TWI408120B - A process for producing isocyanates using diaryl carbonates - Google Patents

Abstract

This invention provides a production process which, in producing an isocyanate without using phosgene, is free from various problems as seen in the prior art and can stably produce the isocyanate at a high yield for a long period of time. The production process comprises the step of reacting diaryl carbonate with an amine compound in the presence of an aromatic hydroxy compound as a reaction solvent to give a reaction mixture containing an aryl carbamate containing a diaryl carbonate-derived aryl group, a diaryl carbonate-derived aromatic hydroxy compound, and a diaryl carbonate, the step of transferring the reaction mixture to a thermal decomposition reactor, and the step of thermally decomposing the aryl carbamate to give an isocyanate. In this production process, the reactor for reacting the diaryl carbonate with the amine compound is different from the reactor for thermal decomposition of the aryl carbamate.

Description

Method for producing isocyanate using diaryl carbonate

The present invention relates to a process for producing an isocyanate which is based on a diaryl carbonate.

Isocyanates are widely used as raw materials for the production of polyurethane foams, paints, adhesives, and the like. The main industrial manufacturing process for isocyanates is to react an amine compound with phosgene (phosgene method), and almost all of the world's production is produced by the phosgene process. However, the phosgene method has many problems.

First, a large amount of phosgene is used as a raw material. The phosgene is extremely toxic. In order to prevent the practitioner from coming into contact with phosgene, special attention must be paid to its operation, and special equipment for removing waste is also needed.

Secondly, in the phosgene method, a large amount of highly corrosive hydrogen chloride is produced as a by-product, so that the treatment for removing the hydrogen chloride is required, and the produced isocyanate mostly contains hydrolyzable chlorine, and thus the phosgene method is used. In the case of the produced isocyanate, the weather resistance and heat resistance of the polyurethane product may be adversely affected.

In view of such a background, a manufacturing method of an isocyanate compound which does not use phosgene is desired. As an example of a method for producing an isocyanate compound which does not use phosgene, a method of thermal decomposition using a urethane is proposed. It has been known for a long time that an isocyanate and a hydroxy compound are obtained by thermal decomposition of a urethane (for example, refer to Non-Patent Document 1). The basic reaction is exemplified by the following formula.

R(NHCOOR') _a → R(NCO) _a +a R'OH (1) (wherein R represents an organic residue of a valence, R' represents a monovalent organic residue, and a represents 1 or more The integer).

Among the urethanes, the aryl urethane having an ester group which is an aromatic group has a lower temperature of the thermal decomposition reaction than the alkyl carbamate whose ester group is an alkyl group (refer to Patent Document 1).

As a method of producing an aryl urethane, various methods have been described so far.

According to the description of Patent Document 2, it is described that an alkyl monoamine and a diaryl carbonate are reacted in the presence of a solvent such as benzene, dioxane or carbon tetrachloride, and are obtained in a yield of 90 to 95%. An alkyl aryl monocarboxylic acid aryl ester. Further, Patent Document 3 proposes a method of continuously producing phenyl methyl carbamate from methylamine and diphenyl carbonate.

However, these methods all use a lower alkyl monoamine as an amine, and a method of producing an alkyl aryl carbamate is not a method of producing an alkyl aryl aryl ester. In the case where an alkyl polyamine such as an alkyldiamine or an alkyltriamine is produced to produce a corresponding alkyl aryl carbamate, there is a problem that is completely different from that in the case of using an alkylmonoamine. The reason for this is that, in the case of an alkylmonoamine, except for the reaction represented by the formula (2), it is produced as a by-product by a side reaction represented by the formula (3) and/or the formula (4). a urea compound, and in the case of an alkyl polyamine such as an alkyl diamine or an alkyl triamine, for example, formed as a secondary The product has a wide variety of urea compounds such as the compound represented by the formula (5) and/or the formula (6) and/or the formula (7).

(wherein R' represents a monovalent alkyl group or an aromatic group, Ar represents a monovalent aromatic group, and p, q, and r each represent an integer of 1 or more).

That is, there is a problem in that the yield of the alkyl polyamino carboxylic acid ester as the target compound is lowered due to the by-product reaction or the like of the various urea compounds; and it is very difficult to self-contain the urea compound or the polyurea compound. The mixture is separated and the target product is purified.

Thus, attempts to produce alkyl aryl carbamates from alkyl polyamines and diaryl carbonates have been very rare, but have been reported several times. For example, according to the specification of Patent Document 4, a method of obtaining phenyl 1,6-hexamethylenediaminecarboxylate by dissolving 1 mol of diphenyl carbonate in 5 times of benzene is proposed. In the solution, a solution in which 1 mol of 1,6-hexamethylenediamine was dissolved in 5 times the amount of benzene was added dropwise, and the mixture was stirred at 80 ° C to carry out a reaction. According to this patent specification, it is described that, in order to carry out the reaction favorably, it is important to use a solvent which does not dissolve the phenyl 1,6-hexamethylenediaminecarboxylate as a product as a reaction solvent, as such. The solvent is preferably a hydrocarbon such as benzene or chlorobenzene.

From this point of view, in Non-Patent Document 3, 0.01 mol of diphenyl carbonate and 0.005 mol of 1,6-hexamethylenediamine are made up by using 40 mL of toluene as a reaction solvent. The reaction was carried out for 20 hours to obtain the target phenyl 1,6-hexamethylenediaminecarboxylate. However, even with such a large amount of toluene, the yield is 93%, and there is a problem that a urea compound or a polyurea compound which must be separated as a by-product is formed.

Further, Patent Document 5 describes a method for producing a diurethane compound by reacting a diaryl carbonate with an amine compound in the presence of a protic acid. However, when the manufacturing method described in Patent Document 5 is industrially carried out, the yield of the urethane compound is not sufficient, and in order to suppress the side reaction, the reaction must be carried out at a low temperature, and the reaction time becomes long. The shortcomings.

Patent Document 6 describes a method of reacting a diaryl carbonate with an aromatic polyamine in the presence of a heterocyclic tertiary amine such as 2-hydroxypyridine. This method has a problem that it is necessary to use a high-priced catalyst such as a reaction substrate or the like, and the reaction rate is low.

According to Patent Document 7, a method for synthesizing an aromatic urethane is disclosed in which an aromatic amine and a diaryl carbonate are present in the presence of a Lewis acid catalyst. The reaction is carried out at a temperature of from 140 ° C to 230 ° C. In this method, the use of the Lewis acid also has a problem of the etching apparatus, or it is difficult to separate and recover from the product.

Patent Document 8 describes a method for producing an alkyl aryl carbamate, which is characterized in that when an alkyl polyamine is reacted with a diaryl carbonate to produce an alkyl polyamino aryl ester, The amine group of the alkyl polyamine is used in an amount of 1 to 3 equivalents of diaryl carbonate, and an aromatic hydroxy compound is used as a reaction solvent to carry out the reaction in a substantially homogeneous dissolved state. According to this patent document, an alkyl polyamino carboxylic acid ester is obtained at a high yield in a high yield of usually 96% or more, preferably 98% or more in a preferred embodiment. However, although it was a very small amount, it was confirmed that a urea compound was formed, so that the formation of a urea compound could not be completely avoided.

On the other hand, in the thermal decomposition reaction of the urethane, various irreversible side reactions such as a thermal modification reaction in which the urethane is poor or a condensation reaction of the isocyanate formed by the thermal decomposition are easily caused. Examples of the side reaction include a reaction for forming a urea bond represented by the following formula (8), or a reaction for producing a carbodiimide represented by the following formula (9), or, for example, the following formula ( 10) The reaction for producing isocyanurates (see Non-Patent Documents 1 and 2).

R-N=C=O+O=C=N-R → R-N=C=N-R+CO ₂ (9)

These side reactions not only cause a decrease in the yield or selectivity of the target isocyanate, but also, in particular, when a polyisocyanate is produced, it is difficult to carry out long-term operation by depositing a polymer-like solid matter and occluding the reactor.

As a method for producing an isocyanate using a urethane as a raw material, various methods have been proposed so far.

According to Patent Document 9, an aromatic diisocyanate and/or a polyisocyanate are produced through the following two steps. Specifically, in the first step, the aromatic primary amine and/or the aromatic primary amine and the O-alkylamine group are present in the presence or absence of a catalyst, and in the presence or absence of urea and an alcohol. The formate is reacted to form an aryl dicarbamate and/or an aryl polyurethane, and the ammonia produced is removed as needed. In the second step, an aromatic isocyanate and/or an aromatic polyisocyanate is obtained by thermal decomposition of an aryldicarbamate and/or an arylpolyurethane.

There are several methods known for the production of corresponding isocyanates and alcohols by thermal decomposition of (cyclic) aliphatics, and in particular aromatic monocarbamates and dicarbamates: A method carried out at a high temperature in a gas phase, or a method carried out in a liquid phase at a lower temperature. However, sometimes the reaction mixture, for example, generates the above-mentioned side reaction, forms a precipitate, a polymerous substance and a plug in the reactor and the recovery device, or, in addition, forms a fixed substance on the wall surface of the reactor for a long period of time. In the case of producing isocyanate, the economic efficiency is poor.

Therefore, in order to improve the yield of thermal decomposition of the urethane, for example, a chemical method is described, for example, using a special catalyst (refer to Patent Document 10, Patent Document 11) or a catalyst using a composition with an inert solvent (refer to the patent literature). 12).

Specifically, in Patent Document 13, as a method for producing hexamethylene diisocyanate, there is described a method of using a methylbenzene toluenesulfonate and a diphenyl group in the presence of dibenzyltoluene as a solvent. The hexamethylene diethyl carbazate is thermally decomposed in the presence of a catalyst mixture of tin dichloride. However, the manufacture of the starting components, as well as the separation and purification and random recovery of the solvent and catalyst mixture, are not described in any detail, and therefore the economic efficiency of the process cannot be judged.

According to the method described in Patent Document 14, the urethane can be easily decomposed into an isocyanate and an alcohol in a carbon-containing fluidized bed without using a catalyst. Further, according to Patent Document 15, hexamethylene dialkyl urethane can be, for example, a gas permeable package containing carbon, copper, brass, steel, zinc, aluminum, titanium, chromium, cobalt or quartz. The hexamethylene diisocyanate is decomposed in the gas phase at a temperature exceeding 300 ° C in the presence or absence of a material. According to Patent Document 14, the method is carried out in the presence of a hydrohalide and/or a hydrohalide donor. However, this method cannot achieve a yield of more than 90% of hexamethylene diisocyanate. The reason for this is that a part of the decomposition product is bonded to form a urethane bond. Therefore, purification of hexamethylene diisocyanate must be further carried out by distillation, often resulting in an increase in yield loss.

Further, Patent Document 16 describes a case where the temperature is lower. The monocarbamate can be decomposed in good yield without the use of a solvent under an advantageous reduced pressure in the presence or absence of a catalyst and/or stabilizer. The decomposition products (monoisocyanate and alcohol) are removed by distillation from the boiling reaction mixture, and are separately collected by condensation. A method of partially removing the reaction mixture in order to remove by-products formed in thermal decomposition is described in a general form. Therefore, by-products can be removed from the bottom of the reactor, but the problem of fixing to the wall surface of the reactor remains, and the problem of long-term operation is not solved. Further, there is no description of the industrial application of the residual portion (containing a large amount of useful components).

According to Patent Document 17, the thermal decomposition of an aliphatic, alicyclic or aromatic polyurethane is carried out at 150 to 350 ° C and 0.001 to 20 bar in the presence of an inert solvent as a catalyst and aid. The hydrogen chloride, organic acid chloride, alkylating agent or organotin chloride of the agent is used in the presence or absence of the agent. The by-products produced, for example, can be continuously removed from the reactor together with the reaction solution, while adding a corresponding amount of a new solvent or a recovered solvent. A disadvantage of this method is that the space-time yield of the polyisocyanate is reduced, for example, by the use of a reflux solvent, and, for example, a large amount of energy is required to include solvent recovery. Further, the auxiliary agent used is volatile under the reaction conditions and can contaminate the decomposition product. Further, the amount of the residual portion of the produced polyisocyanate is large, which is problematic in terms of economic efficiency and reliability of industrial methods.

Patent Document 18 describes a urethane which is supplied in a liquid form along the inner surface of a tubular reactor in the presence of a high boiling point solvent, such as an alicyclic dicarbamate 5-(ethoxyl). Alkylcarbonylamino)-1-(ethoxycarbonylamino group A A method of continuous thermal decomposition of 1,3,3,3-trimethylcyclohexane. This method has the disadvantages of lower yield and lower selectivity in the production of (cyclo)aliphatic diisocyanates. Further, there is no description about the continuity of the recovery of the urethane which is subjected to re-bonding or partial decomposition, and the subsequent treatment with a solvent containing by-products and a catalyst is not described.

It is easily conceivable that if the above-described method for producing an aryl carbamate arylate and a method for producing an isocyanate by thermal decomposition of a urethane are combined, an isocyanate can be produced from a diaryl carbonate and an amine compound. . However, in order to combine the above-described method for producing an aryl carbamate aryl ester with a method for producing an isocyanate by thermal decomposition reaction of an aryl carbamate aryl ester, any one of the following methods is employed: a diaryl carbonate and an amine are used. a reaction solution obtained by reacting a compound, separating an aryl carbamate, and performing a complicated operation of the thermal decomposition reaction of the aryl carbamate; or directly using the reaction liquid obtained by producing an aryl urethane for heat The method of decomposition reaction.

In this regard, Patent Document 19 describes a method in which an aromatic amine and a diaryl carbonate are reacted in the presence of a Lewis acid catalyst to synthesize a urethane compound, followed by synthesis of a urethane. In the diaryl carbonate used for the compound, the urethane compound is thermally decomposed to synthesize an aromatic isocyanate. In the patent document, there is exemplified a method of reacting a urethane-containing reaction solution obtained by reacting an amine compound with a diaryl carbonate in the presence of a Lewis acid catalyst, in the urethane synthesis plant. The thermal decomposition reaction was carried out in the reactor used to produce an isocyanate.

[Patent Document 1] U.S. Patent No. 3,992,430 [Patent Document 2] Japanese Patent Application Laid-Open No. SHO 52-71443 [Patent Document 3] Japanese Patent Application Publication No. SHO 61-183257 [Patent Document 4] German Patent No. 925 496 [Patent Document 5] Japanese Patent Application Laid-Open No. Hei 10-316645 (Patent Document 6) Japanese Patent Application Publication No. Japanese Laid-Open Patent Publication No. 2004-262834 [Patent Document No. 10] Japanese Patent Application Publication No. Hei. No. Hei. US Patent No. 2692275 [Patent Document 11] US Patent No. 3,374,941 [Patent Document 12] US Patent No. 4,081,472 [Patent Document 13] US Patent No. 4,388,426 [Patent Document 14] US Patent No. 4482499 [Patent Document 15] U.S. Patent No. 4,613,466 [Patent Document 16] U.S. Patent No. 4,384,033 [Patent Document 17] U.S. Patent No. 4,388,246 [Patent Document 18] U.S. Patent No. 4,692,550 [Patent Document 19] Japanese Patent Application Publication No. 2004-262835

[Non-Patent Document 1] Berchte der Deutechen Chemischen Gesellschaft, Vol. 3, p. 653, 1870 [Non-Patent Document 2] Journal of American Chemical Society, Vol. 81, p. 2138, 1959 [Non-Patent Document 3] Journal of Polymer Science Polymer Chemistry Edition, Vol. 17, p. 835, 1979

However, since the synthesis reaction and the thermal decomposition reaction of the urethane compound are carried out in the same reactor, it is impossible to select a reactor or a reaction condition corresponding to the synthesis reaction and the thermal decomposition reaction of the urethane compound, respectively. . In fact, according to the exemplification of Patent Document 19, the yield of isocyanate is low. Further, in Patent Document 19, there is no detailed description relating to a method of continuously producing an isocyanate, and it is not satisfactory from the viewpoint of industrially producing isocyanate efficiently.

As described above, in the current state of the art, a method of producing an aryl urethane by using a diaryl carbonate and an amine compound as a raw material, and producing an isocyanate via the urethane urethane has many problems to be solved, and has not yet reached industrialization.

SUMMARY OF THE INVENTION An object of the present invention is to provide a process for producing an isocyanate using a diaryl carbonate and an amine compound without various problems encountered in the prior art.

As a result of intensive studies on the above problems, the inventors of the present invention have found a method for producing an isocyanate which is obtained by reacting a diaryl carbonate with an amine compound under specific conditions and transporting it to heat under specific conditions. In the decomposition reactor, the carbamate contained in the mixture is subjected to thermal decomposition reaction to produce an isocyanate, thereby completing the present invention.

That is, the present invention provides [1] a method for producing an isocyanate comprising the steps of: reacting a diaryl carbonate with an amine compound in a reactor for carrying out a reaction of a diaryl carbonate with an amine compound to obtain a Aryl group derived from diaryl carbonate a reaction mixture of an aryl carbamate, an aromatic hydroxy compound derived from a diaryl carbonate, and a diaryl carbonate; the reaction mixture is sent to a thermal decomposition reactor, wherein the thermal decomposition reactor is passed through a pipe The reactor is connected to carry out a reaction in which a diaryl carbonate is reacted with an amine compound; and an isocyanate is obtained by subjecting the aryl carbamate to a thermal decomposition reaction.

[2] The production method of the above [1], which further comprises the step of washing the high-boiling by-product attached to the thermal decomposition reactor with an acid.

[3] The production method according to the above [1] or [2] wherein the reaction of the diaryl carbonate with the amine compound is based on a condition that the stoichiometric ratio of the diaryl carbonate to the amine group constituting the amine compound is 1 or more Go on.

