A method of obtaining a spatial-obstructed bis-phenols


C07C37/48 - by exchange of hydrocarbon groups which may be substituted, from other compounds, e.g. transalkylation

 

(57) Abstract:

The invention relates to the petrochemical industry, in particular to a method for spatial-obstructed bis-phenols of General formula

< / BR>
where R' is hydrogen, or alkyl WITH1or benzyl; R 'and R" are identical or different and represent CH3WITH4H9by parallelomania mixture of alkyl phenols, which are used or waste 2,6-di-tert-butylphenol obtained by alkylation of phenol with isobutylene, from the stage of rectification, or waste 2,6-di-tert-butyl-4-METHYLPHENOL (BHT) from the stage of regeneration of the methanol. As the alkylating agent used fraction from the stage of selection of 2,6-di-tert-butylphenol composition, wt. %: 2-tert-butylphenol 45,0-60,0, 2,6-di-tert-butylphenol 15,0-25,0, phenol - rest (up to 100), in the amount of 20-50 wt.% the mass alkylphenolic waste. Then conduct a condensation with a lower aldehydes or donor aldehydes in the presence of arylsulfonate at a temperature of 70-140oC. Technical result - target use of waste from obtaining stabilizers for rubber vulcanizers plastics. 1 C.p. f-crystals.

The invention relates to the General formula

< / BR>
where R' is hydrogen or alkyl C1, or benzyl;

R" and R"' are the same or different and represent CH3WITH4H9,

used as an effective, colorless treatment, non-toxic, low volatile stabilizers for rubbers, vulcanizer, plastics and other organic products.

A method of obtaining a spatial-obstructed 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 separation of 4-methyl-2-tert-butylphenol and its condensation with formaldehyde. The condensation is carried out in the presence of acid catalyst in water-emulsion medium containing a surfactant and an organic solvent, at a temperature of 75-90oWith [U.S. Pat. USA 2796445,(1957), S. A. 51 16539 (1957)].

Also known is a method of obtaining 2,2-methylene-bis-(4-methyl-6-tert-butylphenol), including the condensation of 4-methyl-2-tert-butylphenol with formaldehyde in the presence of sulfuric acid in water-emulsion medium under 80oWith the neutralization of the catalyst and the selection of the finished product. The yield of the target product is 85-90% [Chemical industry, 1967, S. 19-21].

oWith a selection of dialkylphenol and further condensation with aldehydes or ketones [A. S. USSR 405665, IPC C 07 C 59/16, 1971].

A method of obtaining 2,2-methylene-bis-(4-methyl-6-tert-butylphenol), including dealkylation of 2,6-di-tert-butyl-4-METHYLPHENOL heated at arylsulfonate catalyst with subsequent condensation of the reaction mass with metallum in the presence of N,N-di-methyl-(3,5-di-tert-butyl-4-oxybenzyl)-amine (base manniche) at a molar ratio arylsulfonate:the basis of manniche 1,00 0,01 to 0,50 [RF Patent 2150461, IPC C 07 C 59/16, 1995].

A method of obtaining a spatial-obstructed bis - or polyphenol interaction dialkylphenols with aldehydes in acidic medium at 60-200oC. as catalysts use of Lewis acid, Bronsted, cation-exchange resin [A. S. USSR N 732232, IPC C 07 C 59/16, 1980].

The disadvantages of the above methods to obtain bis-alkyl phenols include the following: the presence of large amounts of wastewater, utilizing eye-catching olefins, using as raw material the spatial-obstructed ALKYLPHENOLS, which is the target products.

The closest technical solution to sawla the-tert-butylphenol), including parallelomania mixture of BHT and p-cresol when a molar ratio of 1.0:1,3-3,0 in the presence of an acidic catalyst at 55-65oWith the neutralization of the alkylate, highlighting monoalkyl-paracresol by distillation and crystallization with subsequent washing of the obtained product and its condensation with formaldehyde [U.S. Pat. RF 2049087, IPC C 07 C 39/16, 1995].

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

Condensation of monoalkyl-paracresol lead in the environment of water-hydrocarbon emulsions with a 15-20% solution of formaldehyde in water.

