FI68255B - FOERFARANDE OCH ANORDNING FOER FRAMSTAELLNING AV POLYFENOLER - Google Patents

Description

68255

Method and apparatus for making polyphenols

The invention relates to a process for the preparation of polyphenols by oxidation polycondensation in an aqueous medium in the presence of an oxidant and separation of the final product. The invention also relates to an apparatus for producing polyphenols. The invention can be used with particular advantage in the preparation of known and novel polyphenols, the properties of which make them useful as heat-resistant, chemically resistant and radiation-resistant, and as antistatic agents for coatings and other applications. In addition, polyphenols may be useful as starting materials and curing agents in the synthesis of heat-resistant epoxy resins.

The need for a simple and inexpensive process for the commercial production of polyphenols has hitherto been compelling, despite the fact that the polymerization of phenols by oxidative polycondensation has been known to the person skilled in the art.

A process is known for the preparation of polyphenols in an oxygen manner by heteropolycondensation in the presence of a catalyst or catalysts selected from the group consisting of copper chloride, ferric chloride and aluminum chloride (U.S. Pat. No. 3,678,006 and SU inventor certificate 448,186). , but their manufacture is not always profitable. This is because said catalysts are effective only when used in equimolar amounts or in excess relative to the 30 monomers.

The high cost of the catalysts and the fact that they can only be used once in the polycondensation process must be taken into account here.

One process for preparing polyhydroquinone is also described in SU-inventor certificate 440 387. This process comprises oxidizing a hydroquinone polycondensate foundation in a second medium in the presence of an oxidant and separating the final product. Hydrogen peroxide (perhydrol) is mentioned as an oxidant in this method.

To effectively oxidize the monomer, the amount of perhydrol 5 in the reaction mixture must be at least 2.3 moles per mole of monomer. Undoubtedly, this method is advantageous in that only water is formed as a by-product in the polycondensation reaction, which is easy to separate from the final product.

10 Although this method is advantageous, as already mentioned above, it still has some significant drawbacks. The strong corrosive effect of perhydrol requires the use of expensive equipment. In addition, the method in question must take particular account of the explosive nature of perhydrol. Finally, perhydrol, which is used to the greatest extent, is a relatively expensive oxidant.

The object of the present invention was to provide a process and an apparatus for the production of polyphenols which make it possible to use an inexpensive, readily available and safe oxidant in polycondensation due to the conditions of the process and the design of the apparatus without compromising efficiency.

The invention is characterized in that the monomer of the phenol series is mixed with an aqueous alkali solution having a concentration of 5-56% in a molar ratio of 1: 2, 4-1: 0.5 and the suspension is heated to 70-170 ° C and air is passed through the reaction mixture. oxygen acts as an oxidant. 1 2 3 4 5 6 The readily available 2 substance used in this method, i.e. air, makes the method substantially cheaper 3 and does not cause a strong corrosion effect on the equipment.

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Oxygen in the air can be effectively used as the oxidant 5 only under the conditions specified above. In practice, the process is relatively safe and allows the production of sufficiently pure polyphenols in high yield of the final product. The above-mentioned polymers are heat-resistant and are useful both as basic and additional components in the preparation of heat-resistant coatings and in the preparation of various epoxy novolak compounds.

The phenolic acid monomer is preferably mixed with an 11 to 56% aqueous potassium hydroxide solution. Under these conditions, oxidative polycondensation is most intense.

One substance that can be used in the oxidative polycondensation of phenolic acid monomer 10 is 25-56% aqueous sodium hydroxide solution.

The air used as oxidant is preferably treated with alkali. When this is done, the carbon dioxide present in the air and taken up by the alkali will not subsequently have any detrimental effect on the oxidative polycondensation. This allows the yield of phenolic acid monomer to increase. The air is preferably treated with a concentrated alkali solution.

For best results, the relative air flow rate through the reaction mixture should be 0.007 to 20.016 m / h per kg of monomer.

To facilitate the separation of the reaction products, it is recommended to cool the mixture of reaction products to a temperature of 20-80 ° C after the passage of air through the reaction mixture has been stopped.

Cooling Neutralizing the mixture of reaction products with mineral acid and washing it with water to remove salts formed is the simplest step in the process. In this case, the most efficient step is to pass carbon dioxide through the mixture of reaction products after the oxidative polycondensation reaction of the monomer of the phenol series is completed.

When phenol (C 9 H 8 OH), octylphenol and cresol are used as starting materials, for best results, the reaction mixture is heated to 130-155 ° C and, after blowing air, cooled to 50-80 ° C, then stirred in water and carbon dioxide is blown through it.