[4] The production method according to any one of [1] to [3] wherein the diaryl carbonate and the amine compound are reacted in the presence of an aromatic hydroxy compound as a reaction solvent.

[5] The production method according to the above [4], wherein the aromatic hydroxy compound as a reaction solvent is the same as the compound ArOH, and the compound ArOH has the composition of the aromatic aryl carbonate ArOCOOAr (Ar represents an aromatic group, O A structure in which a hydrogen atom is added to a group ArO representing an oxygen atom.

[6] The production method according to any one of [1] to [5] wherein the reaction mixture is supplied as a liquid to a thermal decomposition reactor.

[7] The production method according to the above [6], wherein the reaction mixture is supplied to the thermal decomposition reactor at a temperature ranging from 10 ° C to 180 ° C.

[8] The manufacturing method according to any one of [1] to [7] wherein the supply is continuously The reaction mixture is passed to a thermal decomposition reactor.

[9] The production method according to any one of [1] to [8] wherein the low-boiling component produced in the thermal decomposition reaction is recovered as a gas phase component from a thermal decomposition reactor, and the liquid phase component is recovered. It is recovered from the bottom of the reactor.

[10] The production method according to [9] above, wherein the recovery of the gas phase component and the recovery of the liquid phase component are continuously performed.

[11] The production method of the above [9] or [10], wherein the isocyanate obtained by the thermal decomposition reaction of the aryl carbamate is recovered as a gas phase component in a pyrolysis reactor, and contains carbonic acid The liquid phase component of the diarylate is recovered from the bottom of the reactor.

[12] The production method according to the above [11], which further comprises the step of separating the isocyanate-containing gas phase component recovered from the thermal decomposition reactor by distillation in a distillation column, recovering the isocyanate; and recovering the recovered from the autothermal decomposition reactor The gas phase component of the isocyanate is supplied to the distillation column in the gas phase.

[13] The production method according to [11] or [12] wherein the liquid phase component containing a diaryl carbonate contains a mixture of aryl carbamate, and a part or all of the mixture is supplied to the upper portion of the reactor. .

[14] The production method according to the above [9] or [10] wherein the isocyanate obtained by the thermal decomposition reaction of the aryl carbamate is recovered from the bottom of the reactor subjected to the thermal decomposition reaction as a liquid phase component.

[15] The method according to the above [14], wherein the liquid phase component recovered from the bottom of the reactor contains isocyanate and aryl carbamate, and part or all of the isocyanate is separated from the liquid phase component, leaving part or all of It is supplied to the upper part of the reactor.

[16] The production method according to [14] or [15] wherein the isocyanate-containing mixture recovered from the thermal decomposition reactor is separated by distillation, and the isocyanate is recovered.

[17] The production method according to any one of [1] to [16] wherein the type of the reactor for reacting the diaryl carbonate with the amine compound may be the same as or different from the type of the thermal decomposition reactor. And a reactor in which the reaction of the diaryl carbonate and the amine compound is carried out, and the thermal decomposition reactor is selected from the group consisting of a column reactor and a tank reactor.

[18] The production method according to [17], wherein the thermal decomposition reactor is composed of at least one selected from the group consisting of an evaporation can, a continuous multi-stage distillation column, a packed column, a thin film evaporator, and a falling film evaporator. .

[19] The production method according to any one of [1] to [18] wherein the reaction of the diaryl carbonate with the amine compound is carried out in the presence of a catalyst.

[20] The production method according to any one of [1] to [19] wherein the thermal decomposition reaction is carried out in a liquid phase.

[21] The production method according to any one of [1] to [20] wherein the diaryl carbonate is a compound represented by the following formula (11): (wherein R ¹ represents an aromatic group having a carbon number of 6 to 12).

[22] The method according to the above [21], wherein the diaryl carbonate contains 0.001 ppm to 10% of a metal atom.

[23] The method according to the above [22], wherein the metal atom is selected from One or a plurality of groups of iron, nickel, cobalt, zinc, tin, copper, and titanium.

[24] The production method according to any one of [1] to [23] wherein the diaryl carbonate is produced by the steps comprising the following steps (1) to (3): Step (1) : reacting an organotin compound having a tin-oxygen-carbon bond with carbon dioxide to obtain a reaction mixture containing a dialkyl carbonate; and (2): separating the reaction mixture to obtain a dialkyl carbonate and a residual liquid; 3): The dialkyl carbonate separated in the step (2) is reacted with the aromatic hydroxy compound A to obtain a diaryl carbonate, and the alcohol produced as a by-product is recovered.

[25] The method according to the above [24], wherein the aromatic hydroxy compound A is an aromatic hydroxy compound having 6 to 12 carbon atoms.

[26] The production method according to the above [24] or [25] wherein the diaryl carbonate is produced by further comprising the steps of the following steps (4) and (5): Step (4): The residual liquid obtained in the step (2) is reacted with an alcohol to form an organotin compound having a tin-oxygen-carbon bond and water, and the water is removed from the reaction system; and step (5): obtained in the step (4) The organotin compound having a tin-oxygen-carbon bond is reused as an organotin compound having a tin-oxygen-carbon bond in the step (1).

[27] The production method according to [26], wherein the alcohol recovered in the step (3) Used as part or all of the alcohol of this step (4).

[28] The production method according to any one of [9] to [27] wherein the diaryl carbonate is separated and recovered from the liquid phase component or the gas phase component recovered from the thermal decomposition reactor. The aryl ester is reused as a starting material.

[29] The production method according to [1] or [24] wherein the aromatic hydroxy compound is separated and recovered from the liquid phase component or the gas phase component recovered from the thermal decomposition reactor, and the aromatic hydroxy compound is used as the The aromatic hydroxy compound A in the step (3) or the aromatic hydroxy compound as the reaction solvent is reused.

[30] The production method according to any one of [1] to [29] wherein the amine compound is a polyamine compound.

[31] The production method according to the above [30], wherein the amine compound is a compound represented by the following formula (12): (wherein R ² represents one selected from the group consisting of an aliphatic group having a carbon number of from 1 to 20 selected from an atom selected from carbon and oxygen, and an aromatic group having a carbon number of from 6 to 20, which has n equal atomic valence; n is an integer from 2 to 10).

[32] The production method according to the above [31], wherein the amine compound is a diamine compound wherein n is 2 in the formula (12).

[33] The production method according to any one of [1] to [32] wherein amination is supplied The composition is carried out in a liquid state to a reactor in which a carbonate and an amine compound are reacted.

[34] The production method according to any one of [1] to [33] wherein, when the amine compound is supplied to the reactor for reacting the carbonate with the amine compound, it is used as an alcohol, water, or carbonate. It is carried out in the state of the mixture.

According to the method of the present invention, a diaryl carbonate and an amine compound can be used as a raw material to produce an isocyanate continuously and in good yield in a long period of time.

Hereinafter, the best mode for carrying out the invention (hereinafter referred to as "this embodiment") will be described in detail. The present invention is not limited to the embodiments described below, and various modifications can be made without departing from the spirit and scope of the invention.

The production method of the present embodiment includes a method for producing an isocyanate obtained by reacting a diaryl carbonate with an amine compound in the presence of an aromatic hydroxy compound as a reaction solvent to obtain an aryl group having a diaryl carbonate. a step of reacting an aryl carbamate, an aromatic hydroxy compound derived from a diaryl carbonate, and a diaryl carbonate; a step of transporting the reaction mixture to a thermal decomposition reactor; and by causing the amine group The step of thermally decomposing the aryl formate to obtain an isocyanate, and carrying out the reaction of reacting the diaryl carbonate with the amine compound, is different from the thermal decomposition reactor of the aryl carbamate.

First, the diaryl carbonate and the amine compound used in the production method of the present embodiment will be described.

The diaryl carbonate used in the production method of the present embodiment is of the following formula (13) The compound represented.

(wherein R ¹ represents an aromatic group having a carbon number of 6 to 20).

R ^{1 of the} above formula (13) is preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms, more preferably an aromatic hydrocarbon group having 6 to 12 carbon atoms. May also be used R ¹ is 21 or more carbon atoms of the aromatic hydrocarbon group of a diaryl carbonate, an ester of the isolated isocyanate viewpoint of readily generated from the following group of heat by the decomposition reaction of the carboxylic acid ester, preferably The carbon number constituting R ¹ is 20 or less.

Examples of such R ¹ include a phenyl group, a methylphenyl group (each isomer), an ethylphenyl group (each isomer), a propylphenyl group (each isomer), and butylbenzene. Base (each isomer), pentylphenyl (each isomer), hexylphenyl (each isomer), dimethylphenyl (each isomer), methyl ethylphenyl (variety) Structure), methyl propyl phenyl (each isomer), methyl butyl phenyl (each isomer), methyl amyl phenyl (each isomer), diethyl phenyl (each Isomer), ethyl propyl phenyl (each isomer), ethyl butyl phenyl (each isomer), dipropyl phenyl (each isomer), trimethylphenyl (each Isomer), triethylphenyl (each isomer), naphthyl (each isomer), and the like. Among these diaryl carbonates, R ¹ is preferably a diaryl carbonate having an aromatic hydrocarbon group having 6 to 8 carbon atoms. Examples of such a diaryl carbonate include diphenyl carbonate and carbonic acid. (Methylphenyl) ester (each isomer), di(diethylphenyl) carbonate (each isomer), di(methylethylphenyl) carbonate (each isomer), and the like.

It is preferred that the diaryl carbonates contain metals in the range of preferably 0.001 ppm to 10%, more preferably 0.001 ppm to 5%, and even more preferably 0.002 ppm to 3%. atom. Further, the metal atom may exist as a metal ion or may exist as a metal atom monomer. As the metal atom, a metal atom which may be a divalent or tetravalent atomic value is preferable, and among them, one selected from the group consisting of iron, cobalt, nickel, zinc, tin, copper, and titanium, or a plurality of metals is preferable. The inventors of the present invention were surprised to find that the modification of the aryl urethane formed by the reaction of the diaryl carbonate with the amine compound is achieved by using a diaryl carbonate containing a metal atom in a concentration within the above range. The effect of the reaction. The mechanism for achieving such an effect is not clear, but the inventors have speculated that the metal atoms are coordinated to the urethane bond (-NHCOO-) of the urethane formed in the reaction. The urethane bond is stabilized to suppress a side reaction such as shown by the above formula (4), formula (8) or the like. Further, when the reaction liquid containing the aryl carbamate is transported as follows, the effect of suppressing the modification reaction of the aryl carbamate aryl ester by the metal atom is also determined, and the mechanism is also different from the above.

When the diaryl carbonate is mixed with an amine compound to produce a mixture, and the above-exemplified metal atom is added in the above range in the above-mentioned range, the same effect can be obtained, but the inventors of the present invention conducted an effort to study the result. It has been found that it is difficult to obtain the above effects by adding a metal atom only to a mixture of a diaryl carbonate and an amine compound. The reason for such a result is not clear, but the inventors of the present invention presumed that when the diaryl carbonate contains a metal atom, the diaryl carbonate is coordinated to a metal atom, and in contrast to the diaryl carbonate and the amine. When a metal atom is added to a mixture of compounds, The interaction between a metal atom and a diaryl carbonate, the interaction between the metal atom and the amine compound is large, so that the metal atom is firmly coordinated to the amine compound, and it is difficult to coordinate the urethane of the formed aryl carbamate. key.

The carbonate of the present embodiment is preferably produced by the following method. When the diaryl carbonate produced by the method contains the metal atom as exemplified above in the above preferred range, the diaryl carbonate can be used as it is. ester. When the amount of the metal atom contained in the diaryl carbonate is less than the above range, a metal atom may be added in another manner, for example, as an organic acid salt such as an acetate or a naphthenate, a chloride or an acetamidineacetate complex. And add. Moreover, when it is more than the above range, the amount of the metal atom can be reduced to the above range by, for example, solvent cleaning, distillation purification, crystallization, removal by ion exchange resin, removal by a chelate resin, or the like. And use.

Further, as for the metal atom contained in the above range in the diaryl carbonate, it is basically determined that it does not have a catalytic action of the reaction of the diaryl carbonate with the amine compound, and therefore, it should be combined with the following aryl carbamate The manufacturing catalyst is clearly distinguished.

The amount of the metal component contained in the diaryl carbonate can be quantified by a well-known method, for example, according to the form of the sample or the amount of the metal component contained, from the atomic absorption spectrometry, the inductively coupled plasma luminescence analysis. Method, inductive coupling type plasma mass analysis method, fluorescent X-ray analysis method, X-ray photoelectron spectroscopy, electron beam micro analyzer, secondary ion mass spectrometry and the like are selected.

As a method for producing a diaryl carbonate, a well-known method can be used. Preferably, a method is employed in which an organotin compound having a tin-oxygen-carbon bond is reacted with carbon dioxide to produce a carbonate, and a diaryl carbonate is produced from the carbonate and an aromatic hydroxy compound. That is, the carbonate can be produced by the following procedure.

Step (1): (dialkyl carbonate formation step) a step of reacting an organotin compound having a tin-oxygen-carbon bond with carbon dioxide to obtain a reaction mixture containing a dialkyl carbonate; and step (2): (carbonic acid) An alkyl ester separation step) a step of separating the dialkyl carbonate from the reaction mixture and obtaining a residual liquid; and a step (3): (diaryl carbonate production step), the dialkyl carbonate and the aromatic separated in the step (2) The group hydroxy compound A is reacted to obtain a diaryl carbonate, and the step of recovering the alcohol as a by-product is recovered.

Further, in addition to the steps (1) to (3), the following steps (4) and (5) may be performed.

Step (4): (organic tin compound regeneration step) reacting the residual liquid obtained in the step (B) with an alcohol to form an organotin compound having a tin-oxygen-carbon bond and water, and removing the water from the reaction system Step; (5): (reuse step) the organotin compound having a tin-oxygen-carbon bond obtained in the step (4) as an organic having a tin-oxygen-carbon bond in the step (1) The step of recycling the tin compound.

As the organotin compound used in the step (1), a dialkyltin compound is preferably used. The dialkyltin compound refers to an organotin compound in which two alkyl groups are bonded to a tin atom.

Examples of the dialkyl tin compound include self-selected from the following formula (14) A compound selected from at least one of the group consisting of a dialkyltin compound and a tetraalkyldistannoxane compound represented by the following formula (15).

(wherein R ³ and R ⁴ each independently represent a linear or branched alkyl group having 1 to 12 carbon atoms; and X ¹ and X ² each independently represent an alkoxy group, a decyloxy group and a halogen atom; At least one substituent in the group formed; a and b are each an integer of 0 to 2, a+b=2; c and d are integers of 0 to 2, respectively, and c+d=2).

(wherein R ⁵ , R ⁶ , R ⁷ and R ⁸ each independently represent a linear or branched alkyl group having 1 to 12 carbon atoms; and X ³ and X ⁴ represent an alkoxy group selected from the group consisting of alkoxy groups and argon At least one substituent of the group consisting of a group and a halogen atom; e, f, g, and h are each an integer of 0 to 2, and e+f=2, g+h=2).

R ³ and R ^{4 of the} dialkyltin catalyst represented by the above formula (14), and R ⁵ , R ⁶ and R ^{7 of the} tetraalkyldistannoxane compound represented by the above formula (15) Examples of R ⁸ and the like include methyl group, ethyl group, propyl group (each isomer), butyl group (each isomer), pentyl group (each isomer), and hexyl group (each isomer). Heptyl (each isomer), octyl (each isomer), thiol (each isomer), thiol (each isomer), dodecyl (each isomer), etc. The number of carbon atoms is an alkyl group as an aliphatic hydrocarbon group selected from an integer of 1 to 12. More preferably, the number of carbon atoms constituting the group is a linear or branched alkyl group selected from an integer of 1 to 8, and the number of carbon atoms constituting the group may be outside the range indicated above. A dialkyltin compound of an alkyl group, but sometimes the fluidity is deteriorated or the productivity is impaired. Further, in consideration of the ease of obtaining in industrial production, it is preferably n-butyl or n-octyl.

X ¹ and X ^{2 of the} dialkyl tin compound represented by the above formula (14) and X ³ and X ^{4 of the} tetraalkyldistannoxane compound represented by the formula (15) represent an alkane selected from the group consisting of At least one substituent selected from the group consisting of an oxy group, a decyloxy group and a halogen atom. When the group is an alkoxy group and/or a decyloxy group, it is preferred that the number of carbon atoms constituting the group is selected. The base of an integer from 0 to 12. As such an example, a methoxy group, an ethoxy group, a propoxy group (each isomer), a butoxy group (each isomer), a pentyloxy group (each isomer), and a hexyloxy group are exemplified ( Isomers, heptyloxy (each isomer), octyloxy (each isomer), decyloxy (each isomer), decyloxy (each isomer), etc. are linear or Alkoxy groups composed of a branched saturated alkyl group and an oxygen atom, and an alkyloxy group, a propyloxy group, a butoxy group, a pentyloxy group, a dodecyloxy group or the like are linear or branched. A saturated alkyl group, a carbonyl group and an oxygen atom form a halogen atom such as a decyloxy group, a chloro group or a bromo group. In consideration of fluidity or solubility, it is considered to be used as a catalyst for producing a carbonate, and a further preferred example is an alkoxy group having 4 to 6 carbon atoms.

