0.1; 2,6-di-tert-butyl-4-methylphenol (ionol) 91.8. Add 460 g (46 wt.%) Ortho-fractions of the composition, wt. %: 2-tert-butylphenol (2-TBP) - 60.0; 2,6-DTBF - 15.0; phenol - 25.0 and 43.8 g of benzenesulfonic acid (BSC) at the rate of 3 wt.% per reaction mass. The stirrer is turned on, heated to 145 ^o C and maintained at this temperature for 3 hours. During the reaction, the pressure in the reactor drops from 3.5 atm to almost atmospheric. At the end of the reaction, reduce the temperature of the reaction mixture to 105 ^o C and with constant stirring make 11 g of potassium hydroxide. The neutralization process is carried out for 1.5 hours. At the end of neutralization, the mixer is turned off, and the mixture is left to stand for 1.5 hours without lowering the temperature.

 After settling, the condensed part is separated, consisting of resins, potassium BSK, BSK salt and DMAMF, and transalkylate in the amount of 1390 g of the composition, wt.%: 2-TBP - 5.04; 4-tert-butylphenol (4-TBP) 4.32; 2-tert-butyl-4-methylphenol (2-TB-4-MF) - 40.17; 2,4-DTBF - 39.4; 2,5-DTB-4-MF - 10.38; phenol dimers - 0.69, sent for rectification, with which 557 g of 2-TB-4-MF with a concentration of 98.5 wt.% and 545 g of 2,4-DTBF with a concentration of the main substance of 97.8 wt. % The isolated alkyl phenols (2-TB-4-MF and 2,4-DTBP) are used to produce bis-alkyl phenols by condensing them with the claimed aldehydes or their substituents.

 Example 2

 1000 g of ionol production wastes are loaded into the autoclave, wt.%: 2,6-DTBF - 1.05; DMAMF - 4.0; 4,6-DTB-2-MF - 2.5; phenol dimers - 7.9; resins - 1.0; 2,6-TB-4-MF - 83.55, add 350 g (35 wt.%) Ortho-fractions of the composition, wt. %: phenol - 30; 2-TBP - 45; 2,6-DTBP - 25 and 47.25 g of para-toluenesulfonic acid (3.5 wt.%). The process is carried out as described in example 1, however, to neutralize the alkylate, sodium hydroxide is used in an amount of 14 g. At the end of the process, 1280 g of the composition transalkylate are isolated, wt.%: 2-TBP - 1.7; 4-TBP - 1.17; 4-TBP - 1.17; 2-TB-4-MF - 39.29; 2,4-DTBF - 40.84; 2,6-DTB-4-MF - 11.92; phenol dimers - 5.00; resin - 0.08, by distillation from which 511 g of 2-TB4-MF with a concentration of 98.0 and 520 g of 2,4-DTBP with a concentration of 97.5% are isolated.

 Example 3

 1000 g of ionol production wastes are loaded into the autoclave, wt.%: 2,6-DTBF - 9.8; DMAMF - 2.5; 4,6-DTB-2-MF - 5.0; phenol dimers - 4.1; resins - 0.5; 2,6-DTB-4-MF - 78.1, add 365 g (36.5 wt.%) Of the ortho fraction of the composition, wt. %: phenol - 30.0; 2-TBP - 50.0; 2,6-DTBF - 20.0 and 54.6 g of BSK (4.0 wt.%).

The process is carried out as described in example 1, however, the temperature of the transalkylation process is 120 ^{° C.} and the reaction time is 6 hours. At the end of the process, 1210 g of the transalkylate composition is isolated, wt.%: 2-TBP - 3.50; 4-TBP - 3.04; 2-TB-4-MF - 36.01; 2,4-DTBF - 44.38; 2.6-DTB-4-MF - 10.77; phenol dimers - 2.19; resin - 0.11, by distillation from which 436 g of 2-TB-4-MF with a concentration of 98.6% and 513 g of 2,4-DTBP with a concentration of 97.9% are isolated.

 Example 4

 The process is carried out analogously to example 3, however, the amount of the ortho fraction is 500 g (50% by weight of the waste), and during the rectification of the transalkylate, 2-TB-4-MF and 2,4-DTBF are not separated. At the end of the process, 1410 g of transalkylate composition is isolated, wt.%: 2-TBP - 6.8; 4-TBP - 4.25; 2,6-DTB-4-MF - 4.1; 2,4-DTBF - 42.8; 2-TB-4-MF - 39.9; dimers - 2.05; resin - 0.1, by distillation from which 1120 g of a mixture of 2,4-DTBP and 2-TB-4-MF are isolated, which are used without synthesis for the synthesis of bis-alkyl phenols.