The described method has the following disadvantages:

- use as raw material expensive individual products - ionol and p-cresol;

- use as a catalyst of sulfuric acid, which leads to the resinification of initial and final products, as well as to severe corrosion of the equipment;

- the presence of large amounts of wastewater. Production of 1 ton of antioxidant spent not less than 2100 liters of water;

- additional cleaning monoalkyl-paracresol by recrystallization;

- use emulsifier, polluting wastewater;

- about the need of the invention is the expansion of raw materials, cost reduction target products, reduction of wastewater, disposal of waste 2,6-di-tert-butyl-4-METHYLPHENOL (BHT), which currently do not find a qualified application, simplifying the process and improving the utilization of raw materials.

The technical result is ensured in the proposed method of obtaining spatial-obstructed bisphenol formula

< / BR>
where R' is hydrogen, or alkyl WITH1or benzyl;

R" and R"' are the same or different and represent CH3WITH4H9,

parallelogram mixture of ALKYLPHENOLS, which use waste 2,6-di-tert-butylphenol obtained by alkylation of phenol with isobutylene, from the stage of distillation 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

Resin - 1,5 - 4,0

2,4,6-Tri-tert-butylphenol (2,4,6-TTBP) - the Rest (up to 100)

or waste of ALKYLPHENOLS production of 2,6-di-tert-butyl-4-METHYLPHENOL (BHT) from the stage of regeneration of the methanol composition, wt.%:

2,6-Di-tert-butylphenol (2,6-DTBP) - 1,0 - 10,0

4,6-Di-tert-butyl-2-METHYLPHENOL (4,6-DTB-MF) - 0,5 - 5,0

Dimethylaminomethylphenol - 1,0 - 4,0

Dimers of phenols - 1,0 - the allocation 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 - Rest (up to 100)

in the amount of 20-50 wt.% the mass alkylphenolic waste in the presence of arylsulfonate in the number of 1-4 wt.% on the weight of alkyl phenols at a temperature of 120-145oC, followed by neutralization of the resulting alkylate, allocation of 2,4-dialkylphenol by distillation and condensation with aldehydes or their derivatives, selected from the group of formaldehyde, paraform, acetaldehyde, methylal or benzaldehyde, the selection of the target bis-alkylphenol.

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

Waste of BHT from the stage of selection of 2,6-di-tert-butylphenol and stage of regeneration of the methanol't currently find qualified - burn.

Introduction to waste, containing various alkyl-substituted phenols, ortho-faction allows for a broader use, so is amerikali 2,6-di-tert-butylphenol to 2,4-di-tert-butylphenol and the reaction of alkylation of phenol released with isobutylene to 2-tert-butylphenol and 4-tert-butylphenol, which, in turn, react to parallelomania, which leads to an increase in the yield of 2,4-dialkylphenol.

The feature of using ortho-fractions it is possible to obtain simultaneously two different 2,4-ALKYLPHENOLS.

Thus, with the use of waste products of BHT from the stage of regeneration of the methanol you can get two of the target product:

2,4-di-tert-butylphenol and 2-tert-butyl-4-METHYLPHENOL approximately equal amounts and not separated, to obtain a mixture of the corresponding bis-alkyl phenols.

The separation of the catalyst by filtration, passing through the calcium oxide or the processing of the main agents can dramatically reduce, if not avoid the formation of phenolic wastewater, as well as to increase the output of the intermediate and target products, the loss of which with a water layer inevitable.

Source reagents meet the following requirements:

- Benzosulfimide - TU 6-36-0204229-25-89;

- A pair of toluensulfonate - TU 6-14-144-76;

- Alkylbenzenesulfonate - TU 2481-036-04689375-95;

- Formaldehyde - GOST 1625-89;

- Perform - TU 6-09-3208-78;

- Paraldehyde is recommended THAT 6-09-1682-77;

- Acetaldehyde - GOST 9585-77;

- Methylal - TU 6-09-the new faction THAT 6-09-3661-74; THE 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.