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To obtain a quality product, it is suitable to dry the mixture of neutralized and washed reaction products at a temperature of 80-135 ° C.

To prevent atmospheric contamination, the air passed through the reaction mixture is preferably passed through an al-5 potassium aqueous solution. This step makes it possible to reduce both the basic and additional component losses (monomer and alkali of the phenolic series).

It is recommended to first cool the air passed through the reaction mixture and then pass it through the alkalive-10 silica solution. This makes it unnecessary to heat the alkaline water solution and thus reduces its aggressiveness.

The object of the present invention is also achieved by an apparatus for carrying out the process, the apparatus comprising a boiler with a heater, a shaft with blades mounted on the boiler and connected to a drive for rotating the shaft, a perforated tube mounted on the bottom of the boiler and connected to an air blower. According to the invention, the perforated tube is connected to the air blower for alkali treatment of the air through a chamber for 20 hours. The supply of air through the pretreatment chamber prevents carbon dioxide from entering the boiler and promotes an increase in polyphenol intake as well as the production of a clean product.

The alkali air treatment chamber, constructed as a multistage sorbent, is the simplest and most reliable modification of the apparatus of the invention.

The perforated tube is preferably in communication with a carbon dioxide source. When carbon dioxide is introduced into the mixture of reaction products, it bubbles through the suspension and provides better neutralization of the alkali.

To maintain optimal operating conditions, it is recommended to equip the outlet of the perforated tube with a flow meter.

In order to take advantage of the monomer and alkali losses of the phenol series, it is suitable for the upper part of the boiler to be connected via a pipe to the alkali-filled adsorber.

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To prevent alkali foam from being thrown out, it is recommended to provide the adsorber with a seal made of an alkali-inert fibrous material.

In order to prevent the neutralization of the alkali with carbon-5 dioxide in the neutralization of the mixture of reaction results in the boiler, it is appropriate that the bypass tube is connected past said adsorber to form an excess efflux of carbon dioxide.

It is preferred that the boiler be connected to the adsorber 10 via a reflux condenser. This prevents the alkali from overheating in the adsorber.

In order to check the process in time and to prevent disturbances, the pipe is preferably provided with an inspection glass11a.

The invention will now be described in more detail with reference to the accompanying drawing, which schematically shows an apparatus for carrying out the process according to the invention.

The process for producing polyphenols according to the invention is carried out by an apparatus comprising a boiler 1 provided with a heater 2 in the form of a jacket 3. The jacket 3 communicates with main supply lines 4 and 5 and main lines 6 and 7 for removing steam and cooling water. The shaft 8 provided with wings 9 is mounted on the roof 25 and connected to the drive 10 for rotating the shaft. The upper lid 11 of the boiler 1 is provided with a charging opening 12. A thermocouple 13 is attached to the upper lid 11. The upper part of the boiler 1 communicates with the adsorber 15 through the upper lid 11 by means of a pipe 14. The adsorber 15 is provided with a seal 30 16 made of an alkali-inert fibrous material.

The boiler is connected to the adsorber 15 and through the countercooler 17. The tubes 14 are provided with an inspection opening 18 which is closed with a transparent material. The bypass tube 19 is connected in parallel with the adsorber 15. Pipes 14 and bypass pipe 19 are provided with valves 20 and 21. Main supply pipes 4 and 5 and main lines 6 and 7 for removing steam and cooling water are provided with valves 22, 6 68255 23, 24, 25. Pipes 26 and 27 for supplying washing water and is passed through the side wall of the boiler 1 at different levels for removal. The bottom 28 of the boiler 1 is conical. The charge pipe 29, which is closed by the valve 30, is guided through the base 28. The perforated pipe 31 is mounted on the lower part of the boiler 1. The perforated tube 31 communicates with the air blower 32 through a chamber 33 for treating air with alkali. A humidity separator 35 is included in the main line 34 between the air blower 32 and the chamber 33.

The chamber 33 is constructed as a multi-stage adsorber comprising vessels 36, 37 and 38 which are in series communication with each other by means of siphon tubes 39, 40 and 41 and are filled with an aqueous alkaline solution. The chamber 33 communicates with a perforated tube 31 and a tube 42 provided with a valve 43. A flow meter 44 is mounted at the inlet of the perforated tube 31. The perforated tube 31 communicates with the carbon dioxide source 46 between the source 46 and the perforated tube 31. reduction valves 47 and 48. The carbon dioxide source 46 20 is constructed as a unit of removable (replaceable) vessels 49, 50 and 51 which contain carbon dioxide and are interconnected by a manifold 52.

