Process for preparing polyphenols

A process for preparing polyphenols, including oxidative polycondensation of a phenol in an aqueous medium in the presence of an oxidizer as well as a subsequent separation of the end product. The starting phenol is mixed with an aqueous solution of an alkali of 5 to 56% concentration in a molar ratio between 1:2.4 and 1:0.25 and heated to a temperature between 70.degree. and 170.degree. C., while air, which furnishes oxygen as the oxidizer, is passed through the reaction mixture. An apparatus for carrying out the process of the invention comprises a kettle equipped with a heater, a shaft with blades mounted within said kettle and connected to a drive for revolving the shaft, a perforated pipe assembled at the bottom portion of the kettle and communicating with an air blower. The perforated pipe communicates with the air blower through an air treatment chamber.

BACKGROUND OF THE INVENTION 
1. Field of the Invention 
The present invention relates to the art of preparing polymers, and more 
particularly to processes and apparatus for producing polyphenols. The 
invention is of particular advantage in the case of producing conventional 
and novel polyphenols featuring characteristics which make them suitable 
for the manufacture of heat-resistant, chemically resistant, and 
radiation-resistant materials as well as antistatic materials for coating 
and other applications. Moreover, polyphenols may be useful as starting 
materials and curing agents in the synthesis of heat-resistant epoxy 
resins. 
The problem of providing a straightforward and inexpensive process for 
commercial production of polyphenols is presently needed, even though 
polymerization of phenols by oxidative polycondensation is well known to 
those skilled in the pertinent art. 
2. Description of the Prior Art 
Known in the art is a process for preparing polyphenols by oxidative 
heteropolycondensation in the presence of a catalyst or catalysts selected 
from the group consisting of chloride of copper, chloride of iron, 
chloride of aluminum, and impurities (U.S. Pat. No. 3,678,006 and Soviet 
Inventor's Certificate No. 448,186). 
The polymers obtained in the above process are useful for a wide range of 
applications but the manufacture thereof is not always profitable. This is 
due to the fact that the catalysts specified are effective in equimolar 
ratios or those well in excess of the latter as regards the monomer. 
Here account must be taken of a high cost of the catalysts as well as of 
the fact that they can be used in the polycondensation process but once. 
A process for preparing polyhydroquinone is also described in Soviet 
Inventor's Certificate No. 440,387. This process includes oxidative 
polycondensation of hydroquinone in an aqueous medium in the presence of 
oxidizers as well as separation of the end product. Hydrogen peroxide 
(perhydrol) has been disclosed as an oxidizer in this process. 
To effectively oxidize the monomer, an amount of perhydrol in the reaction 
mixture is to be at least 2.3 mole per one mole of monomer. No doubt the 
process is advantageous in that the reaction of polycondensation results 
in the formation of water only, which is easily separated from the end 
product. 
While this process is advantageous as hereinabove described, it still has 
some significant disadvantages. Thus, an intensive aggressivity of 
perhydrol requires that there be used a costly corrosion-proof processing 
equipment. Furthermore, the process described involves special care in 
view of an explosive nature of perhydrol. Finally, perhydrol, which is 
used in major amounts, is a relatively high-cost material for an oxidizer. 
SUMMARY OF THE INVENTION 
It is a principal object of the present invention to provide a relatively 
low-cost process for preparing polyphenols involving the use of an easily 
available oxidizer. 
Another important object of the present invention is to provide a process 
for preparing a polyphenol in the presence of an oxidizer which is less 
aggressive than conventional oxidizers but causes no decrease in the yield 
of the end product. 
It is a further object of the invention to provide a safe process for 
preparing polyphenols. 
Still another object of the invention is to provide a process for preparing 
heat-resistant polyphenols. 
An additional object of the invention is to provide a process which permits 
the preparation of polyphenols making epoxy-novolac resins highly 
heat-resistant. 
Another object of the present invention is to provide a process for 
preparing polyphenols, making possible the most complete use of auxiliary 
material. 
Yet another object of the invention is to provide a process which makes it 
possible to easily separate and reuse unreacted monomers of phenolic 
series. 
It is an additional object of the present invention to provide a process 
for preparing polyphenols, eliminating pollution of our environment by 
reaction products. 
Another still important object of the present invention is to provide an 
apparatus for carrying out the process, which enables an effective usage 
of a low-cost and easily available oxidizer in polycondensation of 
polyphenols. 
A further object of the invention is to provide an apparatus which permits 
an unreacted monomer of the phenolic series to be separated and reused. 
Another additional object of the present invention is to provide a safe and 
reliable in operation apparatus for preparing polyphenols. 
These and other objects of the present invention are attained by providing 
a process for preparing polyphenols, including oxidative polycondensation 
of a monomer of phenolic series in an aqueous medium in the presence of an 
oxidizer as well as a subsequent separation of the end product, wherein, 
according to the invention, the monomer of phenolic series is mixed with 
an aqueous solution of alkali of 5 to 56% concentration in a molar ratio 
between 1:2.4 and 1:0.25 and heated to a temperature between 70.degree. 
and 170.degree. C., while air, which furnishes oxygen as the oxidizer, is 
passed through the reaction mixture. 