In an autoclave with a stirrer, thermomepart, heating jacket download waste of ionol, ortho-fraction of node separation of 2,6-DTBP and arylsulfonate (benzene, alkyl or p-toluensulfonate). The number of ortho-fraction of 20-50 wt.% from the weight of the loaded waste, and the amount of catalyst is 1-4 wt.% from the mass of the loaded APS.

The resulting mixture was heated under stirring until 120-145oC, kept at this temperature for 3-6 hours, and the pressure in the autoclave is raised to 2.0-3.5 ATM. When the process pressure drops almost to atmospheric. Then the autoclave is cooled, the separated catalyst is passed through the calcium oxide, treated with alkaline agents) and received transulcent sent for rectification.

Selected 2,4-di-alkyl phenol is used to produce bis-alkyl phenols, for which it is loaded into a reactor equipped with a stirrer, thermometer and reflux condenser. There make arylsulfonate in the number of 1-4,0 wt.% on zag the receive mixer and within 1.0 to 2.0 hours metered claimed aldehyde or its derivative in an amount of 1.0 to 1.5 moles per mole of alkylphenol. At the end of the dosing continue stirring the reaction mass for 2-6 hours at a temperature of 70-140oC. In the case of obtaining bis-phenol with a melting point above the reaction temperature (which hampered the work of agitators) after dosing aldehyde in the reactor impose an organic solvent in the amount of 10-50 wt.% to the reaction mass (gasoline nefras, n-pentane, hexane). Upon completion of the reaction is separated catalyst (e.g., filtering) and crystallization of the above solvents emit bis-ALKYLPHENOLS.

The yield of the target products loaded 2,4-dialkylphenol is 92-98% by weight from theoretical.

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

Example 1.

In the autoclave load 1000 g waste of ionol (from the stage of regeneration of methanol) composition, wt.%: 2,6-di-tert-butylphenol (2,6-DTBP) - 2,2; di-methyl-aminomethylphenol (DMMP) - 1,20; 4,6-di-tert-butyl-2-METHYLPHENOL (4,6-DTB-2-MF) - 0,80; dimers of phenols - 3,9; resin - 0,1; 2,6-di-tert-butyl-4-METHYLPHENOL (BHT) - 91,8. Add 460 g (46 wt.%) ortho-fraction composition, wt. %: 2-tert-butylphenol (2-TBP) - 60,0; 2,6-DTBP - 15,0; phenol - 25,0 and 43.8 g of benzosulfimide (BSC) at the rate of 3 wt.% to the reaction mass, the pressure in the reactor drops from 3.5 MPa to about atmospheric. Upon completion of the reaction, reduce the temperature of the reaction mixture to 105oWith and with constant stirring contribute 11 g of potassium hydroxide. The neutralization process are within 1.5 hours. After neutralization turn off the stirrer, and the mixture advocate for 1.5 hours, without reducing the temperature.

After settling condensed separate part consisting of resins, potassium BSC, salt BSC and DAMP and transulcent in the number 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-DTBP to 39.4; 2,5-DCB-4-MF - 10,38; dimers of phenols to 0.69, sent for rectification, which emit 557 g 2-TB-4-MT with a concentration of 98.5 wt.% and 545 g of 2,4-DTBP with the concentration of the basic substance of 97.8 wt. %. Selected ALKYLPHENOLS (2-TB-4-MT and 2.4-DTBP) is used to produce bis-alkyl phenols, condensing them with the claimed aldehydes or their deputies.

Example 2.

In the autoclave load 1000 g waste of ionol composition, wt.%: 2,6-DTBP - 1,05; DAMP - 4,0; 4,6-DTB-2-MF - 2,5; dimers of phenols - 7,9; resin - 1,0; 2,6-TB-4-MF - 83,55 add 350 g (35 wt.%) ortho-fraction composition, wt. %: phenol - 30; 2-TBP - 45; 2,6-DTBP - 25 and 47,25 g of para-toluenesulfonic acid (3.5%). The process is conducted as described in example 1, however, DL is lancalculator composition, wt.% : 2-TBP - 1,7; 4-TBP - 1,17; 4-TBP - 1,17; 2-TB-4-MF - 39,29; 2,4-DTBP - 40,84; 2,6-DTB-4-MF - 11,92; dimers of phenol - 5,00; resin to 0.08, the rectification of which emit 511 g 2-TB-MF concentration 98,0 and 520 g of 2,4-DTBP concentration of 97.5%.