Examples of the dialkyl tin compound represented by the formula (14) include dimethyl-dimethoxy tin, dimethyl-diethoxy tin, and dimethyl-dipropoxy tin ( Each isomer), dimethyl-dibutoxytin (each isomer), dimethyl-dipentyloxytin (each isomer), dimethyl-dihexyloxytin (variety) Structure), dimethyl-diheptyltin (each isomer), dimethyl-dioctyl tin (each isomer), dimethyl-dimethoxy tin (each isomer) ), dimethyl-dimethoxy tin (each isomer), dibutyl-dimethoxy tin (each isomer), dibutyl-diethoxy tin (each isomer), Dibutyl-dipropoxytin (each isomer), dibutyl-dibutoxytin (each isomer), dibutyl-dipentyloxytin (each isomer), dibutyl Base-dihexyloxytin (each isomer), dibutyl-diheptyloxytin (each isomer), dibutyl-dioctyl tin (each isomer), dibutyl- Dimethoxytin (each isomer), dibutyl-dimethoxytin (each isomer), dioctyl-dimethoxy tin (isomeric), dioctyl-diethyl Oxytin (various Structure), dioctyl-dipropoxytin (each isomer), dioctyl-dibutoxytin (each isomer), dioctyl-dipentyloxytin (each isomer) ), dioctyl-dihexyltin (each isomer), dioctyl-diheptyl tin (each isomer), dioctyl-dioctyl tin (each isomer), Dialkyl-dialkyloxy tin such as dioctyl-dimethoxytin (each isomer), dioctyl-dimethoxytin (each isomer), dimethyl-diethyl oxime Base tin, dimethyl-dipropenyl tin oxide (each isomer), dimethyl-dibutylphosphonium tin (each isomer), dimethyl-pentanyl tin oxide (isomeric , dimethyl-bis(dodecyloxy)tin (each isomer), dibutyl-diethoxytin (each isomer), dibutyl-dipropoxy tin oxide (each Isomers), dibutyl-dibutylphosphonium tin (each isomer), dibutyl-dipentyl methoxy tin (each isomer), dibutyl-di(dodecyloxy) Tin (each isomer), dioctyl-diethoxytin (each isomer), dioctyl-dipropoxytin (each isomer), dioctyl-dibutyl Dialkyl groups such as tin oxytin (each isomer), dioctyl-pentanyl pentoxide (each isomer), dioctyl-di(dodecyloxy) tin (each isomer) Dimethoxy tin, dimethyl-tin dichloride, dimethyl-tin dibromide, dibutyl-tin dichloride (each isomer), dibutyl-tin dibromide (different a structure, a dialkyl-dihalide such as dioctyl-tin dichloride (each isomer) or dioctyl-tin dibromide (each isomer).

Among these, preferred are dimethyl-dimethoxy tin, dimethyl-diethoxytin, dimethyl-dipropoxytin (each isomer), dimethyl-di Butoxytin (each isomer), dimethyl-dipentyloxytin (each isomer), dimethyl-dihexyloxytin (each isomer), dimethyl-diheptyloxy Base tin (each isomer), dimethyl-dioctyl tin (each isomer), dimethyl-dimethoxy tin (each isomer), dimethyl-dimethoxy tin (each isomer), dibutyl-dimethoxytin (each isomer), dibutyl-diethoxytin (each isomer), dibutyl-dipropoxytin (each Isomers), dibutyl-dibutoxytin (each isomer), dibutyl-dipentyloxytin (each isomer), dibutyl-dihexyloxytin (isomeric) , dibutyl-diheptyltin (each isomer), dibutyl-dioctyl tin (each isomer), dibutyl-dimethoxy tin (each isomer) , dibutyl-dimethoxytin (each isomer), dioctyl-dimethoxy tin (each isomer), dioctyl-diethoxytin (isomeric), two Octyl-dipropoxytin Structure), dioctyl-dibutoxytin (each isomer), dioctyl-dipentyloxytin (each isomer), dioctyl-dihexyloxytin (each isomer) ), dioctyl-diheptane Oxytin (each isomer), dioctyl-dioctyl tin (each isomer), dioctyl-dimethoxytin (each isomer), dioctyl-dimethoxy group a dialkyl-dialkyloxy tin such as tin (each isomer), more preferably dibutyl-dipropoxytin (each isomer), dibutyl-dibutoxy tin ( Each isomer), dibutyl-dipentyloxytin (each isomer), dibutyl-dihexyloxytin (each isomer), dibutyl-diheptyloxy tin (variety) Structure), dioctyl-dipropoxytin (each isomer), dioctyl-dibutoxytin (each isomer), dioctyl-dipentyloxytin (each isomer) a dialkyl-dialkyloxy tin such as dioctyl-dihexyltin (each isomer) or dioctyl-diheptyloxyn (each isomer), and further preferably dibutyl -dibutoxytin (each isomer), dibutyl-dipentyloxytin (each isomer), dibutyl-dihexyloxytin (each isomer), dibutyl- Diheptyltin (each isomer), dibutyl-dioctyl tin (each isomer), dioctyl-dibutoxytin (each isomer), dioctyl-dipentane Oxytin (each isomer) Dioctyl - dihexyloxy tin (including isomers), dioctyl - diheptyloxy tin (including isomers), dioctyl - dioctyloxy tin (including isomers thereof).

The dialkyl tin compound represented by the above formula (14) exhibits a monomer structure, but may also be a multimeric structure or an associate.

Examples of the tetraalkyldialkoxydistannoxane represented by the formula (15) include 1,1,3,3-tetramethyl-1,3-dimethoxydistannoxane. 1,1,3,3-tetramethyl-1,3-diethoxydistannoxane, 1,1,3,3-tetramethyl-1,3-dipropoxydistannoxane (each isomer), 1,1,3,3-tetramethyl-1,3-dibutoxydistannoxane (each isomer), 1,1,3,3-tetramethyl- 1,3-dipentyloxystannane (each isomer), 1,1,3,3-tetramethyl-1,3-dihexyloxystannane (each isomer), 1,1,3,3-tetramethyl-1,3-diheptyloxydistannoxane , 1,1,3,3-tetramethyl-1,3-dioctoxydistannoxane (each isomer), 1,1,3,3-tetramethyl-1,3- Dimethoxy distannoxane (each isomer), 1,1,3,3-tetramethyl-1,3-dimethoxyoxydistannoxane (each isomer), 1,1, 3,3-tetrabutyl-1,3-dimethoxydistannoxane (each isomer), 1,1,3,3-tetrabutyl-1,3-diethoxyditin oxide Alkanes (each isomer), 1,1,3,3-tetrabutyl-1,3-dipropoxydistannoxane (each isomer), 1,1,3,3-tetrabutyl -1,3-dibutoxydistannoxane (each isomer), 1,1,3,3-tetrabutyl-1,3-dipentyloxydistannoxane (each isomer) 1,1,3,3-tetrabutyl-1,3-dihexyloxystannane (each isomer), 1,1,3,3-tetrabutyl-1,3-diheptane Oxydistanoxane (each isomer), 1,1,3,3-tetrabutyl-1,3-dioctoxydistannoxane (each isomer), 1,1,3, 3-tetrabutyl-1,3-dimethoxyoxystannane (each isomer), 1,1,3,3-tetrabutyl-1,3-dimethoxyoxydistannoxane ( Each isomer), 1,1,3,3-tetraoctyl-1,3-dimethoxydistannoxane (each isomer), 1,1,3,3-tetraoctyl-1 , 3 Diethoxydistannoxane (each isomer), 1,1,3,3-tetraoctyl-1,3-dipropoxydistannoxane (each isomer), 1,1, 3,3-tetraoctyl-1,3-dibutoxydistannoxane (each isomer), 1,1,3,3-tetraoctyl-1,3-dipentyloxydithion Alkanes (each isomer), 1,1,3,3-tetraoctyl-1,3-dihexyloxystannane (each isomer), 1,1,3,3-tetraoctyl -1,3-diheptyloxydistannoxane (each isomer), 1,1,3,3-tetraoctyl-1,3-dioctoxydistannoxane (each isomer) 1,1,3,3-tetraoctyl-1,3-dimethoxyoxystannane (each isomer), 1,1,3,3-tetraoctyl-1,3-dioxin 1,1,3,3-tetraalkyl-1,3-dialkoxy-distannoxane, 1,1,3,3-tetramethyl, etc., such as oxydistannoxane (each isomer) - 1,3-Diethoxydecylstannane, 1,1,3,3-tetramethyl-1,3-dipropoxyoxydistannoxane (isomeric), 1,1, 3,3-Tetramethyl-1,3-dibutoxyoxydistannoxane (each isomer), 1,1,3,3-tetramethyl-1,3-dipentyloxy 2 Tinoxane (each isomer), 1,1,3,3-tetramethyl-1,3-bis(dodecyloxy)distannoxane (each isomer), 1,1,3 , 3-tetrabutyl-1,3-diethoxydecanestane (each isomer), 1,1,3,3-tetrabutyl-1,3-dipropoxydioxytin Oxyalkane (each isomer), 1,1,3,3-tetrabutyl-1,3-dibutoxyoxydistannoxane (each isomer), 1,1,3,3-tetra Butyl-1,3-dipentyloxydistannoxane (each isomer), 1,1,3,3-tetrabutyl-1,3-di(dodecyloxy)ditin oxide Alkanes (each isomer), 1,1,3,3-tetraoctyl-1,3-diethoxydecanestane (each isomer), 1,1,3,3-tetraxin Base-1,3-dipropenyloxydistannoxane (each isomer), 1,1,3,3-tetraoctyl-1,3-dibutoxyoxydistannoxane Structure), 1,1,3,3-tetraoctyl-1,3-dipentyloxydistannoxane (each isomer), 1,1,3,3-tetraxin 1,1,3-bis(dodecyloxy)distannoxane (each isomer), etc. 1,1,3,3-tetraalkyl-1,3-dimethoxyoxydistannoxane, 1 , 1,3,3-tetramethyl-1,3-dichlorodistannoxane, 1,1,3,3-tetramethyl-1,3-dibromodistannoxane, 1,1,3 , 3-tetrabutyl-1,3-dichlorodistannoxane (each isomer), 1,1,3,3-tetrabutyl-1,3-dibromodistannoxane (isomeric , 1,1,3,3-tetraoctyl-1,3-dichlorodistannoxane (each isomer), 1,1,3,3-tetraoctyl-1,3-dibromo 1,1,3,3-tetraalkyl-1,3-dihaloxystannane such as distannoxane (each isomer).

Among these, more preferred are 1,1,3,3-tetramethyl-1,3-dimethoxydistannoxane, 1,1,3,3-tetramethyl-1,3- Diethoxydistannoxane, 1,1,3,3-tetramethyl-1,3-dipropoxydistannoxane (each isomer), 1,1,3,3-tetramethyl base- 1,3-dibutoxydistannoxane (each isomer), 1,1,3,3-tetramethyl-1,3-dipentyloxydistannoxane (each isomer), 1,1,3,3-tetramethyl-1,3-dihexyloxystannane (each isomer), 1,1,3,3-tetramethyl-1,3-diheptyloxy 1, oxanitoxane (each isomer), 1,1,3,3-tetramethyl-1,3-dioctoxydistannoxane (isomers), 1,1,3,3 -tetramethyl-1,3-dimethoxyoxystannane (each isomer), 1,1,3,3-tetramethyl-1,3-dimethoxyoxydistannoxane (each Isomer), 1,1,3,3-tetrabutyl-1,3-dimethoxydistannoxane (each isomer), 1,1,3,3-tetrabutyl-1, 3-diethoxydistannoxane (each isomer), 1,1,3,3-tetrabutyl-1,3-dipropoxydistannoxane (each isomer), 1, 1,3,3-tetrabutyl-1,3-dibutoxydistannoxane (each isomer), 1,1,3,3-tetrabutyl-1,3-dipentyloxy Tinoxane (each isomer), 1,1,3,3-tetrabutyl-1,3-dihexyloxystannane (each isomer), 1,1,3,3-tetra Butyl-1,3-diheptyloxydistannoxane (each isomer), 1,1,3,3-tetrabutyl-1,3-dioctoxydistannoxane (each Isomer), 1,1,3,3-tetrabutyl-1,3-dimethoxyoxystannane (each isomer), 1,1,3,3-tetrabutyl-1, 3-dimethoxydistannoxane (each isomer), 1,1,3,3-tetraoctyl-1,3-dimethoxydistannoxane (each isomer), 1, 1,3,3-tetraoctyl-1,3-diethoxydistannoxane (each isomer), 1,1,3,3-tetraoctyl-1,3-dipropoxy Tinoxane (each isomer), 1,1,3,3-tetraoctyl-1,3-dibutoxydistannoxane (each isomer), 1,1,3,3-tetra Octyl-1,3-dipentoxydistannoxane (each isomer), 1,1,3,3-tetraoctyl-1,3-dihexyloxydistannoxane (isomeric , 1,1,3,3-tetraoctyl-1,3-diheptyloxydistannoxane (each isomer), 1,1,3,3-tetraoctyl-1,3- Dioctyloxystannane (each isomer), 1,1,3,3-tetraoctyl-1,3-dimethoxyoxystannane (each isomer), 1,1,3,3-tetraoctyl-1,3-dioxanium 1,1,3,3-tetraalkyl-1,3-dialkoxy-distannoxane, etc., wherein, further preferably 1, 1, 3, 3-tetrabutyl-1,3-dibutoxydistannoxane (each isomer), 1,1,3,3-tetrabutyl-1,3-dipentyloxydistannoxane ( Each isomer), 1,1,3,3-tetrabutyl-1,3-dihexyloxystannane (each isomer), 1,1,3,3-tetrabutyl-1 , 3-diheptyloxydistannoxane (each isomer), 1,1,3,3-tetrabutyl-1,3-dioctoxydistannoxane (each isomer), 1 1,1,3,3-tetraoctyl-1,3-dibutoxydistannoxane (each isomer), 1,1,3,3-tetraoctyl-1,3-dipentyloxy Distannoxane (each isomer), 1,1,3,3-tetraoctyl-1,3-dihexyloxystannane (each isomer), 1,1,3,3- Tetraoctyl-1,3-diheptyloxydistannoxane (each isomer), 1,1,3,3-tetraoctyl-1,3-dioctoxydistannoxane Structure).

The tetraalkyldialkoxydistannoxane represented by the above formula (15) exhibits a monomer structure, but may also be a multimeric structure or an associate.

It is known that usually an organotin compound is liable to form an association structure, for example, a dialkyltin dialkoxide can form a dimer structure, or a tetraalkyldialkoxydistannoxane can form an association of 2 molecules or 3 molecules. The trapezoidal structure exists, and even if the state of association changes, it is common for the manufacturer to express the compound in a monomer structure.

Further, the dialkyl tin compound described above may be used singly or in combination of two or more kinds.

As a method for producing a dialkyltin compound, the disclosed production method (WO 2005/111049, etc.) can be preferably used. Dialkyl oxidation A step of producing a dialkyltin compound from tin and an alcohol.

As the alcohol used in the present embodiment, methanol, ethanol, propanol (each isomer), butanol (each isomer), pentanol (each isomer), and hexanol (isomeric) are preferably used. And heptanol (each isomer), octanol (each isomer), decyl alcohol (each isomer), decyl alcohol (each isomer), etc., the number of carbon atoms constituting the alcohol is selected from An alcohol of an integer from 1 to 12.

The dialkyl tin oxide used in the alkyltin alkoxide synthesis step uses a dialkyl tin oxide represented by the following formula (16).

(wherein R ⁹ and R ¹⁰ each independently represent a linear or branched alkyl group having 1 to 12 carbon atoms).

Examples of R ⁹ and R ¹⁰ include a methyl group, an ethyl group, a propyl group (each isomer), a butyl group (each isomer), a pentyl group (each isomer), and a hexyl group (each isomer). , heptyl (each isomer), octyl (each isomer), thiol (each isomer), thiol (each isomer), undecyl (each isomer), An alkyl group or the like having an aliphatic hydrocarbon group having 1 to 12 carbon atoms such as a dodecyl group (each isomer). More preferably, it is a linear or branched saturated alkyl group having 1 to 8 carbon atoms, and more preferably n-butyl group or n-octyl group.