An easily availabe material, such as air, used in this process, makes the 
same substantially cheaper, yet involves no intensive attack by corrosion 
upon the processing equipment. Oxygen furnished by air can be effectively 
used as an oxidizer only under the hereinabove specified conditions. When 
practiced, such process is relatively safe and enables preparation of 
sufficiently pure polyphenols at a high yield of the end product. Thus the 
above polymers are heat resistant and useful both as basic and auxiliary 
components for the manufacture of heat resistant coatings as well as for 
preparing various epoxy-novolac compounds. 
A monomer of phenolic acid is preferably mixed with an aqueous solution of 
potassium hydroxide of 11 to 56% concentration. Under such conditions 
oxidative polycondensation is the most intensive. 
A medium for oxidative polycondensation of a monomer of phenolic acid, 
which can be used, is an aqueous solution of sodium hydroxide of 25 to 56% 
concentration. 
Air used as the oxidizer is to be preferably treated with an alkali. In 
doing this, carbon dioxide present in the air is taken up by the alkali 
and subsequently has no adverse effect on the process of oxidative 
polycondensation. This allows the yield of the monomer of phenolic acid to 
be increased. The air is preferably to be treated with a concentrated 
alkaline solution. 
To attain the best results, a relative flow rate in passing the air through 
the reaction mixture should be from 0.007 to 0.016 m.sup.3 /hr per 
kilogram of the monomer. 
To make the reaction products separated easier, it is worthwhile to cool 
the mixture of these reaction products to 20.degree. to 80.degree. C. 
following termination of the step of passing the air through the reaction 
mixture. 
Neutralizing the cooled mixture of the reaction products with a mineral 
acid and washing the same with water to remove salts that are being formed 
are the simplest steps in the process. In this case, the most effective is 
the step of passing carbon dioxide through the mixture of the reaction 
products after the reaction of oxidative polycondensation of a monomer of 
phenolic series has terminated. 
When phenol (C.sub.6 H.sub.5 OH), alkyl phenol (C.sub.8 H.sub.17), and 
cresol are used as starting materials for best results the reaction 
mixture is heated to a temperature of 130.degree. to 155.degree. C. and 
having been blown with the air it is cooled down to between 50.degree. and 
80.degree. C., then mixed with water and blown through with carbon 
dioxide. 
To attain a quality end product, it is appropriate to dry a neutralized and 
washed mixture of the reaction products at a temperature of 80.degree. to 
135.degree. C. 
To prevent pollution of the atmosphere, the air that has been passed 
through the reaction mixture is preferably further passed through an 
aqueous solution of an alkali. This step permits losses of both basic and 
auxiliary components (the monomer of the phenolic series and the alkali) 
to be cut down. 
It is advisable to first cool and then pass through an aqueous alkaline 
solution the air that has been passed through the reaction mixture. This 
rules out heating of the aqueous alkaline solution and thereby decreases 
its aggressivity. 
These and other objects of the invention are also attained by the provision 
of an apparatus for carrying out the process, comprising a kettle equipped 
with a heater, a shaft with blades mounted within said kettle and 
connected to a drive for revolving the same shaft, a perforated pipe 
assembled at the bottom portion of the kettle and communicating with an 
air blower, wherein, according to the invention, the perforated pipe 
communicates with the air blower by way of a chamber for treating air with 
an alkali. Feeding the air through the preliminary treatment chamber 
prevents carbon dioxide from entering the kettle and favors an increase in 
the yield of polyphenol as well as the production of a pure end product. 
The chamber for treating air with an alkali, constructed as a multi-stage 
adsorber, is the simplest and the most reliable modification of the 
apparatus of the invention. 
The preforated pipe preferably communicates with a source of carbon 
dioxide. When introduced into the mixture of the reaction products, carbon 
dioxide bubbles through a suspension and provides for better neutralizing 
of the alkali. 
To maintain optimum operation conditions, it is advisable to provide the 
perforated pipe at its outlet with a flowmeter. 
To utilize the losses of the monomer of phenolic series and the alkali, it 
is appropriate that the kettle at the upper portion thereof communicates 
through a pipe with an adsorber filled with an alkali. 
To prevent foam and the alkali from being thrown out, it is advisable to 
provide the adsorber with a packing made of a fibrous material inert to 
alkalis. 
To prevent neutralization of the alkali with carbon dioxide on neutralizing 
the mixture of the reaction products in the kettle, it is appropriate that 
there be a bypass pipe connected round said adsorber to provide an 
excessive carbon dioxide outflow. 
It is preferred that the kettle communicate with the adsorber through a 
back-flow condenser. This will prevent overheating the alkali in the 
adsorber. 
To exercise a timely check of the process and to prevent a troublesome 
situation, the pipe is preferably provided with a sight glass.

DETAILED DESCRIPTION OF THE INVENTION 
A process for preparing polyphenols of the invention is carried out by 
means of an apparatus comprising a kettle 1 equipped with a heater 2 
constructed in the form of a jacket 3. The jacket 3 communicates with 
feeding main lines 4 and 5 and with main lines 6 and 7 for removal of 
vapor and cooling water. A shaft 8 with blades 9 is mounted within said 
kettle 1 and is connected to a drive 10 for revolving the same shaft. In 
the upper cover 11 of the kettle 1 there is provided a charge opening 12. 