 Example 5

 1000 g of waste from the production of 2,6-DTBF composition, wt. %: 2,6-DTBF - 10.0; 2,4-DTBF - 14.8; 2,4,6-TTBF - 74.5; resins - 1.5, 345 g of the ortho-fraction (34.5 wt.%) composition, wt.%: phenol - 25; 2-TBP - 60; 2,6-DTBF - 15 and 13.45 g of BSK (1 wt.%).

The process is carried out, as in example 1, at a temperature of 130 ^o C. The obtained transalkylate in the amount of 1294 g of the composition, wt.%: 2-TBP - 7.25; 4-TBP - 3.95; 2,4-DTBF - 77.21; 2,4,6-TTBF - 11.0 resins - 0.59 are subjected to rectification and 934 g of 2.4 - fraction are isolated with a basic substance content of 97.5%.

 Example 6

 1000 g of waste from the production of 2,6-DTBF composition, wt. %: 2,6-DTBF - 30.0; 2,4-DTBF - 15.0; 2,4,6-TTBF - 52.5; resins - 2.5; 265 g (26.5 wt.%) Of the ortho-fraction of the composition, wt.%: Phenol - 30.0; 2-TBP - 45; 2,6-DTBP - 25.0 and 37.95 g of paratoluenesulfonic acid - p-TSC (3.0 wt.%).

The process is carried out as in example 1, however, the temperature of the transalkylation reaction is 130 ^{° C.} and the reaction time is 2 hours. The resulting transalkylate in an amount of 1150 g of the composition, wt.%: 2-TBP - 5.65; 4-TBP - 4.78; 2,4-DTBF - 82.7; 2,4,6-TTBF - 6.66; resins - 0.21 are rectified and 925 g of 2.4 - fraction are isolated with a basic substance content of 97.0 wt.%.

 Example 7

 1000 g of waste from the production of 2,6-DTBF composition, wt. %: 2,6-DTBF - 30.0; 2,4-DTBF - 14.5; 2,4,6-TTBF - 51.5; resins - 4.0; 200 g of the ortho fraction (20.0 wt.%) Composition, wt.%: Phenol - 15.0; 2-TBP - 60.0; 2,6-DTBF - 25.0 and 18.95 g of BSK (1.5 wt.%). The process is carried out as in example 1, however, the neutralization of the alkylate is carried out with sodium hydroxide. The resulting transalkylate in an amount of 1020 g of the composition, wt.%: 2-TBP - 0.3; 4-TBP - 0.35; 2,4-DTBF - 83.35; 2,4,6-TTBF - 15.5; resin - 0.5 is subjected to rectification and emit 880 g of 2.4 - fraction with a concentration of the main substance of 98.1%.

 Example 8

 1000 g of waste of 2,6-DTBF composition, wt.% 2,6-DTBF - 10.0 are charged into the autoclave; 2,4-DTBF - 10.0; 2,4,6-TTBF - 78.5; resin - 1.5 and 130 g of a light fraction of the composition, wt. %: 2-TBP - 50.0; 4-TBP - 42.3; 2,4-DTBF - 7.79 and 270 g of the ortho-fraction of the composition, wt. %: phenol - 25.0; 2-TBP - 60.0; 2,6-DTBF - 15.0 (the amount of the ortho-fraction and light fraction is 40 wt.%). Contribute 26 g of BSK (2 wt.%) And the process is conducted, as in example 1.

 The resulting transalkylate in an amount of 1500 g of the composition, wt.%: 2-TBP - 3.8; 4-TBP - 4.81; 2,4-DTBP 82.31; 2,4,6-TTBF - 9.02; resins - 0.15 are rectified and 890 g of a 2.4-fraction are isolated with a concentration of the main substance of 97.9 wt.%.

 Example 9

Conducting condensation of 2-tert-butyl-4-methylphenol with formaldehyde, for which 557 g of 2-TB-4-MF obtained in example 1 and 16.71 g are charged into a reactor with a stirrer, reflux condenser, thermometer and heating bath. (3 wt.%) Benzenesulfonic acid. The mixture is heated to 60 ^{° C.} and, after melting, the stirrer is turned on and a 37% aqueous solution of formaldehyde is dispensed in an amount of 275.4 g (molar ratio of alkyl phenol: formaldehyde 2.0: 1.3) for 2 hours. At the end of dosing, the temperature of the reaction mass is raised to 100 ^o C and stirring is continued for another 4 hours.