Example 3.

In the autoclave load 1000 g waste of ionol composition, wt.%: 2,6-DTBP - 9,8; DAMP - 2,5; 4,6-DTB-2-MF - 5,0; phenol dimers of 4.1; resin - 0,5; 2,6-DTB-4-MF - 78,1 add 365 g (of 36.5 wt.%) ortho-fraction composition, wt. %: phenol - 30,0; 2-TBP - 50,0; 2,6-DTBP - 20,0 and 54.6 g of BSC (4.0 wt%).

The process is conducted as described in example 1, but the temperature of the process transaminirovania 120oC and a reaction time of 6 hours. At the end of the process emit 1210 g of transalkylation composition, wt.%: 2-TBP - 3,50; 4-TBP - 3.04 from; 2-TB-4-MF - 36,01; 2,4-DTBP - 44,38; 2,6-DTB-4-MF - 10,77; dimers of phenol - 2,19; resin - 0,11, the rectification of which emit 436 g 2-TB-4-MF concentration to 98.6% and 513 g of 2,4-DTBP concentration is 97.9%.

Example 4.

The process is carried out analogously to example 3, however, the number of ortho-faction 500 g (50% by weight of waste) and rectification of transalkylation not produce division 2-TB-4-MT and 2.4-DTBP. At the end of the process emit 1410 of transalkylation composition, wt.%: 2-TBP - 6,8; 4-TBP - 4,25; 2,6-DTB-4-MF - 4,1; 2,4-DTBP - 42,8; 2-is selenia used for the synthesis of bis-alkyl phenols.

Example 5.

In the autoclave load 1000 g waste 2,6-DTBP composition, wt. %: 2,6-DTBP - 10,0; 2,4-DTBP - 14,8; 2,4,6-TTBP - 74,5; resin - 1,5, 345 g of ortho-faction (of 34.5 wt.%) composition, wt.%: phenol - 25; 2-TBP - 60; 2,6-DTBP - 15 and 13,45 g BSK (1 wt.%).

The process is conducted as in example 1, at a temperature of 130oC. Received transulcent in the number 1294 g of the composition, wt.%: 2-TBP - 7,25; 4-TBP - 3,95; 2,4-DTBP - 77,21; 2,4,6-TTBP - 11,0 resin 0.59 is subjected to rectification and allocate 934 g of 2,4 - faction with the basic substance content of 97.5%.

Example 6.

In the autoclave load 1000 g waste 2,6-DTBP composition, wt. %: 2,6-DTBP - 30,0; 2,4-DTBP - 15,0; 2,4,6-TTBP - 52,5; resin - 2,5; 265 g (26.5 wt.%) ortho-fraction composition, wt.%: phenol - 30,0; 2-TBP - 45; 2,6-DTBP - 25,0 and 37,95 g paratoluenesulfonyl - p-TJC (3.0 wt.%).

The process is conducted as in example 1 but the reaction temperature of transaminirovania is 130oC and the reaction time is 2 hours. Received transulcent in the amount of 1150 g of the composition, wt.%: 2-TBP - 5,65; 4-TBP - 4,78; 2,4-DTBP - 82,7; 2,4,6-TTBP - 6,66; resin - 0,21 is subjected to rectification and allocate 925 g of 2,4 - faction with the content of the basic substance 97,0 wt.%.

Example 7.

In the autoclave load 1000 g waste 2,6-DTBP composition, 0; 2,6-DTBP - 25,0 and 18,95 g BSC (1.5 wt%). The process is conducted as in example 1, however, the neutralization of alkylate are sodium hydroxide. Received transulcent in the amount of 1020 g of the composition, wt.%: 2-TBP - 0,3; 4-TBP - 0,35; 2,4-DTBP - 83,35; 2,4,6-TTBP - 15,5; resin - 0,5 subjected to rectification and allocate 880 g of 2,4 - faction with the concentration of the basic substance to 98.1%.

Example 8.