A thermocouple 13 is fixed on the upper cover 11. The upper portion of the 
kettle 1 communicates through the cover 11 with an adsorber 15 by means of 
a pipe 14. The adsorber 15 is provided with a packing 16 made of a fibrous 
material inert to alkalis. The kettle 1 communicates with the adsorber 15 
through a back-flow condenser 17. The pipe 14 is provided with a sight 
opening 18 closed with a transparent material. A bypass pipe 19 is 
connected in parallel with the adsorber 15. The pipe 14 and the bypass 
pipe 19 are provided with valves 20 and 21. Feeding main lines 4 and 5, 
and main lines 6 and 7 for removal of vapor and cooling water are provided 
with valves 22, 23, 24, 25 Pipes 26 and 27 for feeding and removal of 
washing water are led out at different levels through the side wall of the 
kettle 1. A bottom 28 of the kettle 1 is constructed conical. A charge 
pipe 29 closed by means of a valve 30 is led out through the bottom 28. A 
perforated pipe 31 is mounted in the lower portion of the kettle 1. The 
perforated pipe 31 communicates with an air blower 32 through a chamber 33 
intended for the treatment of air with alkali. A moisture separator 35 is 
included into the main line 34 between the air blower 32 and the chamber 
33. The chamber 33 is constructed as a multi-stage adsorber containing 
vessels 36, 37, and 38, which vessels communicate in series by means of 
siphon pipes 39, 40, and 41 and are filled with an aqueous alkaline 
solution. The chamber 33 communicates with the perforated pipe 31 and a 
pipe 42 provided with a valve 43. At the inlet of the perforated pipe 31, 
there is mounted a flow meter 44. The perforated pipe 31 communicates with 
a carbon dioxide source 46 by means of a pipe 45. Between the source 46 
and the perforated pipe 31 within the pipe 45 there are mounted in series 
a reduction valve 47 and a valve 48. The carbon dioxide source 46 is 
constructed as a unit of removable vessels 49, 50, 51 which vessels 
contain carbon dioxide and are interconnected by means of a collector 52. 
A process for preparing polyphenols of the invention is carried out as 
follows. The kettle 1 is charged through the charge opening 12 with a 
monomer of the phenolic series and an aqueous alkaline solution in a molar 
ratio between 1:2.4 and 1:0.25. The aqueous alkaline solution is of 5 to 
56% concentration. Under the action of the drive 10, the shaft 8 equipped 
with the blades 9 rotates, thus stirring the monomer of the phenolic 
series and the aqueous alkaline solution. At the same time, the valves 22 
and 24, feeding main lines 4 and main lines 6 for removal of vapor are 
opened. The vapor circulating over the jacket 3 heats the reaction mixture 
up to a temperature of 70.degree. to 170.degree. C. Simultaneously, air is 
fed into the reaction mixture from the air blower 32 through the 
perforated pipe 31. During the passage of the air through the reaction 
mixture, for a certain time polyphenol is formed as a result of the 
oxidative polycondensation of the monomer of the phenolic series. 
According to the preferred modification of the process of the invention, 
the air used as an oxidizer is subjected to preliminary treatment with a 
concentrated alkaline solution within the vessels 36, 37, 38. The blowing 
rate is maintained in the range of 0.007 to 0.016 m.sup.3 /hr per kilogram 
of the monomer by adjusting efficiency of the air blower 32 or passage 
section of the valve 43 according to the readings of the flowmeter 44. 
Thermal conditions within the kettle 1 are maintained by means of the 
valves 22 and 24 according to the readings of the meter connected to the 
thermocouple 13. The air which has been passed through the reaction 
mixture is fed into the adsorber 15 through the pipe 14 and the back-flow 
condenser 17 while the valve 20 is opened and the valve 21 is closed. 
Within the adsorber 15, the air is passed through the aqueous alkaline 
solution, which solution takes up the starting monomer which is unreacted 
and carried out with the air. The air being preliminarily cooled in the 
back-flow condenser 17 does not practically heat the alkali in the 
adsorber 15. Visual control of the production process may be carried out 
through the sight glass 18, which glass makes it possible to fix the 
beginning of intensive foam formation in the reaction mixture. The packing 
16 prevents the throwing of droplets of the aqueous alkaline solution into 
the atmosphere. 
Potassium or sodium hydroxides are used in the preferred modifications of 
the production process to form an aqueous alkaline medium. In doing this, 
an aqueous solution of potassium hydroxide is of 11 to 56% concentration, 
and that of sodium hydroxide is of 25 to 56% concentration. Following the 
termination of the reaction of oxidative polycondensation, the valves 22 
and 24 are closed, the valves 23 and 25 are opened, and feeding of air is 
cut off by closing the valve 43. Water is fed into the jacket 3, thus 
cooling the reaction products down to a temperature of 20.degree. to 
80.degree. C. After cooling, the mixture of the reaction products is 
neutralized with an acid. For this purpose, an aqueous acid solution may 
be used by means of feeding said solution through the charge opening 12. 
According to the preferred modification of the invention, the mixture of 
the reaction products is neutralized by means of feeding carbon dioxide 
into the kettle 1. For this purpose, the valve 48 is opened, and carbon 
dioxide is fed into the kettle 1 from the source 46 through the flowmeter 
44 and the perforated pipe 31. In doing this, the valve 20 is closed and 
the valve 21 is opened. Carbon dioxide which has been passed through the 
mixture of the reaction products is led out into the atmosphere through 
the pipe 14 and the bypass pipe 19. Neutralized mixture of the reaction 
products is settled in the kettle 1 with the drive 10 being switched on. 