The process according to the invention for the preparation of polyphenols is carried out as follows. Boiler 1 is charged through pa-25 riser 12 with a phenolic series monomer and an alkaline aqueous solution in a molar ratio of 1: 2.4 to 1: 0.25. The concentration of the alkaline aqueous solution is 5-56%. Under the influence of the drive device 10, the shaft 8 provided with vanes 9 rotates, thus confusing the monomer of the phenolic series and the alkaline water-30 solution. At the same time, the valves 22 and 24 are opened in the supply main line 4 and in the steam removal main line 6. The steam circulating in the jacket 3 heats the reaction mixture to a temperature of 70-170 ° C. At the same time, air is supplied to the reaction mixture from the air blower 32 through the perforated pipe 31. As it passes through the reaction mixture for a period of time, polyphenol is formed as a result of the oxidative polycondensation of the monomer of the phenol series.

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According to a preferred modification of the inventive process, the air used as oxidant is pretreated with a concentrated alkali solution in vessels 36, 37, 38. The blow rate 3 (speed) is kept in the range 0.007 to 0.016 m / h per 5 kg of monomer by adjusting the fan blower 32 or valve 32 The temperature conditions in the boiler 1 are maintained by means of valves 22 and 24 according to the readings of the meter connected to the thermocouple 13. Air that has passed through the reaction mixture 10 is fed to the adsorber 15 through a pipe 14 and a countercurrent cooler 17 while the valve 20 is opened and the valve 21 is closed. In the adsorber 15, air is passed through an aqueous alkaline solution which takes up the unreacted starting air monomer. The air, which is initially cooled in the countercurrent cooler 17, practically does not heat the alkali in the adsorber 15. Visual inspection of the production process can be carried out through an inspection glass 18, which makes it possible to determine the intensive foaming in the reaction mixture. The seal 16 prevents droplets of alkaline-20 aqueous solution from being thrown into the outside air.

In a preferred modification of the production process, potassium or sodium hydroxide is used to form an aqueous alkaline solution. When this is done, the concentration of the aqueous solution of potassium hydroxide is 11-56% and the concentration of the aqueous solution of sodium hydroxide is 25-56%. After completion of the oxidative polycondensation reaction, valves 22 and 24 are closed, valves 23 and 25 are opened, and the air supply is shut off by closing valve 43. Water is supplied to jacket 3 to cool the reaction products to 20-80 ° C. After cooling, the mixture of reaction products is neutralized with acid. An aqueous acid solution can be used for this purpose by passing it through the charging port 12.

According to a preferred modification of the invention, the mixture of reaction products is neutralized by feeding carbon dioxide to boiler 1. For this purpose, valve 48 is opened and carbon dioxide is fed to boiler 1 from source 46 through flow meter 44 and perforated tube 31. In doing so, 8 68255 with valve 20 closed and valve 21 open. The carbon dioxide that has passed through the mixture of reaction products is discharged into the atmosphere through a pipe 14 and a bypass pipe 19. The neutralized mixture of reaction products settles in boiler 1 with drive 10 switched off. After gravity separation of the resulting suspension, water is passed through lines 26 to remove salts formed and unreacted monomer through lines 27. The neutralized and washed mixture of reaction products is dried at 80-135 ° C. 10 To do this, close the valves 22 and 24 and supply heated steam to the jacket 3.

When phenol (C8H2OH), octyl- (CoH._) -phenol and cresol are used as starting materials, the reaction mixture is heated to 130-155 ° C and, after blowing air, the mixture is cooled to 50-80 ° C, stirred with water and blown through. of carbon dioxide.

The dried polyphenol is removed from the boiler through line 29 by opening valve 30.

The invention will now be described by way of certain examples.

Example 1

Polyphenol was prepared according to the present invention as follows. 18.8 kg of phenol and 20 kg of an aqueous solution of potassium hydroxide with a concentration of 56% were placed in the kettle. Thus, the molar ratio of the components was 1: 1. Phenol and aqueous potassium hydroxide were mixed and heated to 155 ° C. Air was passed through the reaction mixture at a temperature of eight hours. The relative air flow rate 3 was 0.016 m / h per kg of phenol. After completion of the phenol polycondensation reaction, the mixture of reaction products was cooled to 70 ° C. After the mixture was cooled, 30 kg of water was added and 35% hydrochloric acid was added to the mixture to neutralize the alkali. A suspension of polyphenol in water, containing potassium chloride and unreacted phenol, was kept in a saucepan to precipitate. After precipitation of the polymer suspension, potassium chloride and unreacted phenol were washed off with warm water. The washed polymer powder was dried at 80 ° C until all moisture was removed and then removed from the pan.