The alcohol is dehydrated with dialkyltin oxide, the formed water is removed to the outside of the system, and tetraalkyldialkoxydistannoxane and/or dialkyltin dialkoxide is obtained. The temperature at which the reaction is carried out is, for example, in the range of 80 to 180 ° C. In order to distill off the generated water to the outside of the system, the reaction temperature also depends on the reaction pressure, preferably from 100 ° C to 180 ° C, in order to increase the reaction rate. The reaction temperature is preferably a high temperature, and on the other hand, it may cause an adverse reaction such as decomposition at a high temperature, which may cause a decrease in yield. Therefore, the reaction temperature is preferably in the range of 100 ° C to 160 ° C. The reaction pressure is a pressure at which the generated water can be removed to the outside of the system, and is also carried out at 20 to 1 × 10 ⁶ Pa depending on the reaction temperature. The reaction time of the dehydration reaction is not particularly limited and is usually from 0.001 to 50 hours, preferably from 0.01 to 10 hours, more preferably from 0.1 to 2 hours. The reaction is terminated if the desired alkyl tin alkoxide composition is obtained. The progress of the reaction can be confirmed by measuring the amount of water removed to the outside of the system, and the reaction solution can also be sampled and confirmed by the method of ¹¹⁹ Sn-NMR. In order to produce the mixture of the present embodiment in the step (1), it is confirmed that the following composition is obtained to terminate the reaction, that is, the tetraalkyl dialkoxide contained in the alkyl tin alkoxide composition obtained by the above reaction. The molar ratio of the dioxane to the dialkyl tin dialkoxide is represented by the molar % of the two, ranging from 0:100 to 80:20, more preferably 10:90 to 70: A composition of the range of 30. The alcohol to be used may be used as it is in a coexistence state, and the alcohol may be distilled off depending on the case. Because of the advantages of a reactor that can reduce other steps, it is preferred to remove the alcohol as much as possible. The removal method is preferably carried out by a known removal method using distillation, and the distillation apparatus used for the distillation can use a well-known distillation apparatus. As a preferred distillation apparatus, since it can be removed in a short time, a thin film distillation apparatus can be preferably used. The form of the reactor for the dehydration reaction is not particularly limited, and a well-known groove-like or column-shaped reactor can be used. The aqueous low-boiling reaction mixture can be discharged from the reactor in a gas form by distillation, and a high-boiling reaction mixture containing the produced alkyl tin alkoxide or alkyl tin alkoxide mixture can be taken from the lower portion of the reactor. Discharged in liquid form. As such a reactor, for example, a reactor including a stirring tank, a multi-stage stirring tank, a distillation column, a multi-stage distillation column, a multi-tubular reactor, a continuous multi-stage distillation column, a packed column, a thin film evaporator, and a support inside can be used. Various methods such as a forced circulation reactor, a falling film evaporator, a falling drop evaporator, a fine flow phase reactor, a bubble column, and the like are combined, and the like. In order to effectively bias the balance toward the side of the formation system, it is preferred to use a column reactor, and it is preferable to rapidly transfer the formed water to a structure in which the gas-liquid contact area of the gas phase is large. A continuous process using a multi-tubular reactor, a multi-stage distillation column, and a packed column packed with a filler may also be employed, but the dialkyltin oxide used in this step is usually solid, so it is preferable to first use the tank. A method of increasing the amount of dialkyltin dialkoxide in a column reactor followed by a column reactor. If the adverse effect is not caused, the material of the reactor and the line can be any known material, and SUS304, SUS316, SUS316L, etc. are relatively inexpensive, so that they can be preferably used. If necessary, additional measuring instruments such as flow meters and thermometers, and well-known processing devices such as reboilers, pumps, and condensers can be added. Heating can be performed by well-known methods such as steam and heaters. Cooling can also use natural cooling, cooling water, and brine. And other well-known methods.

The step (1) is a step of producing a carbonate by reacting a dialkyltin compound produced by the above method with gaseous carbon dioxide. This step is more It is preferred to use the disclosed method for producing carbonates (WO 03/055840, WO 04/014840, etc.).

The alkyl tin compound supplied to this step may be supplied from the alkyl tin alkoxide synthesis step at the time of startup; sometimes the step of producing the dialkyl tin compound from the following step (4) at the time of continuous production, via the step (5) and supply.

In the step (1), the dialkyltin alkoxide and the gaseous carbon dioxide are first absorbed, and a chemical reaction is carried out to obtain a mixture of a carbon dioxide bond containing a dialkyltin alkoxide. When the chemical reaction is carried out, the dialkylstannane oxide is allowed to react in a liquid state. When the dialkylstannane oxide is a solid, in order to make the dialkylstannane oxide liquid, a method of forming it into a liquid by heating can be preferably used. Further, it may be made into a liquid form by a solvent or the like. The reaction pressure also depends on the temperature of the reaction, preferably in the range of atmospheric pressure ~1 MPa, and further preferably in the range of normal pressure to 0.6 MPa. The reaction temperature also depends on the pressure of the reaction, but is preferably in the range of -40 ° C to 80 ° C. If the fluidity during transportation is considered, the temperature is preferably from 0 ° C to 80 ° C, and the most preferable range is normal temperature ( For example, 20 ° C) ~ 80 ° C. The reaction can be carried out in the range of several seconds to 100 hours, and in view of productivity, etc., it is preferably from several minutes to 10 hours. As the reactor, a well-known tank type reactor or a tower type reactor can be used. Also, a plurality of reactors can be used in combination. Since the reaction is a reaction between a carbon dioxide gas (gas) and an alkyltin alkoxide composition (liquid), in order to carry out the reaction efficiently, it is preferred to enlarge the gas-liquid interface to enlarge the contact area between the gas and the liquid. Such a method of expanding the gas-liquid interface to carry out the reaction can utilize well-known knowledge. For example, if a tank type reactor is used, it is preferred to increase the stirring speed or to generate bubbles in the liquid. If a column reactor is used, It is preferred to use a packed column or a method of using a laminate tower. As an example of such a column type reactor, for example, a layered tower method using a tray such as a bubble tray, a perforated tray, a valve tray, a countercurrent tray, or the like, or a Lacy ring, a Lexin ring, and a buck can be used. Pall ring, Berl saddle, Intalox saddle, Dixon Packing, McMahon Packing, Heli pack, silk Filler towers of various fillers such as Sulzer Packing and Mellapak. If the adverse effect is not caused, the material of the reactor and the line can be any known material, and SUS304, SUS316, SUS316L, etc. are relatively inexpensive, so that they can be preferably used. If necessary, additional measuring instruments such as flow meters and thermometers, and well-known processing devices such as reboilers, pumps, and condensers can be added. Heating can be performed by well-known methods such as steam and heaters. Cooling can also use natural cooling, cooling water, and brine. And other well-known methods. The reaction is usually an exothermic reaction and therefore can be cooled or cooled by the exotherm of the reactor. Alternatively, heating may be carried out if the carbonation reaction is carried out together. A well-known method such as a method of using a water jacket and a method of using an internal coil can be employed for cooling and heating the reactor. The carbon dioxide gas and alkyltin alkoxide composition supplied to the reactor may be supplied to the reactor separately or may be previously mixed before being supplied to the reactor. It can be supplied from multiple parts of the reactor. The end of the reaction can be determined, for example, by ¹¹⁹ Sn-NMR analysis.

Next, a reaction liquid containing a carbonate is obtained from the carbon dioxide bond of the dialkyl tin alkoxide obtained above by the following method.

The reaction condition is in the range of 110 ° C to 200 ° C. In order to increase the reaction rate, it is preferred that the reaction temperature is a high temperature, and on the other hand, it may cause an adverse reaction such as decomposition at a high temperature, and sometimes the yield may be lowered. Preferably, it is in the range of 120 ° C to 180 ° C, and the reaction time is in the range of 0.1 hour to 10 hours, and the reaction pressure is 1.5 MPa to 20 MPa, preferably in the range of 2.0 MPa to 10 MPa. The reaction can be terminated after the desired carbonate is formed in the reactor. The progress of the reaction can be confirmed by the following method: The reaction liquid in the reactor is sampled, and the produced carbonate is analyzed by a method such as ¹ H-NMR or gas chromatography. For example, a carbon dioxide bond of a dialkyl tin alkoxide and/or a dialkyl tin alkoxide contained in a carbon dioxide bond of a dialkyl tin alkoxide and/or a dialkyl tin alkoxide. When the number of moles of the knot is 10% or more, the reaction can be terminated. When the yield of the carbonate is to be increased, the reaction is continued until the value is 90% or more. As the reactor, a well-known reactor can be used, and a column reactor or a tank reactor can be preferably used. If the adverse effect is not caused, the material of the reactor and the line can be any known material, and SUS304, SUS316, SUS316L, etc. are relatively inexpensive, so that they can be preferably used. If necessary, additional measuring instruments such as flow meters and thermometers, and well-known processing devices such as reboilers, pumps, and condensers can be added. Heating can be performed by well-known methods such as steam and heaters. Cooling can also use natural cooling, cooling water, and brine. And other well-known methods.

The step (2) of the present embodiment is a step of separating and recovering the carbonate from the reaction solution containing the carbonate obtained in the above step (1), and obtaining a residual liquid. The separation method can be suitably carried out using a well-known method or Set. A preferred method is a method of separating by distillation.

The reaction liquid carried out from the above step (1) is subjected to batch or semi-batch or continuous distillation to obtain a carbonate and a residual liquid. A preferred distillation method is a method in which the reaction liquid is supplied to a distiller, and the carbonate is separated as a gas phase component from the upper portion of the distiller to the outside of the system, and the residual liquid is discharged as a liquid component from the bottom of the distiller. The temperature of this step also depends on the boiling point or pressure of the carbonate, which is in the range of normal temperature (for example, 20 ° C) to 200 ° C, because the tin compound in the residual liquid may be modified at a high temperature, or the carbonate may be reversely reacted. It is reduced, so it is preferably in the range of normal temperature (for example, 20 ° C) to 150 ° C. The pressure also depends on the kind of the carbonate or the temperature at which the reaction is carried out, and the reaction is usually carried out under normal pressure to reduced pressure. If productivity is considered, it is preferably in the range of 100 Pa to 80 KPa, and most preferably 100 Pa. Range of ~50 KPa. The reaction time can be carried out in the range of 0.01 to 10 hours. If the reaction is carried out at a high temperature for a long period of time, the tin compound contained in the reaction solution may be modified or the carbonate may be reduced by the reverse reaction, so it is preferably 0.01. The range of hours to 0.5 hours is preferably in the range of 0.01 hours to 0.3 hours. As the distiller, a well-known distiller can be used, and a tower distiller, a trough distiller, or a plurality of distillers can be preferably used in combination. Further, a retort-based thin film evaporator and a thin film distiller are preferably a thin film evaporator and a thin film distiller having a distillation column. If the adverse effects are not caused, the material of the distiller and the line can be any known material, and SUS304, SUS316, SUS316L, etc. are relatively inexpensive, so that they can be preferably used. If necessary, additional measuring instruments such as flow meters and thermometers, and well-known processing devices such as reboilers, pumps, and condensers can be added; A well-known method such as steam, a heater, or the like can be used for cooling, such as natural cooling, cooling water, and brine.

The step (3) is a step of reacting the dialkyl carbonate separated in the step (2) with the aromatic hydroxy compound A to obtain a diaryl carbonate, and recovering the alcohol produced as a by-product. Here, the term refers to an aromatic hydroxy compound R ¹ OH the compound corresponding to the compound, the compound R ¹ OH-based group R to the configuration in the carbonate represented by the above formula (1) of ^a diaryl O (R ¹ represents the above-defined The aromatic group, O represents an oxygen atom, and a hydrogen atom is added thereto. Specific examples of the aromatic hydroxy compound A which is preferably used include phenol, methyl phenol (each isomer), ethyl phenol (each isomer), and propyl phenol (each isomer). ), monosubstituted phenols such as butyl phenol (each isomer), amyl phenol (each isomer), hexyl phenol (each isomer), dimethyl phenol (each isomer), diethyl Phenol (each isomer), dipropyl phenol (each isomer), methyl ethyl phenol (each isomer), methyl propyl phenol (each isomer), methyl butyl phenol (each Disubstituted phenols such as isomers, methylpentyl phenol (each isomer), ethyl propyl phenol (each isomer), ethyl butyl phenol (each isomer), trimethyl phenol (each isomer), triethylphenol (each isomer), dimethylethylphenol (each isomer), dimethylpropylphenol (each isomer), dimethylbutylphenol Trisubstituted phenols such as (each isomer), naphthol (each isomer), and the like.

The step (3) of the present embodiment is a step of reacting a component mainly containing a carbonate separated in the step (2) with an aromatic hydroxy compound A to obtain a diaryl carbonate. A method for obtaining an alkyl aryl carbonate or a diaryl carbonate from a dialkyl carbonate and an aromatic hydroxy compound, and has proposed a plurality of parties so far In this embodiment, these techniques can also be preferably used.

The reaction of the step (3) comprises a transesterification reaction of a carbonate with an aromatic hydroxy compound, and an uneven reaction of a dialkyl aryl carbonate obtained by the transesterification reaction.

The transesterification reaction is an equilibrium reaction, and in order to facilitate the reaction, it is preferred to carry out the reaction while discharging the desorbed alcohol in the transesterification reaction. In this case, it is preferred to use the step (3). The boiling point of the aromatic hydroxy compound is higher than the boiling point of the alkyl alcohol constituting the alkyl carbonate obtained in the step (2). In particular, when the steps of the steps (1) to (3) are repeated one or more times, it is preferred that the boiling point of the alkyl alcohol is lower than the standard boiling point of the aromatic hydroxy compound, and the difference in boiling point is preferably 2 °C, if considering the ease of separation, it is preferably 10 °C.

As an example of the dialkyl carbonate used in the step (3), for example, dimethyl carbonate, diethyl carbonate, dipropyl carbonate (each isomer), dibutyl carbonate (each isomer), and carbonic acid are used. Dipentyl ester (each isomer), dihexyl carbonate (each isomer), diheptyl carbonate (each isomer), dioctyl carbonate (each isomer), dinonyl carbonate (variety) Structure), dinonyl carbonate (each isomer), dicyclopentanyl carbonate, dicyclohexyl carbonate, dicycloheptyl carbonate (each isomer), dibenzyl carbonate, diphenylethyl carbonate ( Each isomer), di(phenylpropyl) carbonate (each isomer), di(phenylbutyl) carbonate (each isomer), di(chlorobenzyl) carbonate (isoisomer) , bis(methoxybenzyl) carbonate (each isomer), bis(methoxymethyl) carbonate, bis(methoxyethyl) carbonate (each isomer), carbonic acid (chloroethyl) ester (each isomer), di(cyanoethyl) carbonate (each isomer), methyl ethyl carbonate, methyl propyl carbonate (each isomer), carbonic acid Methyl butyl ester (each isomer), ethyl propyl carbonate (each isomer), ethyl butyl carbonate (each isomer), ethylene carbonate, propylene carbonate, and the like. The carbonate used may be one type or a mixture.

Among the above-mentioned dialkyl carbonates, in the present embodiment, it is preferred to use an alkyl alcohol having a standard boiling point of a carbonate-constituting alcohol which is higher than a standard boiling point of water and having an alkyl group having 4 to 12 carbon atoms, A linear or branched alkenyl alcohol having 4 to 12 alkenyl groups, a cycloalkyl alcohol, or an aralkyl alcohol. If it is considered that the reaction carried out in the step (3) is advantageously carried out while removing the alcohol formed by the reaction of the step (3), it is further preferred that the standard boiling point is lower than the standard of the aromatic hydroxy compound used in the step (3). The boiling point of the alcohol. That is, a dialkyl carbonate composed of an alcohol having a standard boiling point higher than water and having a lower boiling point than the aromatic hydroxy compound is preferred.

The amount of the aromatic hydroxy compound used in the step (3) is 0.1 to 10,000 in terms of stoichiometric ratio relative to the amount of the dialkyl carbonate used in the step (3) after the separation in the step (2). Used within the range of times. The reaction in the step (3) is mainly an equilibrium reaction, so that the amount of the aromatic hydroxy compound is more favorable, and if the amount of use is increased, the reactor becomes larger, and then the separation of the product requires a larger distillation column or the like. Preferably, it is in the range of 1 to 1000 times, more preferably in the range of 1 to 100 times, relative to the dialkyl carbonate.

The compound to be supplied to the step (3) is mainly a dialkyl carbonate or an aromatic hydroxy compound, and may be supplied to a catalyst as needed, or may be mixed with impurities which do not particularly adversely affect the reaction.

These feedstocks may contain, as a product, an alcohol, an alkyl aryl carbonate, a diaryl carbonate, etc., and the reaction is a reversible reaction, so the formation When the concentration of the substance is too high, the reaction rate of the raw material may decrease, which may be undesirable. The ratio of the amount of the dialkyl carbonate to the aromatic hydroxy compound to be supplied may vary depending on the kind and amount of the catalyst, and the reaction conditions. Usually, it is preferred to use the dialkyl carbonate in the raw material. The aromatic hydroxy compound is supplied in a range of 0.01 to 1000 times the molar ratio.

The reaction time of the transesterification reaction in the step (3) also varies depending on the reaction conditions or the type or internal structure of the reactor, and is usually 0.001 to 50 hours, preferably 0.01 to 10 hours, more preferably 0.05 to 5 hours. . The reaction temperature is the temperature in the reactor, and it varies depending on the type of the raw material compound to be used, that is, the dialkyl carbonate and the aromatic hydroxy compound, and is usually in the range of 50 ° C to 350 ° C, preferably 100 ° C to 280 ° C. get on. Further, the reaction pressure varies depending on the type of the raw material compound to be used, the reaction temperature, and the like, and may be any of reduced pressure, normal pressure, and pressure, and is usually carried out in the range of 10 Pa to 20 MPa.

In the present embodiment, a solvent is not necessarily used, and in order to facilitate the reaction operation, an appropriate inert solvent such as an ether, an aliphatic hydrocarbon, an aromatic hydrocarbon, a halogenated aliphatic hydrocarbon, or a halogenated aromatic hydrocarbon may be used as the solvent. Reaction solvent. Further, an inert gas such as nitrogen, helium or argon which is inert to the reaction may be allowed to coexist in the reaction system, and in order to accelerate the distillation of the low-boiling by-product formed, the lower portion of the continuous multi-stage distillation column may be used. An inert gas or a low melting organic compound which is inert to the reaction is introduced in the form of a gas.

When the transesterification reaction of the step (3) is carried out, a catalyst may be added. As described above, the alkyl aryl carbonate and the diaryl carbonate are obtained from the carbonate by transesterification, and the equilibrium of the transesterification reaction is biased toward the reaction system and the reaction rate is slow. When the diaryl carbonate is produced by this method, several proposals have been made for improving the above, and a well-known method can be preferably used in the present embodiment.

The amount of the catalyst used in the present embodiment differs depending on the type of the catalyst to be used, the type of the reactor, the kind of the carbonate and the aromatic hydroxy compound or the amount ratio thereof, the reaction temperature, and the reaction pressure. It is usually used in an amount of 0.0001 to 50% by weight, based on the ratio of the total weight of the carbonate and the aromatic hydroxy compound as the raw material to be supplied. Further, in the case of using a solid catalyst, it is preferred to use a catalyst amount of 0.01 to 75% by volume with respect to the volume of the reactor of the reactor.