In the autoclave load 1000 g waste 2,6-DTBP composition, wt.% 2,6-DTBP - 10,0; 2,4-DTBP - 10,0; 2,4,6-TTBP - 78,5; resin - 1.5 and 130 g light fraction composition, wt. %: 2-TBP - 50,0; 4-TBP - 42,3; 2,4-DTBP - 7,79 and 270 g of ortho-fraction composition, wt. %: phenol - 25,0; 2-TBP - 60,0; 2,6-DTBP - 15,0 (the number of ortho-fraction and light fraction 40 wt.%). Make 26g BSC (2 wt. per cent) and the process is conducted as in example 1.

Received transulcent in the amount of 1500 g of the composition, wt.%: 2-TBP - 3,8; 4-TBP - 4,81; 2,4-DTBP - 82,31; 2,4,6-TTBP - 9,02; resin - 0,15 subjected to rectification and allocate 890 g of 2,4 - faction with the concentration of the basic substance is 97.9 wt.%.

Example 9.

Carry out the condensation of 2-tert-butyl-4-METHYLPHENOL with formaldehyde in the reactor with stirrer, reflux condenser, thermometer and bath for heating load 557 g 2-TB-4-MF obtained in example 1, and 16,71 g (3 wt. %) benzosulfimide. The mixture is heated to 60oAnd, p is,4 g (the molar ratio of alkyl phenol:formaldehyde 2,0:1,3) within 2 hours. At the end of the dispensing temperature of the reaction mass was raised to 100oWith and continue stirring for another 4 hours.

Upon completion of the condensation process to neutralize the catalyst is sodium hydroxide. Then the precipitate is filtered and crystallization from petrol receive 522 g of 2,2-methylene-bis-(4-methyl-6-tert-butylphenol) with a melting point 131-132,5oC.

Example 10.

Charged to the reactor 511 g 2-TB-4-MF obtained in example 2 and 2.55 g BSC (0.5. %). The mixture is heated to 0oAnd, after melting, include a stirrer and with constant stirring metered in over 1 hour to 142.1 g (molar ratio of 2: 1,2) matilla. Condensation lead for 2 hours at a temperature of 135oC. Upon completion of the process to separate the catalyst, passing the reaction mass through a layer of calcium oxide. Crystallization from n-pentane allocate 506 g of 2,2-methylene-bis-(4-methyl-6-tert-butylphenol) with a melting point 131-132,5oC.

Example 11.

Charged to the reactor 436 g 2-TB-4-MF obtained in example 3, and 17,44 g (4 wt.%) alkylbenzenesulfonate. The mixture is heated to 70oWith and with constant stirring metered 58.5 g of acetaldehyde (molar ratio of 2-TB-4-MOF: acetaldehyde is 2:1). Con is stylizacji from hexane allocate 438 g of 1,1-bis(3-methyl-5-tert-butyl-6 oksifenil)-ethane with a melting point 104-105oC.

Example 12.

Charged to the reactor 545 g of 2,4-DTBP obtained in example 1, and 10.9 g (2 wt. %) BSC. The mixture is heated to 65oWith and with constant stirring dosed to 54.3 g Performa (calculated at 95%. The molar ratio of 2:1,3). At the end of dosing in the reaction mass is injected 610 g 100% nefras. The condensation is carried out at constant stirring for 3 hours at a temperature of 145oC. Upon completion of the process to separate the catalyst, washed with neprasam, filtered and allocate 507 g of 2,2-methylene-bis-(4,6-decret-butylphenol) with a melting point 141-142,5oC.

Example 13.

Charged to the reactor 520 g of 2,4-DTBP obtained according to example 2, and 18.2 g of BSC (3.5%). The mixture is heated to 60oWith and with constant stirring dose of 56.8 g of acetaldehyde (molar ratio 2:1,05). At the end of dosing in the reaction mass is injected 119 g of gasoline (20 wt.%) and raise the temperature to 80oC. At this temperature the reaction mass is maintained at a constant stirring for 4 hours. Upon completion of the process to separate the catalyst and crystallization from petrol allocate 512 g of 1,1-bis-(3,5-decret-butyl-6 oksifenil)-ethane with a melting point 162-164oC.

Example 14.