The final product, i.e. polyphenol, the yield was 48% by weight. The polyphenol was in the form of a powder comprising particles having an amor-5 physical structure. Polyphenol had the following properties:

softening point 125 ° C

Decomposition temperature 500 ° C

Polyphenol had good solubility in polar solvents such as acetone, dimethylformamide, sulfuric acid, aqueous aqueous solutions.

Such properties make the obtained polyphenol useful for the production of heat-resistant coatings, for use as a co-curing agent, binder and hardener for cold-curable adhesives in epoxy resins. However, the resulting polymer has good processability due to its relatively low softening point and good solubility.

Example 2 Polyphenol was prepared according to the present invention essentially as shown in Example 1 under the same conditions. However, the reaction mixture was heated to 130 ° C and the air used to pass through the reaction mixture was not pretreated with alkali.

The final product, i.e. polyphenol, the yield was 30% by weight. The polyphenol was in the form of an amorphous powder and had the following properties:

softening point 105 ° C

30 Decomposition temperature 450 ° C

Polyphenol had good solubility in polar solvents such as acetone, dimethylformamide, sulfuric acid, aqueous aqueous solutions.

The use of the polyphenol thus obtained is similar to the polyphenol link of Example 1.

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Example 3

The polyphenol was prepared according to the present invention essentially as shown in Example 1 under the same conditions. However, the reaction mixture was heated to 170 ° C and the air passed through the reaction mixture was not pretreated with alkali.

The final product, i.e. polyphenol, the yield was 55% by weight. The polyphenol was in the form of an amorphous powder and had the following properties:

10 softening point 180 ° C

Decomposition temperature 500 ° C

The polyphenol had good solubility in polar solvents such as aqueous aqueous solutions, sulfuric acid, acetone, dimethylformamide, etc.

The polyphenol obtained is probably the most useful for the same purposes as the polyphenol obtained according to Example 1. Example 4 (comparison)

The polyphenol was prepared essentially as shown in Example 1 under the same conditions.

However, the reaction mixture was heated to 180 ° C, which was above the limit specified in the claims. The results were as follows: polyphenol yield 27% by weight

softening point 210 ° C

25 Decomposition temperature 500 ° C

The polyphenol obtained under these conditions had a high molecular weight, which has a detrimental effect on the solubility of the polyphenol and results in a relatively high softening point. This makes further processing of the obtained polymer difficult.

Example 5

Poly-oC-naphthol was prepared according to the invention as follows. 14.4 kg of Of-naphthol and 25 kg of an aqueous solution of potassium hydroxide at a concentration of 11% were placed in a kettle, the molar ratio of the components being 1: 0.5. The resulting mixture was heated to 98 ° C with constant stirring. Air was passed through the reaction mixture at the same temperature 3 11 68255 for eight hours. The relative flow rate was 0.009 m / h per kg of OC naphthol.

The air fed to the reaction mixture was cooled and passed through a concentrated alkaline aqueous solution into which a solution of OC-naphthol was taken from the air. Thus, the purified air was vented out into the atmosphere. After completion of the polycondensation reaction of the OC-naphthol mixture, the reaction products were cooled to 45 ° C and then neutralized by passing carbon dioxide through them.

A suspension of poly-tfC-naphthol in an aqueous medium formed in the neutralization reaction containing potassium carbonate and unreacted Of-naphthol was separated as follows. The suspension was precipitated for some time in a saucepan and then washed at 20-30 ° C with water to separate the potassium cartonate. The unreacted OC naphthol was separated by washing the suspension with water heated to 70-80 ° C. The rinsed polymer powder was dried at 135 ° C until all moisture was removed and then removed from the pan.

20 The final product, i.e. the intake of poly-OC naphthol was 93

Well-%. The obtained poly-OC naphthol was in the form of an amorphous powder and had the following properties: softening point 200 ° C

Decomposition temperature 550 ° C

Solubility Soluble in polar solvents, exemplified in Example 1

With the exception of the field of application mentioned in Example 1, the poly-fluoro-naphthol obtained in this example can be used as a binder for carbon compositions and organic plastics, e.g. a graphite-containing lubricant. Example 6

Poly-OC-naphthol was prepared according to the invention essentially as in Example 5. However, an aqueous solution of 35 kg of sodium hydroxide (25 kg) was used, which solution was mixed with 14.4 kg of Ofc-naphthol in a molar ratio of 0.5: 1.