As a proposal relating to a catalyst for accelerating the reaction rate, a large number of metal-containing catalysts are known. A well-known transesterification catalyst can also be used in this embodiment. In the method of reacting a carbonate with an aromatic hydroxy compound to produce a mixture comprising an alkyl aryl carbonate and/or an alkyl aryl carbonate and a diaryl carbonate, as such a catalyst, for example, a transition metal halogenation is proposed. a Lewis acid such as a substance or a compound which purifies a Lewis acid, a tin compound such as an organotin alkoxide or an organotin oxide, a salt of an alkali metal or an alkaline earth metal, an alkoxide, a lead compound, copper, iron, or the like. Metal complexes such as zirconium, titanates, mixtures of Lewis acids and proton acids, compounds such as Sc, Mo, Mn, Bi, Te, etc., iron acetate, and the like. The formation of the diaryl carbonate can be produced only in the transesterification reaction, or can be produced by the heterogeneous reaction of the alkyl aryl carbonate formed by the transesterification reaction. The term "unevening reaction" as used herein refers to a reaction of forming a dialkyl carbonate and a diaryl carbonate from two molecules of an alkyl aryl carbonate. The alkyl aryl carbonate further reacts with the aromatic hydroxy compound and also causes the reaction to become a diaryl carbonate due to unevenness. The reaction is faster, so when the diaryl carbonate is desired, the alkyl aryl carbonate is not homogenized to obtain a diaryl carbonate. Either reaction is an equilibrium reaction. In the transesterification reaction for producing an alkyl aryl carbonate, the reaction is carried out while discharging the alkyl alcohol, and in the unevenness step, it is advantageous to carry out the reaction while discharging the dialkyl carbonate. Therefore, the preferred reaction conditions are different in each stage. In the case of continuous reaction, the reaction must be carried out in two stages, and in the case of batchwise, it may be carried out successively in the same reactor.

Therefore, the catalyst for promoting the unevenness reaction can coexist with the above-mentioned transesterification catalyst. More examples of such catalysts have also been proposed. As such a catalyst, for example, a Lewis acid and a transition metal compound capable of generating a Lewis acid, a polymer tin compound, and a compound of the formula R-X(=O)OH (wherein X is selected from Sn and Ti, and R is selected is selected). a compound represented by a monovalent hydrocarbon group, a mixture of a Lewis acid and a protonic acid, a lead catalyst, a titanium or zirconium compound, a tin compound, a compound of Sc, Mo, Mn, Bi, Te, or the like.

The unevenness step is a step of heterogeneizing the alkyl aryl carbonate obtained in the transesterification step to obtain a dialkyl carbonate and a diaryl carbonate. As described above, when the transesterification reaction is carried out, a heterogeneous catalyst may be added to carry out the transesterification reaction together with the heterogeneous reaction, and the transesterification reaction and the heterogeneous reaction may be carried out continuously or in batches. Further, in the transesterification reaction in which the transesterification reaction and the heterogeneous reaction are carried out separately, the diaryl carbonate may be obtained simultaneously with the alkyl aryl carbonate. In this case, the heterogeneous reaction may be directly carried out. The heterogeneous reaction is as shown in the above, which is a step of obtaining an alkyl aryl carbonate by transesterification of a dialkyl carbonate with an aromatic hydroxy compound. In order to facilitate the equilibrium reaction, it is advantageous to carry out the reaction while discharging the alcohol. Since the heterogeneous reaction is also limited by the balance, it is advantageous to carry out the reaction while discharging one of the dialkyl carbonate and the diaryl carbonate formed by the heterogeneous reaction to the outside of the system. In the present embodiment, it is preferred that the alkoxy group and the aryl group are each selected so that the boiling point of the dialkyl carbonate is lower than that of the diaryl carbonate, and the dialkyl carbonate is discharged to the outside of the system. The heterogeneity reaction was carried out. The discharged dialkyl carbonate can be returned to the step before the heterogeneous reaction. If the production amount of the diaryl carbonate is to be increased, it is preferred to return the discharged dialkyl carbonate to the transesterification step.

In the unevenness step, a catalyst for catalyzing the heterogeneous reaction can be used. Many examples of such catalysts have also been proposed. As such a catalyst, for example, a Lewis acid and a transition metal compound capable of generating a Lewis acid, a polymer tin compound, and a compound of the formula R-X(=O)OH (wherein X is selected from Sn and Ti, and R is selected is selected). a compound represented by a monovalent hydrocarbon group, a mixture of a Lewis acid and a protonic acid, a lead catalyst, a titanium or zirconium compound, a tin compound, a compound of Sc, Mo, Mn, Bi, Te, or the like.

As the heterogeneous reaction catalyst of the present embodiment, the same catalyst as the transesterification catalyst used in the transesterification step can be used.

The alkyl aryl carbonate-based alkyl aryl carbonate used in the unevenness step. Examples of the alkyl aryl carbonate include methyl phenyl carbonate, ethyl phenyl carbonate, propyl phenyl carbonate (each isomer), butyl phenyl carbonate (each isomer), and carbene carbonate. Propyl phenyl ester (each isomer), amyl phenyl carbonate (each isomer), hexyl phenyl carbonate (each isomer), heptyl phenyl carbonate (isomeric) , octyl cresyl carbonate (each isomer), decyl carbonate (ethyl phenyl) ester (each isomer), decyl phenyl (butyl phenyl) ester (each isomer), carbonic acid Methyl toluene (each isomer), ethyl toluene carbonate (each isomer), propyl cresyl carbonate (each isomer), butyl toluene carbonate (each isomer), allyl carbonate Methyl toluene (each isomer), methyl ditolyl carbonate (each isomer), methyl (trimethylphenyl) carbonate (each isomer), methyl (chlorophenyl) carbonate (each isomer), methyl (nitrophenyl) carbonate (each isomer), methyl (methoxyphenyl) carbonate (each isomer), methyl (pyridyl) carbonate (each isomer), ethyl cumyl carbonate (each isomer), methyl (benzhydrylphenyl) carbonate (each isomer), ethyl xylyl carbonate (isomeric Benzyl dimethyl cresyl ester (each isomer) and the like. These alkyl aryl carbonates may be used alone or in combination of two or more.

Among the alkyl aryl carbonates, it is preferred in the present embodiment that the alcohol constituting the alkyl aryl carbonate has a boiling point higher than that of water, and the alcohol constituting the alkyl aryl carbonate has a boiling point lower than that of the carbonic acid. The boiling point of the aromatic hydroxy compound of the alkyl aryl ester is, for example, selected from the group consisting of an alkyl alcohol having a linear or branched alkyl group having 4 to 12 carbon atoms, and having a linear or branched carbon number. Preferably, the alkenyl alcohol, cycloalkyl alcohol, or aralkyl alcohol having 4 to 12 alkenyl groups is preferably a dialkyl carbonate formed by removing the heterogeneous reaction in order to facilitate the heterogeneous reaction. It is a dialkyl carbonate having a boiling point lower than that of a diaryl carbonate obtained by a heterogeneous reaction. As such an optimum combination, an alcohol, an alcohol equivalent to an alkoxy group of a metal compound having a metal-carbon-oxygen bond represented by the above formula (14) and formula (15), and a dialkyl carbonate are exemplified. The alcohol is selected from the group consisting of pentanol (each isomer), hexanol (each isomer), and heptanol (each isomer). The aromatic hydroxy compound is an aromatic hydroxy compound selected from the group consisting of phenol and cresol.

The compound supplied to the unevenness step is mainly an alkyl aryl carbonate, and if necessary, a catalyst, and impurities which do not particularly adversely affect the reaction can be mixed.

The amount of the catalyst used in the present embodiment differs depending on the type of the catalyst to be used, the type of the reactor, the type or amount of the alkyl aryl carbonate, the reaction temperature, the reaction temperature, and the like, and the like. The ratio of the weight of the alkyl aryl carbonate to the raw material is usually from 0.0001 to 50% by weight. Further, in the case of using a solid catalyst, it is preferred to use a catalyst amount of 0.01 to 75% by volume with respect to the volume of the reactor of the reactor.

The feedstock may contain an alcohol, an aromatic hydroxy compound, a diaryl carbonate, etc., and the reaction is reversible. Therefore, when the concentration is too high, the reaction rate of the raw material may decrease, so good.

The reaction time of the heterogeneous reaction varies depending on the reaction conditions or the type or internal structure of the reactor, and is usually 0.001 to 50 hours, preferably 0.01 to 10 hours, more preferably 0.05 to 5 hours. The reaction temperature varies depending on the type of the alkyl aryl carbonate to be used, and is usually carried out at a temperature ranging from 50 ° C to 350 ° C, more preferably from 100 ° C to 280 ° C. Further, the reaction pressure varies depending on the type of the raw material compound to be used, the reaction temperature, and the like, and may be any of reduced pressure, normal pressure, and pressure, and is usually carried out in the range of 10 Pa to 20 MPa.

In the unevenness step of the present embodiment, it is not necessary to use a solvent, and in order to facilitate the reaction operation, a suitable inert solvent such as an ether, an aliphatic hydrocarbon, an aromatic hydrocarbon or a halogenated aliphatic hydrocarbon may be used. Halogenated An aromatic hydrocarbon or the like is used as a reaction solvent. Further, an inert gas such as nitrogen, helium or argon which is inert to the reaction may be allowed to coexist in the reaction system, and in order to accelerate the distillation of the low-boiling by-product formed, the lower portion of the continuous multi-stage distillation column may be used. An inert gas or a low melting organic compound which is inert to the reaction is introduced in the form of a gas.

After completion of the heterogeneous reaction, the catalyst, alkyl aryl carbonate, aromatic hydroxy compound, and alcohol are separated by a well-known method to obtain a diaryl carbonate.

The form of the reactor used in the transesterification step and the unevenness step is not particularly limited, and various methods such as a stirring tank method, a multi-stage stirring tank method, a multi-stage distillation column, and the like may be employed. method. These reactors can be used in either batch or continuous mode. In view of the fact that the equilibrium is effectively biased toward the formation side, it is preferred to use a multistage distillation column, and particularly preferably a continuous process using a multistage distillation column. The multi-stage distillation column refers to a multi-stage distillation column in which the theoretical number of stages of distillation is two or more stages, and may be any if continuous distillation is possible. As such a multi-stage distillation column, for example, a tray tower method using a tray such as a bubble tray, a perforated tray, a valve tray, a countercurrent tray, or the like, or a Lacy ring, an Lexin ring, a Pall ring, or the like is used. Arc saddle packing, moment saddle ring packing, Dickson packing, net saddle packing, spiral packing, wire mesh corrugated packing, orifice corrugated packing, etc., which are usually used as multi-stage distillation tower users. Use any one. Further, a laminate-filled mixing tower method in which a laminate portion and a filler-filled portion are combined can be preferably used. When the continuous process is carried out using a multi-stage distillation column, the starting material and the reaction material are continuously supplied to the continuous In the multi-stage distillation column, the transesterification reaction and/or the heterogeneous reaction between the two substances are carried out in the liquid phase or in the gas-liquid phase in the presence of the metal-containing catalyst in the distillation column, and the produced carbonic acid is contained. The high-boiling reaction mixture of the alkyl aryl ester and/or the diaryl carbonate is discharged as a liquid from the lower portion of the distillation column, and on the other hand, the low-boiling reaction mixture containing the by-product formed is distilled from the distillation column. The upper portion is continuously discharged in a gaseous form, thereby producing a diaryl carbonate.

The above is a production example of a diaryl carbonate using a dialkyltin compound. In addition to the above steps (1) to (3), the following steps (4) and (5) can be carried out.

Step (4): reacting the residual liquid obtained in the step (2) with an alcohol to form an organotin compound having a tin-oxygen-carbon bond and water, and removing the water from the reaction system; and step (5): the step (4) The obtained organotin compound having a tin-oxygen-carbon bond is used as the step of the organotin compound having a tin-oxygen-carbon bond in the step (1).

The step (4) is a step of reacting the residual liquid obtained in the step (2) with an alcohol to regenerate the dialkyl tin compound.

As the alcohol used in this step, methanol, ethanol, propanol (each isomer), butanol (each isomer), pentanol (each isomer), and hexanol (each isomer) are preferably used. ), heptanol (each isomer), octanol (each isomer), decyl alcohol (each isomer), decyl alcohol (each isomer), etc., the number of carbon atoms constituting the alcohol is selected from 1 An alcohol of an integer of ~12 is more preferably the same alcohol as that used in the alkyltin alkoxide synthesis step described above.

Preferably, the conditions of the dehydration reaction are also carried out under the same conditions as those for the alkyltin alkoxide synthesis step described above. The reaction is terminated if the desired alkyl tin alkoxide composition is obtained. The progress of the reaction can be confirmed by measuring the amount of water discharged to the outside of the system, and the reaction solution can be sampled and confirmed by the method of ¹¹⁹ Sn-NMR. In order to produce the mixture of the present embodiment in the step (1), it is confirmed that the following composition is obtained to terminate the reaction, that is, the tetraalkyl dialkoxide contained in the alkyl tin alkoxide composition obtained by the above reaction. The molar ratio of the dioxane to the dialkyltin dialpoxide is expressed as a molar percentage of the two, ranging from 0:100 to 80:20, more preferably from 10:90 to 70: A composition of the range of 30. The alcohol to be used may be used as it is in a coexisting state, or may be used by distilling off alcohol according to the case. Because of the advantages of a reactor that can reduce other steps, it is preferred to remove the alcohol as much as possible. The removal method is preferably carried out by using a well-known distillation using distillation, and the distillation apparatus used for the distillation can use a well-known distillation apparatus. As a preferred distillation apparatus, since it can be removed in a short time, a thin film distillation apparatus can be preferably used. In this step, unlike the alkyltin alkoxide synthesis step, dialkyltin oxide as a solid is generally not used, so the reactor is less restrictive. That is, the form of the reactor for the dehydration reaction is not particularly limited, and a well-known groove-like or columnar reactor can be used. The aqueous low-boiling reaction mixture is discharged from the reactor in a gas form by distillation, and the high-boiling reaction mixture containing the alkyl tin alkoxide or alkyl tin alkoxide mixture produced is liquid from the lower portion of the reactor. discharge. As such a reactor, for example, a reactor including a stirring tank, a multi-stage stirring tank, a distillation column, a multi-stage distillation column, a multi-tubular reactor, a continuous multi-stage distillation column, a packed column, a thin film evaporator, and a support inside can be used. Various methods such as a forced circulation reactor, a falling film evaporator, a falling drop evaporator, a fine flow phase reactor, a bubble column, and the like, and a combination thereof. In view of the fact that the equilibrium is effectively biased toward the side of the formation system, it is preferred to use a column reactor, and it is preferred that the formed water is rapidly transferred to a structure in which the gas-liquid contact area of the gas phase is large. Particularly preferred is a continuous process using a multi-tubular reactor, a multi-stage distillation column, and a packed column packed with a filler. If the adverse effect is not caused, the material of the reactor and the line can be any known material, and SUS304, SUS316, SUS316L, etc. are relatively inexpensive, so that they can be preferably used. If necessary, additional measuring instruments such as flow meters and thermometers, and well-known processing devices such as reboilers, pumps, and condensers can be added. Heating can be performed by well-known methods such as steam and heaters. Cooling can also use natural cooling, cooling water, and brine. And other well-known methods.

The dialkyl tin compound produced in the above step (4) is reused as the dialkyl tin compound used in the step (1) by the step (5) (reuse step), and the step (5) is the step ( 4) The obtained organotin compound having a tin-oxygen-carbon bond is used as the step of the organotin compound having a tin-oxygen-carbon bond in the step (1).

<amine compound>

On the other hand, as the amine compound used in the production method of the present embodiment, an amine compound represented by the following formula (17) is used.

(wherein R ² is one selected from the group consisting of an aliphatic group having a carbon number of 1 to 20 selected from carbon or oxygen atoms and an aromatic group having 6 to 20 carbon atoms; n equal atomic price, n is an integer from 2 to 10).

In the above formula (17), it is preferred that n is a polyamine of 2 or more, and further preferably a diamine compound wherein n is 2.

R ^{2 of the} above formula (17) is more preferably an alkyl group having 1 to 20 carbon atoms or a cycloalkyl group having 5 to 20 carbon atoms. As an example of such R ² , it is preferably used: a straight-chain hydrocarbon group such as methyl, dimethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene or octamethyl; cyclopentane, cyclohexane, cycloheptane, cyclooctane Unsubstituted alicyclic hydrocarbon group such as alkane or bis(cyclohexyl)alkane; methylcyclopentane, ethylcyclopentane, methylcyclohexane (each isomer), ethylcyclohexane (different Structure), propylcyclohexane (each isomer), butylcyclohexane (each isomer), pentylcyclohexane (each isomer), hexylcyclohexane (each isomer) Alkyl-substituted cyclohexane; dimethylcyclohexane (each isomer), diethylcyclohexane (each isomer), dibutylcyclohexane (each isomer) Substituting cyclohexane; 1,5,5-trimethylcyclohexane, 1,5,5-triethylcyclohexane, 1,5,5-tripropylcyclohexane (each isomer), a trialkyl-substituted cyclohexane such as 1,5,5-tributylcyclohexane (each isomer); a monoalkyl-substituted benzene such as toluene, ethylbenzene or propylbenzene; xylene or diethylbenzene , Propylbenzene and other dialkyl substituted phenylene; diphenyl alkanes, aromatic hydrocarbons such as benzene. Among them, hexamethylene, phenyl, diphenylmethane, toluene, cyclohexane, xylene, methylcyclohexane, isophorone, and dicyclohexylmethyl are preferably used.