C and under stirring with a dose of 107 g of paraldehyde is recommended (molar ratio 2:0,33). At the end of dosing in the reaction mass is injected 530 g of hexane (50 wt.%) and continue synthesis for 2 hours at 100oC. Upon completion of the filtering process to separate the catalyst and crystallization from hexane allocate 910 g of 1,1-bis-(3,5-decret-butyl-6 oksifenil)-ethane with a melting point 162-163,5oC.

Example 15.

In the autoclave with a capacity of 3 l load 925 g of 2,4-DTBP 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 g of pentane-isopentane fraction (30 wt.%). With constant stirring the reaction is carried out at a temperature of 75oC for 5 hours. At the end of the process, the autoclave is cooled, separate the catalyst, the precipitated crystals filtered off and, after washing with n-pentane allocate 980 g of 2,2-benzylidene-bis-(4,6-decret-butylphenol) with a melting point 142-143,5oC.

Example 16.

Charged to the reactor 1120 g of a mixture of 2,4-di-alkyl phenols, obtained according to example 4 of 22.4 g BSC (2.0 wt.%) and 385 g of the adsorbent (30 wt.%). The mixture is heated to 60oWith and with constant stirring metered 143 g of benzaldehyde (molar ratio of 2.0:1,1). Portrait, washed absorbent and produce 1116 g of a mixture of 1,1-bis-(3,5-decret-butyl-6 oksifenil)-ethane and 2,2-methylene-bis-(4-methyl-6-tert-butylphenol) with a melting point 156-157oC.

From the foregoing it is seen that the proposed method for spatial-obstructed bis-alkyl phenols allows you to efficiently use the waste products of BHT. And achieved a high degree of spatial transformation is obstructed ALKYLPHENOLS in the target bis-ALKYLPHENOLS.

As can be seen from examples 1, 9, 12; 2, 10, 13; 4, 16; 5, 14 and 6, 15 utilization of raw materials excluding return monoalkylphenol is 67-77 wt.%. For the prototype it is 46,51 wt.% (per 1000 kg of finished product is consumed 2150 kg of raw materials).

Use of waste products of BHT as a raw material for producing bis-alkyl phenols will significantly reduce the cost of target products.

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

The use as catalysts of arylsulfatase and almost full iskluceno-obstructed bis-phenols of the formula

< / BR>
where R' is hydrogen, or alkyl WITH1or benzyl;

R" and R"' are identical or different and represent CH3WITH4H9,

including parallelomania mixture of alkyl phenols in the presence of an acid catalyst at elevated temperature, neutralization of alkylate, highlighting monoalkyl-para-alkylphenol by distillation and condensation with the aldehyde and the selection of the target product by crystallization with subsequent washing of the obtained product, characterized in that as the source of a mixture of alkyl phenols using waste 2,6-di-tert-butylphenol obtained by alkylation of phenol with isobutylene, from the stage of distillation 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

Resin - 1,5-4,0

2,4,6-Tri-tert-butylphenol (2,4,6-TTBP) - the Rest (up to 100)

or waste of ALKYLPHENOLS production of 2,6-di-tert-butyl-4-METHYLPHENOL (BHT) from the stage of regeneration of the methanol composition, wt. %:

2,6-Di-tert-butylphenol (2,6-DTBP) - 1,0-10,0

4,6-Di-tert-butyl-2-METHYLPHENOL (4,6-DTB-MF) - 0,5-5,0

Dimethylaminomethylphenol - 1,0-4,0

Dimers of phenols - 1,0-8,0

Resin - 0,1-1,0

2,6-Di-tert-butyl-4-METHYLPHENOL (BHT) - the Rest (up to 100)

and the PR 2,6-Di-tert-butylphenol (2,6-DTBP) - 15,0-25,0

Phenol - Rest (up to 100)

in the amount of 20-50 wt. % the mass alkylphenolic waste in the presence of arylsulfonate in the number of 1-4 wt. % by mass of alkyl phenols at a temperature of 120-145oC, followed by neutralization of the resulting alkylate, allocation of 2,4-dialkylphenol by distillation and condensation him in the presence of arylsulfonate with aldehydes or their derivatives, selected from the group of formaldehyde, paraform, acetaldehyde, paraldehyde is recommended, benzaldehyde or matilal, the selection of the target bis-alkylphenol.