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The resulting mixture was heated to 95 ° C. At this temperature, air was continuously passed through the reaction mixture for eight hours. The flow rate was 0.009 m / h oC-naphthol per kg. The air fed to the reaction mixture was freshly passed through an aqueous solution of sodium hydroxide to separate the carbon dioxide. The air passed through the reaction mixture was then cooled and passed through an aqueous solution of sodium hydroxide to take up the OC-naphthol mixture in air. After the air supply was stopped, the reaction-10 mixture was cooled to 20 ° C. The resulting alkaline aqueous solution of Ot-naphthol was used as a phenol component in the preparation of heat-resistant and heat-stable epoxy resins and as a catalyst in the curing of epoxy-phenol compounds.

15 Example 7

The poly-cC-naphthol was prepared according to the invention essentially as shown in Example 6. However, the following conditions were maintained: 14.4 kg of cc-naphthol were mixed with 40 kg of an aqueous 1: 0.5 molar solution of sodium hydroxide. The concentration of the sodium hydroxide solution was 5%. The resulting mixture was heated to 95 ° C. At this temperature, air was continuously passed through the reaction mixture for eight hours. The relative flow rate was 3 0.009 m / h per kg of 0E-naphthol. The air fed to the reaction mixture was initially passed through an aqueous solution of sodium hydroxide to separate the carbon dioxide. The air passed through the reaction mixture was then cooled and passed through an aqueous solution of sodium hydroxide to take up the Ot-naphthol mixture in the air. After stopping the air supply, the reaction mixture was cooled to 20 ° C. Carbon dioxide was passed through a mixture of reaction products to neutralize sodium hydroxide. The mixture of reaction products thus treated was then kept in a saucepan to precipitate and washed with water at 20-30 ° C to remove sodium carbonate therefrom. The reaction products were then washed with distilled water at 70-80 ° C and the unreacted 6-naphthol was removed.

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The rinsed polymer powder was dried at 80 ° C until all moisture was removed and then the powder was removed from the pan.

The final product, i.e. the yield of poly-β-naphthol was 85% by weight.

The obtained poly-ofc-naphthol was in the form of an amorphous powder and had the following properties;

softening point 170 ° C

Decomposition temperature 500 ° C

Poly-O-naphthol had good solubility in the polar solvents mentioned in Example 1.

Such properties make it possible to use poly-O <-naphthol for the same purposes as mentioned in Example 1.

15 Example 8

Poly-Ot naphthol was prepared according to the invention essentially as shown in Example 5. However, the following conditions were maintained; 14.4 kg of OC-naphthol were mixed with 25 kg of an aqueous solution of potassium hydroxide in a molar-20 ratio of 1: 0.5. The resulting mixture was heated to 70 ° C. At this temperature, air was continuously passed through the reaction mixture for eight hours. The relative flow rate was 0.009 m 2 / h per kg of Otf-naphthol.

The air fed to the reaction mixture was preliminarily passed through an aqueous solution of potassium hydroxide to separate the carbon dioxide from the air.

The air passed through the reaction mixture was then cooled to 45 ° C and neutralized by passing carbon dioxide through it. A suspension of poly-Ot-naphthol in an aqueous solution formed in the neutralization reaction containing potassium carbonate and unreacted Ot-naphthol was separated by gravity. The polymer precipitate obtained in said separation was washed with water having a temperature of 20 to 30 ° C to separate potassium carbonate therefrom, and then washed with distilled water having a temperature of 70 to 80 ° C to separate unreacted OC naphthol. The rinsed polymer powder was dried at 135 ° C, 14 68255 until all moisture was removed and then removed from the pan.

The final product, i.e. poly-Ot-naphthol, the yield was 70% by weight. The obtained poly-Ot naphthol was in the form of an amorphous powder and had the following properties:

softening point 100 ° C

Decomposition temperature 450 ° C

Poly-06 naphthol had good solubility in the polar solvents mentioned in Example 1.

10 Such properties make it possible to use poly-06-naphthol as a plasma-resistant film-forming component used in the manufacture of photoresistors. Example 9

Poly-Ot naphthol was prepared essentially as in Example 8 under the same conditions. However, the reaction mixture was heated to 60 ° C, which was outside the limits defined in the claims.