Examples of such a polyamine compound include hexamethylenediamine, 4,4'-methylenebis(cyclohexylamine) (each isomer), and cyclohexanediamine (each isomer). , an aliphatic diamine such as 3-aminomethyl-3,5,5-trimethylcyclohexylamine (each isomer); phenylenediamine (each isomer), toluenediamine (isoisomer) An aromatic diamine such as 4,4'-methylenediphenylamine. Among them, hexamethylenediamine, 4,4'-methylenebis(cyclohexylamine) (each isomer), cyclohexanediamine (each isomer), 3-amino group A are preferably used. An aliphatic diamine such as a group of 3-,5,5-trimethylcyclohexylamine (each isomer), wherein hexamethylenediamine and 4,4'-methylenebis(cyclohexyl) are more preferably used. Amine), 3-aminomethyl-3,5,5-trimethylcyclohexylamine.

<Reaction of diaryl carbonate with amine compound>

The reaction of the above-described diaryl carbonate with an amine compound will be described.

The reaction of the diaryl carbonate with the amine compound is carried out in the presence of an aromatic hydroxy compound. The aromatic hydroxy compound is preferably a compound in which one hydroxyl group is directly bonded to an aromatic hydrocarbon ring constituting the aromatic hydroxy compound. An aromatic hydroxy compound in which two or more hydroxyl groups are directly bonded to an aromatic hydrocarbon ring constituting the aromatic hydroxy compound can also be used as an aromatic hydroxy compound constituting the composition of the present embodiment, and the diaryl carbonate and In the reaction of the amine compound, the viscosity of the solution may increase, which may cause a decrease in the reaction efficiency, or may decrease the efficiency of the reaction liquid described below.