2. The method according to p. 1, characterized in that as arylsulfonate use or benzoylacetate, or paratoluenesulfonyl.

 

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2 tbl, 1 dwg

FIELD: chemical industry; methods of extraction of phenol and biphenols from the homogeneous reactionary mixtures.

SUBSTANCE: the invention is pertaining to the method of extraction of phenol and biphenols from the homogeneous reactionary mixtures of the direct oxidation of benzene by hydrogen peroxide. The method includes delivery of the reactionary mixture containing benzene, water, phenol, the sulfolane and the reaction by-products (biphenols) in еру distillation plant consisting of two or more columns for production of one or more products basically consisting of the azeotropic mixture of benzene with water and phenol, and also the product consisting of sulfolane, phenol and the reaction by-products. The stream including sulfolane is mixed with the water solution of the base and benzene for formation of the salts of the phenols and the subsequent stratification of the mixture, extraction by benzene and separation in the flow column containing benzene and sulfolane, which is returned in the reactor. From the same column separate the stream including sodium phenolates in the water solution, which is treated with the sulfuric acid for extraction of the phenols from their salts. At the stage of the extraction separate the extracting solvent, after distillation of which in the tailings bottom product receive the biphenols water solution. The separated organic solvent recirculates in the system. The technical result of the invention is improvement of the process of separation of phenols and biphenols from the complex azeotropic mixtures containing sulfolane.

EFFECT: the invention ensures the improved process of separation of phenols and biphenols from the complex azeotropic mixtures containing sulfolane.

9 cl, 1 ex, 1 dwg, 1 tbl

FIELD: chemistry.

SUBSTANCE: method involves two stages: a) cooling of a liquid mixture containing bisphenol-A and water in a bisphenol-A chiller with bisphenol crystals formation in the liquid phase; b) separation of bisphenol-A crystals from the liquid phase; c) at least, partial separation the liquid phase into bisphenol-rich organic phase and water-rich phase; d) feeding of phenol and at least a part of the bisphenol-rich organic phase to the adduct followed by formation of phenol and bisphenol-A crystal adduct in a mother solution; e) separation of crystal adduct from the mother solution; g) contact of at least a part of the mother solution obtained at the stage e) with a catalyst of isomerisation of bisphenol-A isomers into bisphenol-A; and h) recycling of at least a part of the mother solution processed at the stage g) through the stage d).

EFFECT: improved purity and output of the composition.

12 cl, 2 dwg, 1 ex

FIELD: chemistry.

SUBSTANCE: invention claims modified ion exchange resin, where at least one compound selected out of the following (A) and (B) compounds is linked by ion link to functional acid group of acid ion exchange resin, so that compound is linked by ion link to 0.1-50 mol % of total functional acid group number present in acid ion exchange resin: compound (A) is represented by formula 1, where P is phosphor atom; S is sulfur atom; H is hydrogen atom; R1 is alkylene group including 1 to 6 carbon atoms, where one fragment can include phenylene group; and each R2, R3 and R4 are independently (1) alkyl group including 1 to 6 carbon atoms, or (3) aryl group including 5 to 10 carbon atoms; and compound (B) is represented by formula 2, where P is phosphor atom; S is sulfur atom; H is hydrogen atom; each of R1 and R2 is alkylene group including 1 to 6 carbon atoms, where one fragment can include phenylene group; and each R3 and R4 are independently an aryl group including 5 to 10 carbon atoms. Also invention claims catalyst for obtaining bisphenols, based on this resin, and method of bisphenol obtaining. Invention claims methods of obtaining modified ion exchange resin (versions).

EFFECT: obtained catalyst with high selectivity to bisphenols, obtaining of bisphenol A with high acetone conversion grade.

9 cl, 10 ex

FIELD: chemistry.