The results were as follows: yield of 20 poly-06-alpha-naphthol 50% by weight

softening point 60 ° C

Decomposition temperature 400 ° C

The low values of heat resistance and softening point prevent the poly-OC naphthol thus obtained from being used as a binder in the manufacture of coatings.

Example 10

Poly-Ot-naphthol was prepared according to the invention as follows: 14.4 kg of gtaphthol were mixed with 61 kg of an aqueous solution of potassium hydroxide at a concentration of 22%, so that the molar ratio was 1: 2.4. The resulting mixture was heated to 80 ° C. At this temperature, air was continuously passed through the reaction mixture for six hours. The flow rate was 3 0.007 m / h per kg of naphthol. The air fed to the reaction mixture was first passed through an aqueous solution of potassium hydroxide to remove carbon dioxide. The air passed through the reaction mixture was then cooled and passed through an aqueous solution of potassium hydroxide which took up the N-naphthol mixture in air. After the supply of air to the reaction mixture was completed, the mixture was cooled to 45 ° C and then neutralized by passing carbon dioxide through it. The suspension of polymer 5 formed in the neutralization reaction in an aqueous medium containing carbon dioxide and unreacted monomer was separated by gravity. The resulting poly-β-naphthol precipitate was further separated from this separation as shown in Example 8.

The final product, i.e. the yield of poly-β-naphthol was 78% by weight. The properties of the poly - / $ - naphthol obtained in the form of an amorphous powder were:

softening point 110 ° C

Decomposition temperature 450 ° C

Poly- [3-naphthol had good solubility in the polar solvents mentioned in Example 1.

Such properties make it possible to use poly -? - naphthol for the same purposes as mentioned in Example 1.

Example 11 Poly-N-naphthol was prepared according to the invention as follows: 14.4 kg / N-naphthol was mixed with 14 kg of an aqueous solution of potassium hydroxide having a concentration of 11% to give a molar ratio of 1: 0.25. The resulting mixture was heated to 80 ° C. At this temperature, air was blown through the reaction mixture continuously for eight hours.

3

The relative flow rate was 0.007 m / h / J of naphthol per kg. The air blown into the reaction mixture was first passed through an aqueous solution of potassium hydroxide to remove carbon dioxide from the air. The air that had passed through the reaction mixture was then cooled and passed through an aqueous solution of potassium hydroxide to remove the β-naphthol it contained. When the air supply was complete, the reaction mixture was cooled to 45 ° C. Neutralization of said mixture and separation of the final product, i. separation of poly / β-naphthol, was performed as in Example 5, but the resulting polymer was dried at 80 ° C.

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The final product, i.e. poly (i) naphthol, the yield was 20% by weight. The obtained poly-β-naphthol was in the form of an amorphous powder and had the following properties:

softening point 200 ° C

5 Decomposition temperature> 500 ° C

The poly- / S-naphthol had good solubility in the polar solvents mentioned in Example 1.

Example 12 (comparison)

Poly [3-naphthol ”was prepared essentially as in Example 9, maintaining the same conditions. However, β-naphthol was mixed with potassium hydroxide in a molar ratio of 1: 3. Thus, the molar ratio was outside the range defined in the claims.

The results were as follows: yield of 15 poly -? - naphthol 40% by weight

softening point 50 ° C

Decomposition temperature 300 ° C

As can be seen from the numerical values given above, the poly-β-naphthol thus obtained has poor heat resistance. In addition, the extensibility of the reaction mixture is so high that it results in a significant reduction in contact between the mixture and air, and it significantly affects the power consumption required for agitation.

Example 13 (Comparative) 25 Poly (i) naphthol was prepared essentially as in Example 11 under the same conditions. However, γ-naphthol was mixed with potassium hydroxide in a molar ratio of 1: 0.2. This ratio was outside the range of ratios defined in the claims.

The results were as follows: poly- / 3-naphthol yield 15% by weight

softening point 50 ° C

Decomposition temperature 300 ° C

The commercial implementation of such a modification of the production process does not make sense due to the end product, i.e. very low yields of poly / β-naphthol.