An aromatic hydroxy compound used as a reaction between a diaryl carbonate and an amine compound, Can be listed: phenol, Methyl-phenol (each isomer), Ethyl-phenol (each isomer), Propyl-phenol (each isomer), Butyl-phenol (each isomer), Pentyl-phenol (each isomer), Hexyl-phenol (each isomer), Heptyl-phenol (each isomer), Octyl-phenol (each isomer), Mercapto-phenol (each isomer), Mercapto-phenol (each isomer), Dodecyl-phenol (each isomer), Phenyl-phenol (each isomer), Phenoxyphenol (each isomer), Monosubstituted phenols such as cumyl-phenol (each isomer), Dimethyl-phenol (each isomer), Diethyl-phenol (each isomer), Dipropyl-phenol (each isomer), Dibutyl-phenol (each isomer), Dipentyl-phenol (each isomer), Dihexyl-phenol (each isomer), Diheptyl-phenol (each isomer), Dioctyl-phenol (each isomer), Dimercapto-phenol (each isomer), Dimercapto-phenol (each isomer), Di(dodecyl)-phenol (each isomer), Diphenyl-phenol (each isomer), Diphenoxyphenol (each isomer), Dicumyl-phenol (each isomer), Methyl-ethyl-phenol (each isomer), Methyl-propyl-phenol (each isomer), Methyl-butyl-phenol (each isomer), Methyl-pentyl-phenol (each isomer), Methyl-hexyl-phenol (each isomer), Methyl-heptyl-phenol (each isomer), Methyl-octyl-phenol (each isomer), Methyl-mercapto-phenol (each isomer), Methyl-mercapto-phenol (each isomer), Methyl-dodecyl-phenol (each isomer), Methyl-phenyl-phenol (each isomer), Methyl-phenoxyphenol (each isomer), Methyl-cumyl-phenol (each isomer), Ethyl-propyl-phenol (each isomer), Ethyl-butyl-phenol (each isomer), Ethyl-pentyl-phenol (each isomer), Ethyl-hexyl-phenol (each isomer), Ethyl-heptyl-phenol (each isomer), Ethyl-octyl-phenol (each isomer), Ethyl-mercapto-phenol (each isomer), Ethyl-mercapto-phenol (each isomer), Ethyl-dodecyl-phenol (each isomer), Ethyl-phenyl-phenol (each isomer), Ethyl-phenoxyphenol (each isomer), Ethyl-cumyl-phenol (each isomer), Propyl-butyl-phenol (each isomer), Propyl-pentyl-phenol (each isomer), Propyl-hexyl-phenol (each isomer), Propyl-heptyl-phenol (each isomer), Propyl-octyl-phenol (each isomer), Propyl-mercapto-phenol (each isomer), Propyl-mercapto-phenol (each isomer), Propyl-dodecyl-phenol (each isomer), Propyl-phenyl-phenol (each isomer), Propyl-phenoxyphenol (each isomer), Propyl-cumyl-phenol (each isomer), Butyl-pentyl-phenol (each isomer), Butyl-hexyl-phenol (each isomer), Butyl-heptyl-phenol (each isomer), Butyl-octyl-phenol (each isomer), Butyl-mercapto-phenol (each isomer), Butyl-mercapto-phenol (each isomer), Butyl-dodecyl-phenol (each isomer), Butyl-phenyl-phenol (each isomer), Butyl-phenoxyphenol (each isomer), Butyl-cumyl-phenol (each isomer), Pentyl-hexyl-phenol (each isomer), Butyl-heptyl-phenol (each isomer), Butyl-octyl-phenol (each isomer), Amyl-decyl-phenol (each isomer), Amyl-decyl-phenol (each isomer), Amyl-dodecyl-phenol (each isomer), Pentyl-phenyl-phenol (each isomer), Pentyl-phenoxyphenol (each isomer), Amyl-cumyl-phenol (each isomer), Hexyl-heptyl-phenol (each isomer), Hexyl-octyl-phenol (each isomer), Hexyl-fluorenyl-phenol (each isomer), Hexyl-fluorenyl-phenol (each isomer), Hexyl-dodecyl-phenol (each isomer), Hexyl-phenyl-phenol (each isomer), Hexyl-phenoxyphenol (each isomer), Hexyl-isopropylphenyl-phenol (each isomer), Heptyl-octyl-phenol (each isomer), Heptyl-fluorenyl-phenol (each isomer), Heptyl-fluorenyl-phenol (each isomer), Heptyl-dodecyl-phenol (each isomer), Heptyl-phenyl-phenol (each isomer), Heptyl-phenoxyphenol (each isomer), Heptyl-cumyl-phenol (each isomer), Octyl-fluorenyl-phenol (each isomer), Octyl-fluorenyl-phenol (each isomer), Octyl-dodecyl-phenol (each isomer), Octyl-phenyl-phenol (each isomer), Octyl-phenoxyphenol (each isomer), Octyl-cumyl-phenol (each isomer), Mercapto-mercapto-phenol (each isomer), Mercapto-dodecyl-phenol (each isomer), Mercapto-phenyl-phenol (each isomer), Mercapto-phenoxyphenol (each isomer), Mercapto-cumyl-phenol (each isomer), Dodecyl-phenyl-phenol (each isomer), Dodecyl-phenoxyphenol (each isomer), Disubstituted phenols such as dodecyl-cumyl-phenol (each isomer), Trimethyl-phenol (each isomer), Triethyl-phenol (each isomer), Tripropyl-phenol (each isomer), Tributyl-phenol (each isomer), Tripentyl-phenol (each isomer), Trihexyl-phenol (each isomer), Triheptyl-phenol (each isomer), Trioctyl-phenol (each isomer), Triterpene-phenol (each isomer), Triterpene-phenol (each isomer), Tris(dodecyl)-phenol (each isomer), Triphenyl-phenol (each isomer), Triphenyloxyphenol (each isomer), Triisopropylphenyl-phenol (each isomer), Dimethyl-ethyl-phenol (each isomer), Dimethyl-propyl-phenol (each isomer), Dimethyl-butyl-phenol (each isomer), Dimethyl-pentyl-phenol (each isomer), Dimethyl-hexyl-phenol (each isomer), Dimethyl-heptyl-phenol (each isomer), Dimethyl-octyl-phenol (each isomer), Dimethyl-mercapto-phenol (each isomer), Dimethyl-mercapto-phenol (each isomer), Dimethyl-dodecyl-phenol (each isomer), Dimethyl-phenyl-phenol (each isomer), Dimethyl-phenoxyphenol (each isomer), Dimethyl-cumyl-phenol (each isomer), Diethyl-methyl-phenol (each isomer), Diethyl-propyl-phenol (each isomer), Diethyl-butyl-phenol (each isomer), Diethyl-pentyl-phenol (each isomer), Diethyl-hexyl-phenol (each isomer), Diethyl-heptyl-phenol (each isomer), Diethyl-octyl-phenol (each isomer), Diethyl-mercapto-phenol (each isomer), Diethyl-mercapto-phenol (each isomer), Diethyl-dodecyl-phenol (each isomer), Diethyl-phenyl-phenol (each isomer), Diethyl-phenoxyphenol (each isomer), Diethyl-isopropylphenyl-phenol (each isomer), Dipropyl-methyl-phenol (each isomer), Dipropyl-ethyl-phenol (each isomer), Dipropyl-butyl-phenol (each isomer), Dipropyl-pentyl-phenol (each isomer), Dipropyl-hexyl-phenol (each isomer), Dipropyl-heptyl-phenol (each isomer), Dipropyl-octyl-phenol (each isomer), Dipropyl-indenyl-phenol (each isomer), Dipropyl-indenyl-phenol (each isomer), Dipropyl-dodecyl-phenol (each isomer), Dipropyl-phenyl-phenol (each isomer), Dipropyl-phenoxyphenol (each isomer), Dipropyl-cumyl-phenol (each isomer), Dibutyl-methyl-phenol (each isomer), Dibutyl-ethyl-phenol (each isomer), Dibutyl-propyl-phenol (each isomer), Dibutyl-pentyl-phenol (each isomer), Dibutyl-hexyl-phenol (each isomer), Dibutyl-heptyl-phenol (each isomer), Dibutyl-octyl-phenol (each isomer), Dibutyl-mercapto-phenol (each isomer), Dibutyl-mercapto-phenol (each isomer), Dibutyl-dodecyl-phenol (each isomer), Dibutyl-phenyl-phenol (each isomer), Dibutyl-phenoxyphenol (each isomer), Dibutyl-cumyl-phenol (each isomer), Dipentyl-methyl-phenol (each isomer), Dipentyl-ethyl-phenol (each isomer), Dipentyl-propyl-phenol (each isomer), Dipentyl-butyl-phenol (each isomer), Dipentyl-hexyl-phenol (each isomer), Dipentyl-heptyl-phenol (each isomer), Dipentyl-octyl-phenol (each isomer), Dipentyl-indenyl-phenol (each isomer), Dipentyl-indenyl-phenol (each isomer), Dipentyl-dodecyl-phenol (each isomer), Dipentyl-phenyl-phenol (each isomer), Dipentyl-phenoxyphenol (each isomer), Dipentyl-cumyl-phenol (each isomer), Dihexyl-methyl-phenol (each isomer), Dihexyl-ethyl-phenol (each isomer), Dihexyl-propyl-phenol (each isomer), Dihexyl-butyl-phenol (each isomer), Dihexyl-pentyl-phenol (each isomer), Dihexyl-heptyl-phenol (each isomer), Dihexyl-octyl-phenol (each isomer), Dihexyl-indenyl-phenol (each isomer), Dihexyl-indenyl-phenol (each isomer), Dihexyl-dodecyl-phenol (each isomer), Dihexyl-phenyl-phenol (each isomer), Dihexyl-phenoxyphenol (each isomer), Dihexyl-isopropylphenyl-phenol (each isomer), Diheptyl-methyl-phenol (each isomer), Diheptyl-ethyl-phenol (each isomer), Diheptyl-propyl-phenol (each isomer), Diheptyl-butyl-phenol (each isomer), Diheptyl-pentyl-phenol (each isomer), Diheptyl-hexyl-phenol (each isomer), Diheptyl-octyl-phenol (each isomer), Diheptyl-indenyl-phenol (each isomer), Diheptyl-indenyl-phenol (each isomer), Diheptyl-dodecyl-phenol (each isomer), Diheptyl-phenyl-phenol (each isomer), Diheptyl-phenoxyphenol (each isomer), Diheptyl-isopropylphenyl-phenol (each isomer), Dioctyl-methyl-phenol (each isomer), Dioctyl-ethyl-phenol (each isomer), Dioctyl-propyl-phenol (each isomer), Dioctyl-butyl-phenol (each isomer), Dioctyl-pentyl-phenol (each isomer), Dioctyl-hexyl-phenol (each isomer), Dioctyl-heptyl-phenol (each isomer), Dioctyl-decyl-phenol (each isomer), Dioctyl-decyl-phenol (each isomer), Dioctyl-dodecyl-phenol (each isomer), Dioctyl-phenyl-phenol (each isomer), Dioctyl-phenoxyphenol (each isomer), Dioctyl-isopropylphenyl-phenol (each isomer), Dimercapto-methyl-phenol (each isomer), Dimercapto-ethyl-phenol (each isomer), Dimercapto-propyl-phenol (each isomer), Dimercapto-butyl-phenol (each isomer), Dimercapto-pentyl-phenol (each isomer), Dimercapto-hexyl-phenol (each isomer), Dimercapto-heptyl-phenol (each isomer), Dimercapto-octyl-phenol (each isomer), Dimercapto-indenyl-phenol (each isomer), Dimercapto-dodecyl-phenol (each isomer), Dimercapto-phenyl-phenol (each isomer), Dimercapto-phenoxyphenol (each isomer), Dimercapto-isopropylphenyl-phenol (each isomer), Dimercapto-methyl-phenol (each isomer), Dimercapto-ethyl-phenol (each isomer), Dimercapto-propyl-phenol (each isomer), Dimercapto-butyl-phenol (each isomer), Dimercapto-pentyl-phenol (each isomer), Dimercapto-hexyl-phenol (each isomer), Dimercapto-heptyl-phenol (each isomer), Dimercapto-octyl-phenol (each isomer), Dimercapto-indenyl-phenol (each isomer), Dimercapto-dodecyl-phenol (each isomer), Dimercapto-phenyl-phenol (each isomer), Dimercapto-phenoxyphenol (each isomer), Dimercapto-isopropylphenyl-phenol (each isomer), Di(dodecyl)-methyl-phenol (each isomer), Di(dodecyl)-ethyl-phenol (each isomer), Di(dodecyl)-propyl-phenol (each isomer), Di(dodecyl)-butyl-phenol (each isomer), Di(dodecyl)-pentyl-phenol (each isomer), Di(dodecyl)-hexyl-phenol (each isomer), Di(dodecyl)-heptyl-phenol (each isomer), Di(dodecyl)-octyl-phenol (each isomer), Di(dodecyl)-fluorenyl-phenol (each isomer), Di(dodecyl)-fluorenyl-phenol (each isomer), Di(dodecyl)-dodecyl-phenol (each isomer), Di(dodecyl)-phenyl-phenol (each isomer), Di(dodecyl)-phenoxyphenol (each isomer), Di(dodecyl)-isopropylphenyl-phenol (each isomer), Diphenyl-methyl-phenol (each isomer), Diphenyl-ethyl-phenol (each isomer), Diphenyl-propyl-phenol (each isomer), Diphenyl-butyl-phenol (each isomer), Diphenyl-pentyl-phenol (each isomer), Diphenyl-hexyl-phenol (each isomer), Diphenyl-heptyl-phenol (each isomer), Diphenyl-octyl-phenol (each isomer), Diphenyl-mercapto-phenol (each isomer), Diphenyl-mercapto-phenol (each isomer), Diphenyl-dodecyl-phenol (each isomer), Diphenyl-phenoxyphenol (each isomer), Diphenyl-isopropylphenyl-phenol (each isomer), Diphenoxymethyl-phenol (each isomer), Diphenoxyethyl-phenol (each isomer), Diphenoxypropyl-phenol (each isomer), Diphenoxybutyl-phenol (each isomer), Diphenoxypentyl-phenol (each isomer), Diphenoxyhexyl-phenol (each isomer), Diphenoxyheptyl-phenol (each isomer), Diphenoxyoctyl-phenol (each isomer), Diphenoxynonyl-phenol (each isomer), Diphenoxynonyl-phenol (each isomer), Diphenoxydodecyl-phenol (each isomer), Diphenoxyphenyl-phenol (each isomer), Diphenoxyisopropyl phenyl-phenol (each isomer), Dicumyl-methyl-phenol (each isomer), Dicumyl-ethyl-phenol (each isomer), Dicumyl-propyl-phenol (each isomer), Dicumyl-butyl-phenol (each isomer), Dicumyl-pentyl-phenol (each isomer), Dicumyl-hexyl-phenol (each isomer), Diisopropylphenyl-heptyl-phenol (each isomer), Dicumyl-octyl-phenol (each isomer), Dicumyl-mercapto-phenol (each isomer), Dicumyl-mercapto-phenol (each isomer), Dicumyl-dodecyl-phenol (each isomer), Dicumyl-phenyl-phenol (each isomer), Dicumyl-phenoxyphenol (each isomer), Methyl-ethyl-propyl-phenol (each isomer), Methyl-ethyl-butyl-phenol (each isomer), Methyl-ethyl-pentyl-phenol (each isomer), Methyl-ethyl-hexyl-phenol (each isomer), Methyl-ethyl-heptyl-phenol (each isomer), Methyl-ethyl-octyl-phenol (each isomer), Methyl-ethyl-fluorenyl-phenol (each isomer), Methyl-ethyl-fluorenyl-phenol (each isomer), Methyl-ethyl-dodecyl-phenol (each isomer), Methyl-ethyl-phenyl-phenol (each isomer), Methyl-ethyl-phenoxyphenol (each isomer), Methyl-ethyl-isopropylphenyl-phenol (each isomer), Methyl-propyl-butyl-phenol (each isomer), Methyl-propyl-pentyl-phenol (each isomer), Methyl-propyl-hexyl-phenol (each isomer), Methyl-propyl-heptyl-phenol (each isomer), Methyl-propyl-octyl-phenol (each isomer), Methyl-propyl-indenyl-phenol (each isomer), Methyl-propyl-indenyl-phenol (each isomer), Methyl-propyl-dodecyl-phenol (each isomer), Methyl-propyl-phenyl-phenol (each isomer), Methyl-propyl-phenoxyphenol (each isomer), Methyl-propyl-isopropylphenyl-phenol (each isomer), Methyl-butyl-pentyl-phenol (each isomer), Methyl-butyl-hexyl-phenol (each isomer), Methyl-butyl-heptyl-phenol (each isomer), Methyl-butyl-octyl-phenol (each isomer), Methyl-butyl-mercapto-phenol (each isomer), Methyl-butyl-mercapto-phenol (each isomer), Methyl-butyl-dodecyl-phenol (each isomer), Methyl-butyl-phenyl-phenol (each isomer), Methyl-butyl-phenoxyphenol (each isomer), Methyl-butyl-cumyl-phenol (each isomer), Methyl-pentyl-hexyl-phenol (each isomer), Methyl-pentyl-heptyl-phenol (each isomer), Methyl-pentyl-octyl-phenol (each isomer), Methyl-pentyl-indolyl-phenol (each isomer), Methyl-pentyl-indolyl-phenol (each isomer), Methyl-pentyl-dodecyl-phenol (each isomer), Methyl-pentyl-phenyl-phenol (each isomer), Methyl-pentyl-phenoxyphenol (each isomer), Methyl-pentyl-cumyl-phenol (each isomer), Methyl-hexyl-heptyl-phenol (each isomer), Methyl-hexyl-octyl-phenol (each isomer), Methyl-hexyl-indolyl-phenol (each isomer), Methyl-hexyl-indolyl-phenol (each isomer), Methyl-hexyl-dodecyl-phenol (each isomer), Methyl-hexyl-phenyl-phenol (each isomer), Methyl-hexyl-phenoxyphenol (each isomer), Methyl-hexyl-cumyl-phenol (each isomer), Ethyl-propyl-butyl-phenol (each isomer), Ethyl-propyl-pentyl-phenol (each isomer), Ethyl-propyl-hexyl-phenol (each isomer), Ethyl-propyl-heptyl-phenol (each isomer), Ethyl-propyl-octyl-phenol (each isomer), Ethyl-propyl-indenyl-phenol (each isomer), Ethyl-propyl-indenyl-phenol (each isomer), Ethyl-propyl-dodecyl-phenol (each isomer), Ethyl-propyl-phenyl-phenol (each isomer), Ethyl-propyl-phenoxyphenol (each isomer), Ethyl-propyl-isopropylphenyl-phenol (each isomer), Ethyl-butyl-phenol (each isomer), Ethyl-butyl-pentyl-phenol (each isomer), Ethyl-butyl-hexyl-phenol (each isomer), Ethyl-butyl-heptyl-phenol (each isomer), Ethyl-butyl-octyl-phenol (each isomer), Ethyl-butyl-mercapto-phenol (each isomer), Ethyl-butyl-mercapto-phenol (each isomer), Ethyl-butyl-dodecyl-phenol (each isomer), Ethyl-butyl-phenyl-phenol (each isomer), Ethyl-butyl-phenoxyphenol (each isomer), Ethyl-butyl-cumyl-phenol (each isomer), Ethyl-pentyl-hexyl-phenol (each isomer), Ethyl-pentyl-heptyl-phenol (each isomer), Ethyl-pentyl-octyl-phenol (each isomer), Ethyl-pentyl-indolyl-phenol (each isomer), Ethyl-pentyl-indolyl-phenol (each isomer), Ethyl-pentyl-dodecyl-phenol (each isomer), Ethyl-pentyl-phenyl-phenol (each isomer), Ethyl-pentyl-phenoxyphenol (each isomer), Ethyl-pentyl-cumyl-phenol (each isomer), Ethyl-hexyl-heptyl-phenol (each isomer), Ethyl-hexyl-octyl-phenol (each isomer), Ethyl-hexyl-indolyl-phenol (each isomer), Ethyl-hexyl-indolyl-phenol (each isomer), Ethyl-hexyl-dodecyl-phenol (each isomer), Ethyl-hexyl-phenyl-phenol (each isomer), Ethyl-hexyl-phenoxyphenol (each isomer), Ethyl-hexyl-cumyl-phenol (each isomer), Ethyl-heptyl-octyl-phenol (each isomer), Ethyl-heptyl-indenyl-phenol (each isomer), Ethyl-heptyl-indenyl-phenol (each isomer), Ethyl-heptyl-dodecyl-phenol (each isomer), Ethyl-heptyl-phenyl-phenol (each isomer), Ethyl-heptyl-phenoxyphenol (each isomer), Ethyl-heptyl-isopropylphenyl-phenol (each isomer), Ethyl-octyl-phenol (each isomer), Ethyl-octyl-indenyl-phenol (each isomer), Ethyl-octyl-indenyl-phenol (each isomer), Ethyl-octyl-dodecyl-phenol (each isomer), Ethyl-octyl-phenyl-phenol (each isomer), Ethyl-octyl-phenoxyphenol (each isomer), Ethyl-octyl-isopropylphenyl-phenol (each isomer), Ethyl-fluorenyl-fluorenyl-phenol (each isomer), Ethyl-indenyl-dodecyl-phenol (each isomer), Ethyl-indenyl-phenyl-phenol (each isomer), Ethyl-mercapto-phenoxyphenol (each isomer), Ethyl-indenyl-cumyl-phenol (each isomer), Ethyl-indenyl-dodecyl-phenol (each isomer), Ethyl-indenyl-phenyl-phenol (each isomer), Ethyl-mercapto-phenoxyphenol (each isomer), Ethyl-indenyl-cumyl-phenol (each isomer), Ethyl-dodecyl-phenyl-phenol (each isomer), Ethyl-dodecyl-phenoxyphenol (each isomer), Ethyl-dodecyl-cumyl-phenol (each isomer), Ethyl-phenyl-phenoxyphenol (each isomer), Ethyl-phenyl-cumyl-phenol (each isomer), Propyl-butyl-phenol (each isomer), Propyl-butyl-pentyl-phenol (each isomer), Propyl-butyl-hexyl-phenol (each isomer), Propyl-butyl-heptyl-phenol (each isomer), Propyl-butyl-octyl-phenol (each isomer), Propyl-butyl-mercapto-phenol (each isomer), Propyl-butyl-mercapto-phenol (each isomer), Propyl-butyl-dodecyl-phenol (each isomer), Propyl-butyl-phenyl-phenol (each isomer), Propyl-butyl-phenoxyphenol (each isomer), Propyl-butyl-cumyl-phenol (each isomer), Propyl-pentyl-phenol (each isomer), Propyl-pentyl-hexyl-phenol (each isomer), Propyl-pentyl-heptyl-phenol (each isomer), Propyl-pentyl-octyl-phenol (each isomer), Propyl-pentyl-indolyl-phenol (each isomer), Propyl-pentyl-indolyl-phenol (each isomer), Propyl-pentyl-dodecyl-phenol (each isomer), Propyl-pentyl-phenyl-phenol (each isomer), Propyl-pentyl-phenoxyphenol (each isomer), Propyl-pentyl-cumyl-phenol (each isomer), Propyl-hexyl-phenol (each isomer), Propyl-hexyl-heptyl-phenol (each isomer), Propyl-hexyl-octyl-phenol (each isomer), Propyl-hexyl-decyl-phenol (each isomer), Propyl-hexyl-decyl-phenol (each isomer), Propyl-hexyl-dodecyl-phenol (each isomer), Propyl-hexyl-phenyl-phenol (each isomer), Propyl-hexyl-phenoxyphenol (each isomer), Propyl-hexyl-cumyl-phenol (each isomer), Propyl-heptyl-octyl-phenol (each isomer), Propyl-heptyl-fluorenyl-phenol (each isomer), Propyl-heptyl-fluorenyl-phenol (each isomer), Propyl-heptyl-dodecyl-phenol (each isomer), Propyl-heptyl-phenyl-phenol (each isomer), Propyl-heptyl-phenoxyphenol (each isomer), Propyl-heptyl-cumyl-phenol (each isomer), Propyl-octyl-fluorenyl-phenol (each isomer), Propyl-octyl-fluorenyl-phenol (each isomer), Propyl-octyl-dodecyl-phenol (each isomer), Propyl-octyl-phenyl-phenol (each isomer), Propyl-octyl-phenoxyphenol (each isomer), Propyl-octyl-isopropylphenyl-phenol (each isomer), Propyl-mercapto-mercapto-phenol (each isomer), Propyl-mercapto-dodecyl-phenol (each isomer), Propyl-mercapto-phenyl-phenol (each isomer), Propyl-mercapto-phenoxyphenol (each isomer), Propyl-mercapto-isopropylphenyl-phenol (each isomer), Propyl-mercapto-dodecyl-phenol (each isomer), Propyl-mercapto-phenyl-phenol (each isomer), Propyl-mercapto-phenoxyphenol (each isomer), Propyl-mercapto-isopropylphenyl-phenol (each isomer), Propyl-dodecyl-phenyl-phenol (each isomer), Propyl-dodecyl-phenoxyphenol (each isomer), Propyl-dodecyl-cumylphenol-phenol (each isomer), Methyl-phenol (each isomer), Ethyl-phenol (each isomer), Propyl-phenol (each isomer), Butyl-phenol (each isomer), Pentyl-phenol (each isomer), Hexyl-phenol (each isomer), Heptyl-phenol (each isomer), Octyl-phenol (each isomer), Mercapto-phenol (each isomer), Mercapto-phenol (each isomer), Dodecyl-phenol (each isomer), Phenyl-phenol (each isomer), Phenoxyphenol (each isomer), Propiyl-phenol (each isomer), Propyl-phenyl-phenoxyphenol (each isomer), Propyl-phenyl-isopropylphenyl-phenol (each isomer), Propyl-phenoxyisopropylphenyl-phenol (each isomer), Propyl-butyl-pentyl-phenol (each isomer), Propyl-butyl-hexyl-phenol (each isomer), Propyl-butyl-heptyl-phenol (each isomer), Propyl-butyl-octyl-phenol (each isomer), Propyl-butyl-mercapto-phenol (each isomer), Propyl-butyl-mercapto-phenol (each isomer), Propyl-butyl-dodecyl-phenol (each isomer), Propyl-butyl-phenyl-phenol (each isomer), Propyl-butyl-phenoxyphenol (each isomer), Propyl-butyl-cumyl-phenol (each isomer), Propyl-pentyl-phenol (each isomer), Propyl-pentyl-hexyl-phenol (each isomer), Propyl-pentyl-heptyl-phenol (each isomer), Propyl-pentyl-octyl-phenol (each isomer), Propyl-pentyl-indolyl-phenol (each isomer), Propyl-pentyl-indolyl-phenol (each isomer), Propyl-pentyl-dodecyl-phenol (each isomer), Propyl-pentyl-phenyl-phenol (each isomer), Propyl-pentyl-phenoxyphenol (each isomer), Propyl-pentyl-cumyl-phenol (each isomer), Propyl-hexyl-heptyl-phenol (each isomer), Propyl-hexyl-octyl-phenol (each isomer), Propyl-hexyl-decyl-phenol (each isomer), Propyl-hexyl-decyl-phenol (each isomer), Propyl-hexyl-dodecyl-phenol (each isomer), Propyl-hexyl-phenyl-phenol (each isomer), Propyl-hexyl-phenoxyphenol (each isomer), Propyl-hexyl-cumyl-phenol (each isomer), Propyl-heptyl-octyl-phenol (each isomer), Propyl-heptyl-fluorenyl-phenol (each isomer), Propyl-heptyl-fluorenyl-phenol (each isomer), Propyl-heptyl-dodecyl-phenol (each isomer), Propyl-heptyl-phenyl-phenol (each isomer), Propyl-heptyl-phenoxyphenol (each isomer), Propyl-heptyl-cumyl-phenol (each isomer), Propyl-octyl-fluorenyl-phenol (each isomer), Propyl-octyl-fluorenyl-phenol (each isomer), Propyl-octyl-dodecyl-phenol (each isomer), Propyl-octyl-phenyl-phenol (each isomer), Propyl-octyl-phenoxyphenol (each isomer), Propyl-octyl-isopropylphenyl-phenol (each isomer), Propyl-mercapto-mercapto-phenol (each isomer), Propyl-mercapto-dodecyl-phenol (each isomer), Propyl-mercapto-phenyl-phenol (each isomer), Propyl-mercapto-phenoxyphenol (each isomer), Propyl-mercapto-isopropylphenyl-phenol (each isomer), Propyl-mercapto-dodecyl-phenol (each isomer), Propyl-mercapto-phenyl-phenol (each isomer), Propyl-mercapto-phenoxyphenol (each isomer), Propyl-mercapto-isopropylphenyl-phenol (each isomer), Propyl-dodecyl-phenyl-phenol (each isomer), Propyl-dodecyl-phenoxyphenol (each isomer), Propyl-dodecyl-cumylphenol-phenol (each isomer), Propyl-phenyl-phenoxyphenol (each isomer), Propyl-phenyl-isopropylphenyl-phenol (each isomer), Butyl-pentyl-hexyl-phenol (each isomer), Butyl-pentyl-heptyl-phenol (each isomer), Butyl-pentyl-octyl-phenol (each isomer), Butyl-pentyl-indolyl-phenol (each isomer), Butyl-pentyl-indolyl-phenol (each isomer), Butyl-pentyl-dodecyl-phenol (each isomer), Butyl-pentyl-phenyl-phenol (each isomer), Butyl-pentyl-phenoxyphenol (each isomer), Butyl-pentyl-cumyl-phenol (each isomer), Butyl-hexyl-heptyl-phenol (each isomer), Butyl-hexyl-octyl-phenol (each isomer), Butyl-hexyl-indolyl-phenol (each isomer), Butyl-hexyl-indolyl-phenol (each isomer), Butyl-hexyl-dodecyl-phenol (each isomer), Butyl-hexyl-phenyl-phenol (each isomer), Butyl-hexyl-phenoxyphenol (each isomer), Butyl-hexyl-cumyl-phenol (each isomer), Butyl-heptyl-octyl-phenol (each isomer), Butyl-heptyl-indolyl-phenol (each isomer), Butyl-heptyl-indolyl-phenol (each isomer), Butyl-heptyl-dodecyl-phenol (each isomer), Butyl-heptyl-phenyl-phenol (each isomer), Butyl-heptyl-phenoxyphenol (each isomer), Butyl-heptyl-cumyl-phenol (each isomer), Butyl-octyl-fluorenyl-phenol (each isomer), Butyl-octyl-fluorenyl-phenol (each isomer), Butyl-octyl-dodecyl-phenol (each isomer), Butyl-octyl-phenyl-phenol (each isomer), Butyl-octyl-phenoxyphenol (each isomer), Butyl-octyl-isopropylphenyl-phenol (each isomer), Butyl-mercapto-fluorenyl-phenol (each isomer), Butyl-mercapto-dodecyl-phenol (each isomer), Butyl-mercapto-phenyl-phenol (each isomer), Butyl-mercapto-phenoxyphenol (each isomer), Butyl-mercapto-isopropylphenyl-phenol (each isomer), Butyl-mercapto-dodecyl-phenol (each isomer), Butyl-mercapto-phenyl-phenol (each isomer), Butyl-mercapto-phenoxyphenol (each isomer), Butyl-mercapto-isopropylphenyl-phenol (each isomer), Butyl-dodecyl-phenol (each isomer), Butyl-dodecyl-phenyl-phenol (each isomer), Butyl-dodecyl-phenoxyphenol (each isomer), Butyl-dodecyl-cumylphenol-phenol (each isomer), Butyl-phenyl-phenol (each isomer), Butyl-phenyl-phenoxyphenol (each isomer), Butyl-phenyl-isopropylphenyl-phenol (each isomer), Pentyl-hexyl-heptyl-phenol (each isomer), Pentyl-hexyl-octyl-phenol (each isomer), Pentyl-hexyl-indolyl-phenol (each isomer), Pentyl-hexyl-indolyl-phenol (each isomer), Pentyl-hexyl-dodecyl-phenol (each isomer), Pentyl-hexyl-phenyl-phenol (each isomer), Amyl-hexyl-phenoxyphenol (each isomer), Amyl-hexyl-cumyl-phenol (each isomer), Pentyl-heptyl-octyl-phenol (each isomer), Pentyl-heptyl-fluorenyl-phenol (each isomer), Pentyl-heptyl-fluorenyl-phenol (each isomer), Pentyl-heptyl-dodecyl-phenol (each isomer), Butyl-heptyl-phenyl-phenol (each isomer), Butyl-heptyl-phenoxyphenol (each isomer), Butyl-heptyl-cumyl-phenol (each isomer), Pentyl-octyl-decyl-phenol (each isomer), Pentyl-octyl-decyl-phenol (each isomer), Amyl-octyl-dodecyl-phenol (each isomer), Butyl-octyl-phenyl-phenol (each isomer), Amyl-octyl-phenoxyphenol (each isomer), Amyl-octyl-isopropylphenyl-phenol (each isomer), Pentyl-indenyl-fluorenyl-phenol (each isomer), Amyl-decyl-dodecyl-phenol (each isomer), Amyl-decyl-phenyl-phenol (each isomer), Amyl-decyl-phenoxyphenol (each isomer), Amyl-decyl-cumyl-phenol (each isomer), Amyl-decyl-dodecyl-phenol (each isomer), Amyl-decyl-phenyl-phenol (each isomer), Amyl-decyl-phenoxyphenol (each isomer), Amyl-decyl-cumyl-phenol (each isomer), Amyl-decyl-dodecyl-phenol (each isomer), Amyl-decyl-phenyl-phenol (each isomer), Amyl-decyl-phenoxyphenol (each isomer), Amyl-decyl-cumyl-phenol (each isomer), Pentyl-dodecyl-phenyl-phenol (each isomer), Amyl-dodecyl-phenoxyphenol (each isomer), Amyl-dodecyl-cumyl-phenol (each isomer), Butyl-phenyl-phenoxyphenol (each isomer), Butyl-phenyl-cumylphenol-phenol (each isomer), Hexyl-heptyl-octyl-phenol (each isomer), Hexyl-heptyl-fluorenyl-phenol (each isomer), Hexyl-heptyl-fluorenyl-phenol (each isomer), Hexyl-heptyl-dodecyl-phenol (each isomer), Hexyl-heptyl-phenyl-phenol (each isomer), Hexyl-heptyl-phenoxyphenol (each isomer), Hexyl-heptyl-isopropylphenyl-phenol (each isomer), Hexyl-octyl-fluorenyl-phenol (each isomer), Hexyl-octyl-fluorenyl-phenol (each isomer), Hexyl-octyl-dodecyl-phenol (each isomer), Hexyl-octyl-phenyl-phenol (each isomer), Hexyl-octyl-phenoxyphenol (each isomer), Hexyl-octyl-isopropylphenyl-phenol (each isomer), Hexyl-indenyl-fluorenyl-phenol (each isomer), Hexyl-fluorenyl-dodecyl-phenol (each isomer), Hexyl-fluorenyl-phenyl-phenol (each isomer), Hexyl-fluorenyl-phenoxyhexyl-fluorenyl-dodecyl-phenol (each isomer), Hexyl-fluorenyl-phenyl-phenol (each isomer), Hexyl-fluorenyl-phenoxyphenol (each isomer), Hexyl-indenyl-cumyl-phenol (each isomer), Hexyl-dodecyl-phenyl-phenol (each isomer), Hexyl-dodecyl-phenoxyphenol (each isomer), Hexyl-dodecyl-cumylphenol-phenol (each isomer), Hexyl-phenyl-phenoxyphenol (each isomer), Hexyl-phenyl-isopropylphenyl-phenol (each isomer), Heptyl-octyl-fluorenyl-phenol (each isomer), Heptyl-octyl-fluorenyl-phenol (each isomer), Heptyl-octyl-dodecyl-phenol (each isomer), Heptyl-octyl-phenyl-phenol (each isomer), Heptyl-octyl-phenoxyphenol (each isomer), Heptyl-octyl-isopropylphenyl-phenol (each isomer), Heptyl-fluorenyl-fluorenyl-phenol (each isomer), Heptyl-fluorenyl-dodecyl-phenol (each isomer), Heptyl-fluorenyl-phenyl-phenol (each isomer), Heptyl-fluorenyl-phenoxyphenol (each isomer), Heptyl-fluorenyl-cumyl-phenol (each isomer), Heptyl-fluorenyl-dodecyl-phenol (each isomer), Heptyl-fluorenyl-phenyl-phenol (each isomer), Heptyl-fluorenyl-phenoxyphenol (each isomer), Heptyl-fluorenyl-cumyl-phenol (each isomer), Heptyl-dodecyl-phenyl-phenol (each isomer), Heptyl-dodecyl-phenoxyphenol (each isomer), Heptyl-dodecyl-cumyl-phenol (each isomer), Heptyl-phenyl-phenoxyphenol (each isomer), Heptyl-phenyl-isopropylphenyl-phenol (each isomer), Octyl-fluorenyl-fluorenyl-phenol (each isomer), Octyl-decyl-dodecyl-phenol (each isomer), Octyl-fluorenyl-phenyl-phenol (each isomer), Octyl-nonyl-phenoxyphenol (each isomer), Octyl-decyl-isopropylphenyl-phenol (each isomer), Octyl-decyl-dodecyl-phenol (each isomer), Octyl-fluorenyl-phenyl-phenol (each isomer), Octyl-nonyl-phenoxyphenol (each isomer), Octyl-decyl-isopropylphenyl-phenol (each isomer), Octyl-dodecyl-phenyl-phenol (each isomer), Octyl-dodecyl-phenoxyphenol (each isomer), Octyl-dodecyl-cumyl-phenol (each isomer), Octyl-dodecyl-phenyl-phenol (each isomer), Octyl-dodecyl-phenoxyphenol (each isomer), Octyl-dodecyl-cumyl-phenol (each isomer), Octyl-phenyl-phenoxyphenol (each isomer), Octyl-phenyl-isopropylphenyl-phenol (each isomer), Mercapto-mercapto-dodecyl-phenol (isomers), Mercapto-mercapto-phenyl-phenol (each isomer), Mercapto-mercapto-phenoxyphenol (each isomer), Mercapto-mercapto-isopropylphenyl-phenol (each isomer), Mercapto-dodecyl-phenyl-phenol (each isomer), Mercapto-dodecyl-phenoxyphenol (each isomer), Mercapto-dodecyl-cumylphenol-phenol (each isomer), Mercapto-phenyl-phenoxyphenol (each isomer), Mercapto-phenyl-isopropylphenyl-phenol (each isomer), Mercapto-dodecyl-phenyl-phenol (each isomer), Mercapto-dodecyl-phenoxyphenol (each isomer), Mercapto-dodecyl-cumylphenol-phenol (each isomer), Mercapto-phenyl-phenoxyphenol (each isomer), Mercapto-phenyl-isopropylphenyl-phenol (each isomer), Dodecyl-phenyl-phenoxyphenol (each isomer), Dodecyl-phenyl-cumylphenyl-phenol (each isomer), Trisubstituted phenols such as phenyl-phenoxyisopropylphenyl-phenol (each isomer). Among the aromatic hydroxy compounds, Better to use the equivalent of compound R ¹ OH compound, the compound R ¹ OH is based on the base R which constitutes the diaryl carbonate ¹ O(R ¹ In the above-defined aromatic group, O represents an oxygen atom) and a hydrogen atom is added thereto. The reason for this is that the kind of the compound in the reaction mixture obtained by the reaction of the diaryl carbonate with the amine compound can be reduced, and the separation operation can be simplified.