After the gravitational separation of the suspension formed, water is fed 
through the pipes 26 to remove formed salts and unreacted monomer through 
the pipes 27. Neutralized and washed mixture of the reaction products is 
dried at a temperature of 80.degree. to 135.degree. C. For this purpose, 
the valves 22 and 24 are closed, thus feeding heated vapor into the jacket 
3. 
When using phenol (C.sub.6 H.sub.5 OH), alkyl phenol (C.sub.8 H.sub.17) and 
cresol as starting materials, the reaction mixture is heated to a 
temperature of 130.degree. to 155.degree. C. and after blowing with air 
said mixture is cooled to a temperature of 50.degree. to 80.degree. C., 
mixed with water and blown through with carbon dioxide. 
The dried polyphenol is discharged through the pipe 29 by means of opening 
the valve 30. 
Now the invention will be illustrated by the specific examples thereof 
which follow. 
EXAMPLE 1 
Polyphenol was prepared according to the present invention as follows. To 
the kettle was added 18.8 kg of phenol and 20 kg of an aqueous solution of 
potassium hydroxide. The aqueous solution of potassium hydroxide was of 
56% concentration. Thus, molar ratio of the components was 1:1. Phenol and 
the aqueous solution of potassium hydroxide were mixed and heated to a 
temperature of 155.degree. C. Air was passed through the reaction mixture 
at the same temperature for 8 hours. A relative flow rate of the air was 
0.016 m.sup.3 /hr per kilogram of phenol. Following the termination of the 
polycondensation reaction of phenol, the mixture of the reaction products 
was cooled to a temperature of 70.degree. C. After the mixture had been 
cooled, 30 kg of water and 22 kg of a 35% muriatic acid was added to the 
mixture to neutralize the alkali. The suspension of polyphenol in the 
aqueous medium, containing potassium chloride and unreacted phenol, was 
held in the kettle to settle. After settling of the polymer suspension, 
potassium chloride and unreacted phenol were washed out with warm water. 
The washed powder of the polymer was dried at 80.degree. C. until all the 
moisture was removed, and then discharged from the kettle. 
The yield of the end product, i.e. polyphenol, was 48% by weight. 
Polyphenol was in the form of powder consisting of particles having an 
amorphous structure. The polyphenol was of the following characteristics: 
______________________________________ 
softening point, .degree.C. 
125 
decomposition temperature, .degree.C. 
500 
______________________________________ 
The polyphenol showed good solubility in polar solvents such as acetone, 
dimethylformamide, sulphuric acid, aqueous alkaline solutions. 
Such characteristics make the polyphenol obtained useful for manufacturing 
heat resistant coatings, for application as curing agent to cold-setting 
adhesives, as a binder and hardener to epoxy resins. Yet the polymer 
obtained shows a good processibility due to a relatively low softening 
point and good solubility. 
EXAMPLE 2 
Polyphenol was prepared according to the present invention basically as 
disclosed in Example 1, following the same conditions. However, the 
reaction mixture was heated to a temperature of 130.degree. C., and the 
air applied for passing through the reaction mixture was not subjected to 
preliminary treatment with alkali. 
The yield of the end product, i.e. polyphenol, was 30% by weight. 
Polyphenol was in the form of amorphous powder and was of the following 
characteristics: 
______________________________________ 
softening point, .degree.C. 
105 
decomposition temperature, .degree.C. 
450 
______________________________________ 
The polyphenol showed good solubility in polar solvents such as acetone, 
dimethylformamide, sulphuric acid, aqueous alkaline solutions. 
Application of the polyphenol thus obtained is similar to that described in 
Example 1. 
EXAMPLE 3 
Polyphenol was prepared according to the present invention basically as 
disclosed in Example 1, following the same conditions. However, the 
reaction mixture was heated to a temperature of 170.degree. C. and the air 
applied for passing through the reaction mixture was not subjected to 
preliminary treatment with alkali. 
The yield of end product, i.e. polyphenol, was 55% by weight. Polyphenol 
was in the form of an amorphous powder and was of the following 
characteristics: 
______________________________________ 
softening point, .degree.C. 
180 
decomposition temperature, .degree.C. 
500 
______________________________________ 
The polyphenol showed good solubility in polar solvents such as aqueous 
alkaline solutions, sulphuric acid, acetone, dimethylformamide etc. 
The polyphenol obtained may be the most useful for the same purpose as the 
polyphenol obtained according to Example 1. 
EXAMPLE 4 (NEGATIVE) 
Polyphenol was prepared basically as disclosed in Example 1, following the 
same conditions. However, the reaction mixture was heated to a temperature 
of 180.degree. C., which temperature was above the limits specified in the 
claims. 
The results appeared to be as follows: 
______________________________________ 
yield of polyphenol, % by weight 
27 
softening point, .degree.C. 
210 
decomposition temperature, .degree.C. 
500 
______________________________________ 
The polyphenol obtained under such conditions is of a high molar weight 
which weight has an adverse effect on solubility of said polyphenol and 
results in a comparatively high melting point. It makes difficult further 
processing of the obtained polymer. 
EXAMPLE 5 
Poly-.alpha.-naphthol was prepared according to the invention as follows. 