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Example 14

According to the invention, poly (C 8 H 1) -alkylphenol was prepared essentially as shown in Example 1. However, the following conditions were maintained: 41 kg of octylphenol was mixed with 20 kg of an aqueous solution of potassium hydroxide at a concentration of 56% to give a molar ratio of 1: 1. . The resulting mixture was heated to 155 ° C. At this temperature, air was continuously passed through the reaction mixture for eight hours. The relative flow rate of n-10 was 0.009 m / h per kg of octylphenol. The air fed to the reaction mixture was first passed through an aqueous solution of potassium hydroxide to remove carbon dioxide from the air. The air that had passed through the reaction mixture was then cooled and passed through an aqueous solution of potassium hydroxide to remove the mixture therein. After the air supply was stopped, the reaction mixture was cooled to 20 ° C. The final product, i.e. polyalkylphenol, neutralization was performed as in Example 1.

The final product, i.e. polyalkylphenol, the yield was 20 to 70% by weight. The resulting polyalkylphenol was in the form of a stretchable liquid and had the following properties:

Decomposition temperature> 300 ° C

Polyalkylphenol (C 9 H 2) had good solubility in petroleum hydrocarbons. This makes it possible to use said polymer in the production of cheap and non-toxic varnishes.

Example 15 (comparison)

Poly (CqH17) alkylphenol was prepared essentially as shown in Example 14 under the same conditions. However, the temperature conditions for heating the reaction mixture were outside the range defined in claim 10. The reaction mixture was heated to 110 ° C.

The results were as follows: yield of 35 polyalkylphenols 10% by weight

Decomposition temperature 300 ° C

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It is understood that the commercial implementation of such a modification of the production process does not make sense due to the very low yield of the final product. Example 16 Polycresol was prepared according to the invention essentially as described in Example 1. However, the following conditions were maintained. 22 kg of polycresol were mixed with 29 kg of aqueous potassium hydroxide solution so that the molar ratio became 1: 1.

The concentration of the aqueous potassium hydroxide solution was 39%. The resulting mixture was heated to 155 ° C. At this temperature, air was passed through the reaction mixture continuously for eight hours. The relative flow rate was 3 0.016 m / h per kg of cresol. The II-15α fed to the reaction mixture was first passed through an aqueous solution of potassium hydroxide to remove carbon dioxide from the air. The air passed through the reaction mixture was then cooled and passed through an aqueous solution of potassium hydroxide to remove paracresol in the air. After completion of the air supply, the reaction mixture was cooled to 80 ° C, stirred in water and neutralized with sulfuric acid. After settling and gravity separation, the reaction product suspension was washed with water at 20-30 ° C to remove potassium chloride. The reaction products were then washed with distilled water at 70-80 ° C and the unreacted paracresol was removed. The rinsed polymer powder was dried at 80 ° C until the moisture was removed and then the product was removed from the pan.

The final product, i.e. polycresol, the yield was 40 wt% to 30%. Polycresol was obtained in the form of an amorphous powder and had the following properties:

softening point 65 ° C

Decomposition temperature 500 ° C

Polycresol had good solubility in the polar solvents mentioned in Example 1.

Such properties make it possible to use polycresol for the same purposes as mentioned in Example 1.

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Example 17

According to the invention, polyhydroquinone was prepared essentially as described in Example 7. However, the following conditions were maintained: 25 kg of hydroquinone 5 was mixed with 27 kg of an aqueous sodium hydroxide solution in a molar ratio of 1: 0.5. The concentration of the aqueous sodium hydroxide solution was 15%. The resulting mixture was heated to 98 ° C. At this temperature, air was passed through the mixture continuously for 3 hours. The flow rate was 0.016 m / h per kg of hydroquinone. The air fed to the reaction mixture was first passed through an aqueous solution of sodium hydroxide to remove carbon dioxide in the air. The air passed through the reaction mixture was then cooled and passed through an aqueous solution of sodium hydroxide to remove the hydroquinone mixtures in the air. After stopping the air supply, the reaction mixture was cooled to 45 ° C.

Neutralization of said mixture and separation of the final product was performed as shown in Example 5, but the resulting polymer was dried at 130 ° C.

20 The final product, i.e. polyhydroquinone, intake was

80% by weight. The polyhydroquinone was obtained in the form of an amorphous powder and had the following properties: softening point 295 ° C

Decomposition temperature> 500 ° C

Polyhydroquinone had good solubility in the polar solvents mentioned in Example 1.

Such properties make it possible to use polyhydroquinone for the same purposes as given in Example 5.

30 Example 18 (comparison)

Polyhydroquinone was prepared essentially as in Example 17 under the same conditions. However, the concentration of sodium hydroxide was 4%, which is outside the range defined in the claims.

35 The results were as follows: yield of polyhydroquinone 20% by weight

softening point 295 ° C

Decomposition temperature 500 ° C

20 6 8 2 5 5

Due to the end product, i.e. polyhydroquinone, low yield, it is not recommended to implement this modification of the production process for economic reasons.