SUBSTANCE: cumane hydroperoxide is decomposed in presence of acid catalyst from sulfated metal in order to transform cumane hydroperoxide into mass, which after decomposition contains mainly phenol and acetone, and mass reaction after decomposition is carried out, preferably without intermediate purification, in presence of cation catalyst, composed of cation-exchange resin and mercaptane promoter or promoter in form of mercaptoalkane acid in order to transform phenol and acetone in mass after decomposition mainly into diphenol A.

EFFECT: high product output with low admixture formation without necessity of stages of intermediate purification.

10 cl, 3 dwg, 6 ex

FIELD: chemistry.

SUBSTANCE: cumane hydroperoxide is decomposed in presence of catalyst from processed with acid clay in order to transform cumane hydroperoxide into mass, which after decomposition contains mainly phenol and acetone, and mass reaction after decomposition is carried out in presence of cation catalyst, composed of cation-exchange resin and mercaptane promoter or promoter in form of mercaptoalkane acid in order to transform phenol and acetone in mass after decomposition mainly into diphenol A.

EFFECT: high product output with low admixture formation without necessity of stages of intermediate purification.

10 cl, 3 dwg, 4 ex

FIELD: chemistry.

SUBSTANCE: claimed invention relates to method of obtaining bisphenol-A by interaction of phenol and acetone in presence of solid acid catalyst, in particular ion-exchange resin, and inert stripping agent (versions). One of method versions includes reaction of phenol and acetone with formation of bisphenole-A and water with anti-current and multi-stage contact with solid acid catalyst in presence of means for stripping, boiling within range from 50 to 90°C in conditions of condensation pressure, and which is inert in reaction conditions, as a result of which means for stripping removes water from reaction medium, and acetone dissolves in phenol.

EFFECT: ensuring of catching of practically all acetone in reaction zone and reaching almost 100% conversion.

15 cl, 1 tbl, 1 dwg, 1 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a method of producing a bisphenol synthesis catalyst. The method of producing a bisphenol synthesis catalyst, which contains an acidic cation-exchange resin on which a sulphur-containing amine compound is adsorbed, involves bringing the acidic cation-exchange resin into contact with acidic waste water, which contains a sulphur-containing amine compound, released from the catalyst synthesis stage. The waste water has initial concentration of the said sulphur-containing amine compound equal to or less than 170 parts per million (wt) and contact with the said circulating resin is done until the said concentration falls to 5 parts per million (wt) or less.

EFFECT: considerable removal of sulphur-containing amine compound from waste water after catalyst synthesis.

3 cl

FIELD: chemistry.

SUBSTANCE: method involves the following stages: a) reaction of phenol and acetone in the presence of acid catalyst to obtain reaction mix containing bisphenol A. Further, b) water is removed from reaction mix by distillation, with distillation column operated at 100°C to 150°C in the bottom column part and at 20°C to 80°C in the top column part, 50 mbar to 300 mbar absolute pressure in the top column part and 100 mbar to 300 mbar absolute pressure in the bottom column part. Bisphenol A adduct with phenol is removed from reaction mix before distillation at b) stage by crystallisation and filtration.

EFFECT: maximum retention of unreacted residual acetone in reaction solution.

9 cl, 1 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a method for continuous extraction of phenol from a partial stream formed during production of bisphenol A, where said partial stream contains 40-90 wt % phenol, 5-40 wt % bisphenol A, as well as 5-40 wt % by-products of the reaction of phenol and acetone to bisphenol A, in which a) a partial stream is fed into a vacuum distillation column containing at least 5 theoretical separation steps, b) in the vacuum distillation column phenol is distilled through the head part, c) a first portion of the stream from the base of the column is released from the process, and d) a second portion of the stream from the base of the column is continuously fed into the reactor in which there is isomerisation and splitting of bisphenol A and by-products contained in the stream from the base of the column to form phenol at temperature higher than 190°C and hydrodynamic holding for at least 120 minutes in the presence of an acid catalyst and then returned to the vacuum distillation column. Mass flow of the portion of the stream from the base of the column fed into the reactor is more than 30% of the mass flow of the partial stream at step a) fed into the vacuum distillation column.

EFFECT: method enables efficient processing of streams coming from production of bisphnol A to obtain highly pure phenol with high output.

5 cl, 1 tbl, 7 ex, 1 dwg

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