To the kettle was added 14.4 kg of .alpha.-naphthol and 25 kg of an 
aqueous solution of potassium hydroxide. Said solution of potassium 
hydroxide was of 11% concentration, the molar ratio between said 
components being 1:0.5. The mixture obtained was heated to 98.degree. C. 
at continuous mixing. Air was passed through the reaction mixture at the 
same temperature for 8 hours. A relative flow rate was 0.009 m.sup.3 /hr 
per kilogram of .alpha.-naphthol. 
The air being fed into the reaction mixture was cooled and passed through 
an aqueous solution of concentrated alkali in which solution the 
admixtures of .alpha.-naphthol brought out with the air were taken up. 
Thus cleaned air was led out into atmosphere. Following the termination of 
the polycondensation reaction of .alpha.-naphthol the mixture of the 
reaction products was cooled to a temperature of 45.degree. C. and then 
neutralized by passing carbon dioxide therethrough. 
The suspension of poly-.alpha.-naphthol in an aqueous medium being formed 
in the neutralization reaction and containing potassium carbonate and 
unreacted .alpha.-naphthol, was separated as follows. The suspension was 
settled for some time in the kettle and then washed with water having a 
temperature of 20.degree. to 30.degree. C. to separate potassium 
carbonate. Unreacted .alpha.-naphthol was separated by washing the 
suspension with water heated to a temperature of 70.degree. to 80.degree. 
C. The flushed powder of the polymer was dried at 135.degree. C. until all 
the moisture was removed and then was discharged from the kettle. 
The yield of the end product, i.e. poly-.alpha.-naphthol. was 93% by 
weight. Poly-.alpha.-naphthol obtained in the form of amorphous powder was 
of the following characteristics: 
______________________________________ 
softening point, .degree.C. 
200 
decomposition temperature, .degree.C. 
550 
solubility soluble in 
polar solvents 
specified in 
Example 1. 
______________________________________ 
Apart from the fields of application specified in Example 1, 
poly-.alpha.-naphthol obtained according to this example may be used as a 
binder for carbon compositions and organic plastics, e.g. 
graphite-containing grease. 
EXAMPLE 6 
Poly-.alpha.-naphthol was prepared according to the invention basically as 
disclosed in Example 5. However, an aqueous solution of sodium hydroxide 
in an amount of 25 kg was used, which solution was mixed with 14.4 kg of 
.alpha.-naphthol in a molar ratio of 0.5:1. 
The mixture obtained was heated to a temperature of 95.degree. C. At this 
temperature air was continuously passed through the reaction mixture for 8 
hours. A specific flow rate was 0.009 m.sup.3 /hr per kilogram of 
.alpha.-naphthol. The air being fed into the reaction mixture was 
preliminarily passed through an aqueous solution of sodium hydroxide to 
separate carbon dioxide. The air which had been passed through the 
reaction mixture was then cooled and was passed through the aqueous sodium 
hydroxide solution to take up the admixture of .alpha.-naphthol contained 
therein. Following the termination of air feeding, the reaction mixture 
was cooled to a temperature of 20.degree. C. 
The obtained aqueous alkaline solution of .alpha.-naphthol was used as a 
phenolic component in manufacturing heat-resistant and heat stable epoxy 
resins, and as a catalyst for hardening epoxy-phenolic compounds. 
EXAMPLE 7 
Poly-.alpha.-naphthol was prepared according to the invention basically as 
disclosed in Example 6. However, the following conditions were maintained: 
.alpha.-naphthol in an amount of 14.4 kg was mixed with 40 kg of an 
aqueous solution of sodium hydroxide in a molar ratio of 1:0.5. The 
aqueous solution of sodium hydroxide was of 5% concentration. The mixture 
obtained was heated to a temperature of 95.degree. C. At this temperature, 
air was continuously passed through the reaction mixture for 8 hours. A 
relative flow rate was 0.009 m.sup.3 /hr per kilogram of .alpha.-naphthol. 
The air being fed into the reaction mixture was preliminarily passed 
through an aqueous solution of sodium hydroxide to separate carbon 
dioxide. The air which had been passed through the reaction mixture was 
then cooled and was passed through the aqueous solution of sodium 
hydroxide to take up the admixture of .alpha.-naphthol contained therein. 
Following the termination of air feeding, the reaction mixture was cooled 
to a temperature of 20.degree. C. Carbon dioxide was passed through the 
mixture of the reaction products to neutralize sodium hydroxide. The 
mixture of the reaction products thus processed was then held in the 
kettle to settle and was washed with water having a temperature of 
20.degree. to 30.degree. C. to remove sodium carbonate therefrom. Then the 
reaction products were washed with distilled water having a temperature of 
70.degree. to 80.degree. C., and unreacted .alpha.-naphthol was removed. 
The flushed powder of the polymer was dried at 80.degree. C. until all the 
moisture was removed and then was discharged from the kettle. 
The yield of an end product, i.e. poly-.alpha.-naphthol, was 85% by weight. 
Poly-.alpha.-naphthol obtained in the form of an amorphous powder was of 
the following characteristics: 
______________________________________ 
softening point, .degree.C. 
170 
decomposition temperature, .degree.C. 
500 
______________________________________ 
The poly-.alpha.-naphthol showed good solubility in polar solvents 
specified in Example 1. 
Such characteristics make it possible to apply poly-.alpha.-naphthol for 
the same purposes as those specified in Example 1. 