Upon completion of the condensation process, the catalyst is neutralized with sodium hydroxide. Then the precipitate is filtered and crystallization from gasoline gives 522 g of 2,2-methylene-bis- (4-methyl-6-tert-butylphenol) with a melting point of 131-132.5 ^o C.

 Example 10

511 g of 2-TB-4-MF obtained in example 2 and 2.55 g of BSK (0.5 wt.%) Are loaded into the reactor. The mixture is heated to 0 ^{° C.} and, after melting, the stirrer is turned on and 142.1 g (molar ratio 2: 1.2) of methylal are metered in for 1 hour. The condensation is carried out for 2 hours at a temperature of 135 ^o C. Upon completion of the process, the catalyst is separated by passing the reaction mass through a layer of calcium oxide. Crystallization from n-pentane isolated 506 g of 2,2-methylene-bis- (4-methyl-6-tert-butylphenol) with a melting point of 131-132.5 ^o C.

 Example 11

436 g of 2-TB-4-MF obtained in Example 3 and 17.44 g (4% by weight) of alkylbenzenesulfonic acid are charged to the reactor. The mixture is heated to 70 ^{° C.} and 58.5 g of acetaldehyde are metered in with constant stirring (molar ratio of 2-TB-4-MF: acetaldehyde is 2: 1). The condensation is carried out for 5 hours at a temperature of 70 ^o C. Upon completion of the process, the catalyst is separated off and crystallization from hexane 438 g of 1,1-bis (3-methyl-5-tert-butyl-6-hydroxyphenyl) -ethane with a melting point of 104 -105 ^o C.

 Example 12

545 g of 2,4-DTBP obtained in Example 1 and 10.9 g (2% by weight) of BSK are charged into the reactor. The mixture is heated to 65 ^{° C.} and 54.3 g of paraform (based on 95%. Molar ratio 2: 1.3) are metered with constant stirring. At the end of dosing, 610 g of 100% nefras are introduced into the reaction mass. The condensation is carried out with constant stirring for 3 hours at a temperature of 145 ^o C. At the end of the process, the catalyst is separated off, washed with nefras, filtered and 507 g of 2,2-methylene-bis- (4,6-ditret-butylphenol) are isolated with a melting point of 141 -142.5 ^o C.

 Example 13

520 g of 2,4-DTBP obtained in Example 2 and 18.2 g of BSK (3.5 wt.%) Are charged into the reactor. The mixture is heated to 60 ^{° C.} and 56.8 g of acetaldehyde are dosed with constant stirring (molar ratio 2: 1.05). At the end of dosing, 119 g of gasoline (20 wt.%) Is introduced into the reaction mass and the temperature is raised to 80 ^° C. At this temperature, the reaction mass is kept under constant stirring for 4 hours. Upon completion of the process, the catalyst is separated off and crystallization from gasoline gives 512 g of 1,1-bis- (3,5-ditret-butyl-6-hydroxyphenyl) ethane with a melting point of 162-164 ^o C.

 Example 14

934 g of 3,5-DTBP obtained in Example 5 and 18.68 g (2 wt.%) Of BSK are loaded into the reactor. The mixture is heated to 70 ^{° C.} and 107 g of paraldehyde are dosed with constant stirring (molar ratio 2: 0.33). At the end of dosing, 530 g of hexane (50 wt.%) Is introduced into the reaction mass and synthesis is continued for 2 hours at 100 ^° C. At the end of the process, the catalyst is separated by filtration and 910 g of 1,1-bis- are isolated from hexane (3, 5-ditret-butyl-6-hydroxyphenyl) ethane with a melting point of 162-163.5 ^o C.

 Example 15

925 g of 2,4-DTBF obtained in Example 6 and 23.12 g of para-toluenesulfonic acid (2.5 wt.%), 231 g of benzaldehyde (molar ratio 2: 1.3) and 354 are loaded into a 3 liter autoclave g of pentane-isopentane fraction (30 wt.%). With constant stirring, the reaction is carried out at a temperature of 75 ^o C for 5 hours. At the end of the process, the autoclave is cooled, the catalyst is separated off, the precipitated crystals are filtered off, and after washing with n-pentane, 980 g of 2,2-benzylidene-bis- (4,6-ditret-butylphenol) with a melting point of 142-143.5 ^° C are isolated ^.