Example 19 (Comparative) 5 Polyhydroquinone was prepared essentially as in Example 17 under the same conditions. However, the concentration of sodium hydroxide was 60%, i.e. outside the range defined in the claims.

The results were as follows: yield of 10 polyhydroquinones 20% by weight

The commercial implementation of such a modification of the production process does not make sense due to the very low yield of the final product. In addition, the extensibility of the reaction mixture in the polymer manufacturing process is so high that it results in a significant reduction in contact between the mixture and air and significantly affects the power consumption required for agitation.

Example 20 (comparison)

Polyhydroquinone was prepared essentially as in Example 17 under the same conditions. However, the amount of air blown through the mixture was 0.017 m / h per kg of monomer, i. outside the range defined in the claims.

The results were as follows: yield of 25 polyhydroquinones 30% by weight

softening point 295 ° C

Decomposition temperature 500 ° C

In the oxidative polycondensation process, intense foaming of the reaction mixture was observed. By-products 30 were formed in large quantities.

Example 21 (comparison)

Polyhydroquinone was prepared essentially as in Example 17 under the same conditions. However, the amount of air blown through the reaction mixture was 35 0.006 m / h per kg of hydroquinone. The final product, i.e. hydroquinone, the yield was 35% by weight. The polyhydroquinone was obtained in the form of an amorphous powder having the following properties: 21 68255

softening point 295 ° C

Decomposition temperature 500 ° C

However, since the large number of blend parts was difficult to separate in this modification of the production process, it was not possible to use the obtained polymer for epoxy-phenol compounds.

Claims (10)

A process for the preparation of polyphenols by oxidizing poly-5 by condensing a phenol series monomer in an aqueous medium in the presence of an oxidant and separating the end, characterized in that the phenol series monomer is mixed with an aqueous alkali solution having a concentration of 5-56% in a molar ratio of 1: 2.4-1: 0.5 and suspension is heated to 70-170 ° C and air is passed through the reaction mixture, the oxygen of which acts as an oxidant. Process according to Claim 1, characterized in that the monomer of the phenol series is mixed with an aqueous solution of potassium hydroxide having a concentration of 11 to 56% or with an aqueous solution of sodium hydroxide having a concentration of 25 to 56%. Process according to Claim 1, characterized in that the air used as oxidant is pretreated, e.g. with alkali. Process according to Claim 1, characterized in that air is passed through the reaction mixture at a feed rate of 0.007 to 0.016 m / h per kg of monomer. Process according to Claim 1, characterized in that, after passing through the air 30, the mixture of reaction products is cooled to a temperature of 20 to 80 ° C, after which the cooled mixture of reaction products is neutralized with mineral acid and washed with water to remove salts formed. Process according to Claim 5, characterized in that, using phenol (CH OH), octyl (CO 2) phenol and cresol as starting material, the reaction mixture OD 10 / is heated to a temperature of 130 to 155 ° C and that, after purging the air, the reaction mixture is cooled. to 50-80 ° C, mixed with water and blown through carbon dioxide. Process according to Claim 5, characterized in that the neutralized and washed mixture of reaction products is dried at a temperature of 80 to 135 ° C. 23 68255 Process according to Claim 1, characterized in that the air which has passed through the reaction mixture is cooled and then passed through an aqueous alkali solution. An apparatus for carrying out the process according to claim 8, comprising a reaction vessel (1) having a heater (2); a shaft (8) provided with vanes (9) mounted in the reaction vessel (1) and connected to a drive device (10) for rotating the shaft; a perforated tube (31) fitted to the lower part of the reaction vessel (1) and communicating with the air supply device (32), characterized in that the perforated tube (31) is connected to the air supply device (32) through an air-alkali treatment chamber (33), and the alkali treatment chamber (33) has a multi-stage adsorber and that the perforated tube (31) is connected to a carbon dioxide source 15 (46). Apparatus according to claim 9, characterized in that the flow meter (44) is arranged at the inlet of the perforated tube (31) and the upper part of the reaction vessel (1) is connected via a tube (14) to an adsorber 20 (15) filled with alkali, the adsorber (15) is provided with a seal (16) made of an alkali-inert fiber, that the bypass tube (19) is connected in parallel with the adsorber (15) to remove excess carbon dioxide, and that the reaction vessel (1) is connected to the adsorber (15) by a countercooler (17) through. 24 Patentkrav 68255