EXAMPLE 8 
Poly-.alpha.-naphthol was prepared according to the invention basically as 
disclosed in Example 5. However, the following conditions were maintained: 
.alpha.-naphthol in an amount of 14.4 kg was mixed with 25 kg of an 
aqueous solution of potassium hydroxide in a molar ratio of 1:0.5. The 
mixture obtained was heated to a temperature of 70.degree. C. At this 
temperature, air was continuously passed through the reaction mixture for 
8 hours. A relative flow rate was 0.009 m.sup.3 /hr per kilogram of 
.alpha.-naphthol. 
The air being fed into the reaction mixture was preliminarily passed 
through an aqueous solution of potassium hydroxide to separate carbon 
dioxide therefrom. 
The air which had been passed through the reaction mixture was then cooled 
to a temperature of 45.degree. C. and was neutralized by passing carbon 
dioxide therethrough. The suspension of poly-.alpha.-naphthol in an 
aqueous medium being formed in the neutralization reaction and containing 
potassium carbonate and unreacted .alpha.-naphthol was separated by the 
gravitational method. The precipitate of a polymer obtained in said 
separation was washed out with water having a temperature of 20.degree. to 
30.degree. C. to remove potassium carbonate therefrom, and then was washed 
with distilled water having a temperature of 70.degree. to 80.degree. C. 
to separate unreacted .alpha.-naphthol. The flushed powder of the polymer 
was dried at a temperature of 135.degree. C. until all the moisture was 
removed and then was discharged from the kettle. 
The yield of end product, i.e. poly-.alpha.-naphthol, was 70% by weight. 
Poly-.alpha.-naphthol obtained in the form of an amorphous powder was of 
the following characteristics: 
______________________________________ 
softening point, .degree.C. 
100 
decomposition temperature, .degree.C. 
450 
______________________________________ 
The poly-.alpha.-naphthol showed good solubility in polar solvents 
specified in Example 1. 
Such characteristics make it possible to use poly-.alpha.-naphthol as a 
plasma-resistant film forming component applied in manufacturing 
photoresistors. 
EXAMPLE 9 
Poly-.alpha.-naphthol was prepared basically as disclosed in Example 8 
while maintaining the same conditions. However, the reaction mixture was 
heated to a temperature of 60.degree. C. which temperature was beyond the 
limits specified in the claims. 
The results appeared to be as follows: 
______________________________________ 
yield of poly-.alpha.-naphthol, % by weight 
50 
softening point, .degree.C. 
60 
decomposition temperature, .degree.C. 
400 
______________________________________ 
Low values of heat resistance and softening point prevent the use of 
poly-.alpha.-naphthol thus obtained as a binder and in manufacturing 
coatings. 
EXAMPLE 10 
Poly-.beta.-naphthol was prepared according to the invention as follows: 
.beta.-naphthol in an amount of 14.4 kg was mixed with 61 kg of an aqueous 
solution of potassium hydroxide of 22% concentration and having the molar 
ratio of 1:2.4. The mixture obtained was heated to a temperature of 
80.degree. C. At this temperature, air was continuously passed through the 
reaction mixture for 6 hours. A specific flow rate was 0.007 m.sup.3 /hr 
per kilogram of .beta.-naphthol. The air being fed into the reaction 
mixture was preliminarily passed through an aqueous solution of potassium 
hydroxide to remove carbon dioxide. The air which had been passed through 
the reaction mixture was then cooled and was passed through the aqueous 
solution of potassium hydroxide to take up the admixture of 
.alpha.-naphthol contained therein. Following the termination of air 
feeding the reaction mixture was cooled to a temperature of 45.degree. C. 
and was then neutralized by passing carbon dioxide therethrough. The 
suspension of polymer in the aqueous medium being formed in the reaction 
of neutralization and containing carbon dioxide and unreacted monomer, was 
separated by the gravitational method. The precipitate of 
poly-.beta.-naphthol obtained during said separation was separated as 
disclosed in Example 8. 
The yield of an end product, i.e. poly-.beta.-naphthol, was 78% by weight. 
Poly-.beta.-naphthol obtained in the form of an amorphous powder was of 
the following characteristics: 
______________________________________ 
softening point, .degree.C. 
110 
decomposition temperature, .degree.C. 
450 
______________________________________ 
The poly-.beta.-naphthol showed good solubility in polar solvents specified 
in Example 1. 
Such characteristics make it possible to apply poly-.beta.-naphthol for the 
same purposes as those specified in Example 1. 
EXAMPLE 11 
Poly-.beta.-naphthol was prepared according to the invention as follows: 
.beta.-naphthol in an amount of 14.4 kg was mixed with 14 kg of an aqueous 
solution of potassium hydroxide of 11% concentration and having the molar 
ratio of 1:0.25. The mixture obtained was heated to a temperature of 
80.degree. C. At this temperature, air was continuously passed through the 
reaction mixture for 8 hours. A relative flow rate was 0.007 m.sup.3 /hr 
per kilogram of .beta.-naphthol. The air being fed into the reaction 
mixture was preliminarily passed through an aqueous solution of patassium 
hydroxide to remove carbon dioxide therefrom. The air which had been 
passed through the reaction mixture was then cooled and was passed through 
the aqueous solution of potassium hydroxide to take up the admixture of 
.beta.-naphthol contained therein. Following the termination of air 
feeding, the reaction mixture was cooled to a temperature of 45.degree. C. 