 Example 16

1120 g of a mixture of 2,4-di-alkylphenols obtained according to Example 4, 22.4 g of BSK (2.0 wt.%) And 385 g of absorbent (30 wt.%) Are loaded into the reactor. The mixture is heated to 60 ^{° C.} and 143 g of benzaldehyde are dosed with constant stirring (molar ratio 2.0: 1.1). After dosing, the synthesis is continued for another 3 hours at a temperature of 105 ^o C. Then the catalyst is separated, filtered, washed with absorbent and 1116 g of a mixture of 1,1-bis (3,5-ditret-butyl-6-hydroxyphenyl) ethane and 2 , 2-methylene-bis- (4-methyl-6-tert-butylphenol) with a melting point of 156-157 ^o C.

 From the foregoing it can be seen that the proposed method for producing spatially-hindered bis-alkyl phenols allows the qualified use of ionol production waste. Moreover, a high degree of conversion of space-hindered alkyl phenols to the target bis-alkyl phenols is achieved.

 As can be seen from examples 1, 9, 12; 2, 10, 13; 4, 16; 5, 14 and 6, 15 the degree of use of raw materials excluding return monoalkylphenols is 67-77 wt.%. According to the prototype, it is 46.51 wt.% (2150 kg of raw material is consumed per 1000 kg of the finished product).

 The use of waste products of ionol as a raw material for the production of bis-alkyl phenols will significantly reduce the cost of the target products.

 It should also be noted that the proposed method can drastically reduce wastewater and simplify the technology: there is no need to prepare an emulsion medium, aldehyde solution, and water-salt solution.

 The use of arylsulfonic acids as catalysts and the almost complete exclusion of the aqueous medium contribute to the reduction of equipment corrosion.

Claims (2)

1. The method of obtaining spatially hindered bis-phenols of the formula

where R 'is hydrogen or C ₁ alkyl or benzyl;
R ″ and R ″ ″ are the same or different and are CH ₃ , C ₄ H ₉ ,
including the alkylation of a mixture of alkyl phenols in the presence of an acid catalyst at elevated temperature, the neutralization of alkylate, the separation of monoalkyl-para-alkyl phenol by distillation and its condensation with an aldehyde and the isolation of the target product by crystallization, followed by washing the resulting product, characterized in that the waste product is used as the initial mixture of alkyl phenols 2,6-di-tert-butylphenol obtained by alkylation of phenol with isobutylene, from the rectification stage of the composition, wt. %:
2,6-Di-tert-butylphenol (2,6-DTBP) - 1.0-30.0
2,4-Di-tert-butylphenol (2,4-DTBP) - 10.0-15.0
Resins - 1.5-4.0
2,4,6-Tri-tert-butylphenol (2,4,6-TTBF) - Other (up to 100)
or waste alkylphenols production of 2,6-di-tert-butyl-4-methylphenol (ionol) from the methanol recovery stage of the composition, wt. %:
2,6-Di-tert-butylphenol (2,6-DTBP) - 1.0-10.0
4,6-Di-tert-butyl-2-methylphenol (4,6-DTB-2MF) - 0.5-5.0
Dimethylaminomethylphenol - 1.0-4.0
Phenol Dimers - 1.0-8.0
Resins - 0.1-1.0
2,6-Di-tert-butyl-4-methylphenol (ionol) - Else (up to 100)
and ortho-fractions from the stage of separation of 2,6-di-tert-butylphenol composition, wt. %:
2-Tert-butylphenol (2-TBP) - 45.0-60.0
2,6-Di-tert-butylphenol (2,6-DTBP) - 15.0-25.0
Phenol - Else (up to 100)
in an amount of 20-50 wt. % by weight of alkyl phenol waste in the presence of arylsulfonic acid in an amount of 1-4 wt. % by weight of alkyl phenols at a temperature of 120-145 ^o С, followed by neutralization of the obtained alkylate, isolation of 2,4-dialkyl phenol by distillation and condensation in the presence of arylsulfonic acid with aldehydes or their derivatives selected from the group: formaldehyde, paraform, acetaldehyde, paraldehyde, benzaldehyde or methylal, by isolating the desired bis-alkylphenol.  2. The method according to p. 1, characterized in that as arylsulfonic acid use either benzosulfonic acid or paratoluenesulfonic acid.