Neutralization of said mixture and separation of the end product, i.e. 
poly-.beta.-naphthol, were carried out as disclosed in Example 5 but the 
polymer obtained was dried at a temperature of 80.degree. C. 
The yield of the end product, i.e. poly-.beta.-naphthol was 20% by weight. 
Poly-.beta.-naphthol obtained in the form of amorphous powder was of the 
following characteristics: 
______________________________________ 
softening point, .degree.C. 
200 
decomposition temperature, .degree.C. 
&gt;500 
______________________________________ 
The poly-.beta.-naphthol showed good solubility in polar solvents specified 
in Example 1. 
EXAMPLE 12 (NEGATIVE) 
Poly-.beta. naphthol was prepared basically as disclosed in Example 9 while 
maintaining the same conditions. However, naphthol was mixed with 
potassium hydroxide in the molar ratio of 1:3. 
Thus, the molar ratio was beyond the range specified in the claims. 
The results appeared to be as follows: 
______________________________________ 
yield of poly-.beta.-naphthol, % by weight 
40 
softening point, .degree.C. 
50 
decomposition temperature, .degree.C. 
300 
______________________________________ 
As can be seen from the above data, poly-.beta.-naphthol thus obtained is 
of a low heat resistance. Furthermore, the ductility of the reaction 
mixture is so high that it results in significant decrease in contact 
between the mixture and air and considerably affects specific power 
consumption required for stirring. 
EXAMPLE 13 (NEGATIVE) 
Poly-.beta.-naphthol was prepared basically as disclosed in Example 11 
while maintaining the same conditions. However, .beta.-naphthol was mixed 
with potassium hydroxide in the molar ratio of 1:0.2. Such a ratio was 
beyond the range specified in the claims. 
The results appeared to be as follows: 
______________________________________ 
yield of poly-.beta.-naphthol, % by weight 
15 
softening point, .degree.C. 
50 
decomposition temperature, .degree.C. 
300 
______________________________________ 
The commercial realization of such a modification of the production process 
is inexpedient because of an extremely low yield of the end product, i.e. 
poly-.beta.-naphthol. 
EXAMPLE 14 
Polyalkyl phenol (C.sub.8 H.sub.17) was prepared according to the invention 
basically as disclosed in Example 1. However, the following conditions 
were maintained: alkyl phenol (C.sub.8 H.sub.17) in an amount of 41 kg was 
mixed with 20 kg of an aqueous solution of potassium hydroxide of 56% 
concentration and having the molar ratio of 1:1. The mixture obtained was 
heated to a temperature of 155.degree. C. At this temperature, air was 
continuously passed through the reaction mixture for 8 hours. A relative 
flow rate was 0.009 m.sup.3 /hr per kilogram of alkyl phenol (C.sub.8 
H.sub.17). The air being fed into the reaction mixture was preliminarily 
passed through the aqueous solution of potassium hydroxide to remove 
carbon dioxide therefrom. The air which had been passed through the 
reaction mixture was then cooled and was passed through the aqueous 
solution of potassium hydroxide to take up the admixture contained 
therein. Following the termination of air feeding, the reaction mixture 
was cooled to a temperature of 20.degree. C. Neutralization and separation 
of the end product, i.e. polyalkyl phenol, was carried out as disclosed in 
Example 1. 
The yield of the end product, i.e. polyalkyl phenol, was 70% by weight. 
Polyalkyl phenol obtained in the form of a ductile liquid was of the 
following characteristics: 
EQU decomposition temperature, .degree.C.&gt;300 
The polyalkyl phenol (C.sub.8 H.sub.17) showed good solubility in the oil 
hydrocarbons. This allows said polymer to be employed in preparing cheap 
and nontoxic varnishes. 
EXAMPLE 15 (negative) 
Polyalkyl phenol (C.sub.8 H.sub.17) was prepared basically as disclosed in 
Example 14 while maintaining the same conditions. However, temperature 
conditions of heating the reaction mixture were beyond the limits of the 
range specified in claim 10 of the claims. In particular, the reaction 
mixture was heated to a temperature of 110.degree. C. 
The results appeared to be as follows: 
______________________________________ 
yield of polyalkyl phenol, % by weight 
10 
decomposition temperature, .degree.C. 
300 
______________________________________ 
It will be understood that the commercial realization of such a 
modification of the production process is inexpedient because of an 
extremely low yield of the end product. 
EXAMPLE 16 
Polycresol was prepared according to the invention basically as disclosed 
in Example 1. However, the following conditions were maintained. 
Polycresol in an amount of 22 kg was mixed with 29 kg of an aqueous 
solution of potassium hydroxide in the molar ratio of 1:1. 
The aqueous solution of potassium hydroxide was of 39% concentration. The 
mixture obtained was heated to a temperature of 155.degree. C. At this 
temperature, air was continuously passed through the reaction mixture for 
8 hours. A relative flow rate was 0.016 m.sup.3 /hr per kilogram of 
cresol. The air being fed into the reaction mixture was preliminarily 
passed through an aqueous solution of potassium hydroxide to remove carbon 
dioxide therefrom. The air which had been passed through the reaction 
mixture was then cooled and was passed through the aqueous solution of 
potassium hydroxide to take up the admixtures of paracresol contained 
therein. Following the termination of air feeding, the reaction mixture 
was cooled to a temperature of 80.degree. C., mixed with water and 
neutralized with sulphuric acid. After settling and gravitational 
separation, the suspension of the reaction products was washed with water 
having a temperature of 20.degree. to 30.degree. C. to remove potassium 
chloride. Then the reaction products were washed with distilled water 
having a temperature of 70.degree. to 80.degree. C., and unreacted 
para-cresol was removed. Flushed powder of the polymer was dried at 
80.degree. C. until all the moisture was removed and was discharged from 
the kettle. 
The yield of the end product, i.e. polycresol, was 40% by weight. The 
polycresol obtained in the form of amorphous power was of the following 
characteristics: 
______________________________________ 
softening point, .degree.C. 
65 
decomposition temperature, .degree.C. 
500 
______________________________________ 
The polycresol showed good solubility in polar solvents specified in 
Example 1. 
Such characteristics make it possible to employ the polycresol for the same 
purpose as the polyphenol obtained according to Example 1. 
EXAMPLE 17 
Polyhydroquinone was prepared according to the invention basically as 
disclosed in Example 7. However, the following conditions were maintained: 
hydroquinone in an amount of 25 kg was mixed with 27 kg of an aqueous 
solution of sodium hydroxide in the molar ratio of 1:0.5. The aqueous 
solution of sodium hydroxide was of 15% concentration. The mixture 
obtained was heated to a temperature of 98.degree. C. At this temperature, 
air was continuously passed through the reaction mixture for 5 hours. A 
specific flow rate was 0.016 m.sup.3 /hr per kilogram of hydroquinone. The 
air being fed into the reaction mixture was preliminarily passed through 
an aqueous solution of sodium hydroxide to remove carbon dioxide. The air 
which had been passed through the reaction mixture was then cooled and was 
passed through the aqueous solution of sodium hydroxide to take up the 
admixture of hydroquinone. Following the termination of air feeding, the 
reaction mixture was cooled to a temperature of 45.degree. C. 
Neutralization of the mixture and separation of the end product were 
carried out as disclosed in Example 5, but the polymer obtained was dried 
at a temperature of 130.degree. C. 
The yield of the end product, i.e. polyhydroquinone, was 80% by weight. The 
polyhydroquinone obtained in the form of amorphous powder was of the 
following characteristics: 
______________________________________ 
softening point, .degree.C. 
295 
decomposition temperature, .degree.C. 
&gt;500 
______________________________________ 
The polyhydroquinone showed good solubility in polar solvents such as 
specified in Example 1. 
Such characteristics make it possible to employ the polyhydroquinone for 
the same purposes as those given in Example 5. 
EXAMPLE 18 (negative) 
Polyhydroquinone was prepared basically as disclosed in Example 17 while 
maintaining the same conditions. However, an aqueous solution of sodium 
hydroxide was of 4% concentration, which concentration being beyond the 
limits of the range specified in the claims. 
The results appeared to be as follows: 
______________________________________ 
yield of polyhydroquinone, % by weight 
20 
softening point, .degree.C. 
295 
decomposition temperature, .degree.C. 
500 
______________________________________ 
Because of the low yield of the end product, i.e. polyhydroquinone, it is 
not advisable to realize this modification of the production process from 
the economic point of view. 
EXAMPLE 19 (negative) 
Polyhydroquinone was prepared basically as disclosed in Example 17 while 
maintaining the same conditions. However, the concentration of the aqueous 
solution of sodium hydroxide was 60%, i.e. said concentration was beyond 
the limits of the range specified in the claims. 
The results appeared to be as follows: 
______________________________________ 
yield of polyhydroquinone, % by weight 
20 
______________________________________ 
Commercial realization of such a modification of the production process is 
inexpedient because of an extremely low yield of the end product. 
Furthermore, in the process of preparing the polymer, the ductility of the 
reaction mixture is so high that it results in significant decrease in 
contact between the mixture and air and considerably affects specific 
power consumption required for stirring. 
EXAMPLE 20 (negative) 
Polyhydroquinone was prepared basically as diclosed in Example 17 while 
maintaining the same conditions. However, the rate of air blown through 
the mixture was 0.017 m.sup.3 /hr per kilogram of the monomer, i.e. said 
blowing rate of air was beyond the limits of the range specified in the 
claims. 
The results appeared to be as follows: 
______________________________________ 
yield of polyhydroquinone, % by weight 
30 
softening point, .degree.C. 
295 
decomposition temperature, .degree.C. 
500 
______________________________________ 
In the process of oxidative polycondensation, an intensive foaming of the 
reaction mixture was observed. By-products were formed in large quantity. 
EXAMPLE 21 (negative) 
Polyhydroquinone was prepared basically as disclosed in Example 17 while 
maintaining the same conditions. 
However, the blowing rate of air through the reaction mixture was 0.006 
m.sup.3 /hr per kilogram of hydroquinone. 
The yield of the end product, i.e. hydroquinone, was 35% by weight. 
Polyhydroquinone obtained in the form of amorphous powder was of the 
following characteristics: 
______________________________________ 
softening point, .degree.C. 
295 
decomposition temperature, .degree.C. 
500 
______________________________________ 
However, a great number of admixtures which were difficult to separate in 
this modification of the production process did not allow the polymer 
obtained to be employed for epoxyphenolic compounds. 
While the invention has been described herein in terms of specific 
Examples, numerous variations may be made in the invention without 
departing from the spirit and scope thereof as set forth in the appended 
claims.