The amine compound is preferably supplied in a liquid state to a reactor for producing an aryl carbamate. In general, the amine compound exemplified above is mostly solid at normal temperature (for example, 20 ° C). In this case, the amine compound may be heated to a temperature above the melting point and supplied as a liquid, but at an excessively high temperature. When an amine compound is supplied, a side reaction such as a thermal modification reaction may be generated by heating. Therefore, it is preferred that the amine compound be a mixture with the above aromatic hydroxy compound, diaryl carbonate or water at a lower temperature. It is supplied in a liquid state.

The reaction conditions for the reaction of the diaryl carbonate with the amine compound vary depending on the compound to be reacted, and the diaryl carbonate is in the range of from 1 to 1000 times in terms of stoichiometric ratio with respect to the amine group of the amine compound. The reaction rate is such that the reaction is completed earlier. Preferably, the diaryl carbonate is an excess relative to the amine group of the amine compound. If the size of the reactor is considered, it is preferably in the range of 1.1 to 50 times, and further preferably 1.5. ~10 times the range. The amount of the aromatic hydroxy compound used is, in terms of stoichiometric ratio, the aromatic hydroxy compound in the range of from 1 to 100 times, more preferably from 1.2 to 50 times, and more preferably from the amine group of the amine compound. 1.5 to 10 times. The reaction temperature is usually in the range of 0 ° C to 150 ° C. In order to increase the reaction rate, high temperature is preferable, and on the other hand, an adverse reaction may be caused at a high temperature. Therefore, it is preferably in the range of 10 ° C to 100 ° C. In order to fix the reaction temperature, a well-known cooling device and heating device can be provided in the above reactor. Further, the reaction pressure varies depending on the type of the compound to be used or the reaction temperature, and may be any of reduced pressure, normal pressure, and pressure, and is usually carried out in the range of 20 to 1 × 10 ⁶ Pa. The reaction time (the residence time in the case of the continuous method) is not particularly limited and is usually 0.001 to 50 hours, preferably 0.01 to 20 hours, more preferably 0.1 to 10 hours. Further, a reaction liquid may be used. For example, it is confirmed by liquid chromatography that a desired amount of the aryl carbamate is formed, and the reaction is terminated.

In the present embodiment, it is preferred that the reaction between the diaryl carbonate and the amine compound does not use a catalyst. In the thermal decomposition reaction of the following reaction mixture and the urethane contained in the reaction mixture, if the aryl carbamate is heated in the presence of a metal component derived from a catalyst, the urethane is sometimes produced. Thermal modification reaction of aryl ester, and the like. When a reaction between a diaryl carbonate and an amine compound is carried out, a catalyst may be used, and after the step of removing the catalyst, the reaction mixture is transported or thermally decomposed, but the step is increased, which is disadvantageous.

However, in order to complete the reaction in a short time, lower the reaction temperature and the like, it is not possible to deny the use of the catalyst. In general, an aromatic amine compound has lower reactivity than an aliphatic amine. Therefore, when an aromatic amine compound is used as an amine compound, the use of a catalyst may be effective. When a catalyst is used, for example, an organometallic compound or an inorganic metal compound such as tin, lead, copper or titanium, an alkali metal or an alkali metal alkoxide such as lithium, sodium, potassium, calcium or strontium methoxide may be used. An alkaline catalyst such as an ethoxide or a butoxide (each isomer).

In the present embodiment, it is preferred that the reaction solvent is not used except for the above aromatic hydroxy compound and/or the remaining diaryl carbonate. In the prior art, there is described a method of using an inert reaction solvent with respect to an isocyanate and a urethane formed by a thermal decomposition reaction of a diaryl urethane, but if such an inert solvent is used, Heat score from the following urethane The separation of the isocyanate or the aromatic hydroxy compound formed by the reaction is troublesome, and is therefore inferior.

The reactor used for the reaction of the diaryl carbonate with the amine compound can be a well-known tank reactor, a column reactor, a distillation column, and if the starting material or the reaction material is not adversely affected, the reactor and the line are The material can be any known material, and SUS304, SUS316, SUS316L, etc. are relatively inexpensive, so that they can be preferably used.

<Amino aryl ester>

By this reaction, a reaction mixture containing an aryl carbamate, a residual diaryl carbonate, and an aromatic hydroxy compound is obtained.

The aryl carbamate is a compound represented by the following formula (18).

(wherein R ² is a group defined above, and represents a group derived from an amine compound, R ¹ is a group defined above, and represents a group derived from a diaryl carbonate, n is an integer of 2 to 10, and the number of amine groups with an amine compound For the same number).

Examples of the urethane represented by the above formula (18) include N,N' -hexanediyl-bis-carbamic acid diphenyl ester and N,N '-hexanediyl-bis-amine. Di(methylphenyl) carbamic acid ester (each isomer), N,N' -hexanediyl-bis-carbamic acid di(ethylphenyl) ester (each isomer), N, N' -Hexyl-bis-aminocarbamic acid di(propylphenyl) ester (each isomer), N,N '-hexanediyl-bis-aminocarbamic acid di(butylphenyl) ester (variety Structure), N,N' -hexanediyl-bis-carbamic acid di(pentylphenyl) ester (each isomer), diphenyl-4,4'-methylene-dicyclohexylamine Carbamate, bis(methylphenyl)-4,4'-methylene-dicyclohexylcarbamate, di(ethylphenyl)-4,4'-methylene-bicyclo Hexyl carbazate, bis(propylphenyl)-4,4'-methylene-dicyclohexylcarbamate (each isomer), di(butylphenyl)-4,4 '-Methylene-dicyclohexylcarbamate (each isomer), bis(pentylphenyl)-4,4'-methylene-dicyclohexylcarbamate (isomeric , bis(hexylphenyl)-4,4'-methylene-dicyclohexyl Carbamate (each isomer), bis(heptylphenyl)-4,4'-methylene-dicyclohexylcarbamate (each isomer), bis(octylphenyl) -4,4'-methylene-dicyclohexylcarbamate (each isomer), 3-(phenoxycarbonylamino-methyl)-3,5,5-trimethylcyclo Phenyl hexyl carbamate, 3-(methylphenoxycarbonylamino-methyl)-3,5,5-trimethylcyclohexylaminocarboxylic acid (methylphenoxy) ester (each isomer) , 3-(ethylphenoxycarbonylamino-methyl)-3,5,5-trimethylcyclohexylaminocarboxylic acid (ethylphenyl) ester (each isomer), 3-(C) Phenoxycarbonylamino-methyl)-3,5,5-trimethylcyclohexylaminocarbamic acid (propyl phenyl) ester (each isomer), 3-(butylphenoxycarbonylamine (methyl)-3,5,5-trimethylcyclohexylaminocarbamic acid (butylphenyl) ester (each isomer), 3-(pentylphenoxycarbonylamino-methyl)- 3,5,5-trimethylcyclohexylaminocarbamic acid (pentylphenyl) ester (each isomer), 3-(hexylphenoxycarbonylamino-methyl)-3,5,5-three Methylcyclohexylaminocarbamic acid (hexylphenyl) ester (each isomer), 3-(heptyl) Phenoxycarbonylamino-methyl)-3,5,5-trimethylcyclohexylaminocarboxylic acid (heptylphenyl) ester (each isomer), 3-(octylphenoxycarbonylamino) -Methyl)-3,5,5-trimethylcyclohexylaminocarbamic acid (octylphenyl) ester (each isomer), toluene-diphenyldicarboxylate (each isomer), toluene - di(methylphenyl) dicarbamate (each isomer), di(ethylphenyl)-diaminocarbamate (each isomer), toluene-diaminocarbamic acid di(propyl) Phenyl phenyl) ester (each isomer), toluene-diaminocarbamic acid di(butylphenyl) ester (each isomer), toluene-diaminocarbamic acid di(pentylphenyl) ester (variety) Structure), toluene-diaminocarbamic acid di(hexylphenyl) ester (each isomer), toluene-diaminocarbamic acid di(heptylphenyl) ester (each isomer), toluene-diamine group Di(octylphenyl)carboxylate (each isomer), N,N' -(4,4'-methylene-diphenyl)-dicarbamic acid diphenyl ester, N,N' -( 4,4'-methylene-diphenyl)-bis(methylphenyl) biscarboxylate, N,N' -(4,4'-methylene-diphenyl)-diamino Di(ethylphenyl)carboxylate, N,N '-( 4,4'-methylene-diphenyl)-diaminopropyl bis(propylphenyl) ester, N,N' -(4,4'-methylene-diphenyl)-diamino Di(butylphenyl)carboxylate, N,N' -(4,4'-methylene-diphenyl)-diaminocarbamic acid di(pentylphenyl) ester, N,N' -(4 , 4'-methylene-diphenyl)-diaminohexyl bis(hexylphenyl) ester, N,N' -(4,4'-methylene-diphenyl)-diaminocarboxylic acid Amino acid such as (heptylphenyl) ester, N,N' -(4,4'-methylene-diphenyl)-diaminocarbamic acid bis(octylphenyl) ester (each isomer) Aromatic ester.

<Transportation of urethane reaction liquid>

The reaction liquid containing the aryl carbamate produced by the above method is preferably taken out from the reactor in which the reaction is carried out, and transported to a reactor for performing the thermal decomposition reaction of the aryl carbamate (hereinafter, referred to as In the thermal decomposition reactor, the thermal decomposition reaction of the aryl carbamate is carried out. By thus distinguishing the reactor for producing the aryl urethane and the thermal decomposition reactor, the reactor corresponding to each reaction can be selected, and the reaction conditions can be flexibly set, so that the yield of each reaction can be improved.

These aryl carbamates are easy to form hydrogen bonds between molecules by constituting a urethane bond of an aryl carbamate, and therefore have a relatively high melting point. When such an aryl carbamate is transported, for example, a shaped processor which pulverizes or processes the solid urethane into pellets can be carried. However, in the case of transporting the shaped aryl aryl carbamate, it often causes clogging of the transport line, or in order to stably transport a certain amount of amine groups when the shape of the aryl carbamate is not uniform. The aryl formate requires a complicated apparatus or a step of controlling the shape of the aryl urethane to a certain range. Therefore, the aryl carbamate is preferably supplied to the thermal decomposition reactor in a liquid form.

As a method of supplying the aryl carbamate to the thermal decomposition reactor in a liquid form, it is preferred to use a method of supplying the reaction mixture obtained by the reaction of a diaryl carbonate and an amine compound.

It is also possible to use a method in which the aryl carbamate is heated to a temperature higher than the melting point to transport the aryl carbamate into a liquid form, but if it is also considered to prevent solidification during transportation, the urethane amide must be heated. To a temperature above the melting point (for example, 200 ° C). In the case where the aryl carbamate is maintained at such a high temperature, the thermal decomposition reaction of the aryl carbamate aryl ester is often produced at a non-ideal position to form an isocyanate or to produce a thermal modification reaction of the aryl carbamate carboxylic acid ester as described above.

On the other hand, the reaction mixture obtained by the reaction of the diaryl carbonate and the amine compound is liquid at normal temperature (20 ° C), or may be lower than the aryl urethane even if it is solid at normal temperature. Since the temperature of the melting point becomes a uniform liquid, the thermal modification reaction of the aryl carbamate aryl ester can be suppressed.

Further, the inventors of the present invention were surprised to find that if the aryl carbamate is transported as a reaction mixture obtained by the reaction of the diaryl carbonate with an amine compound, the heat of the aryl carbamate is inhibited. A reduction in the aryl carbamate resulting from the modification reaction or the like. The reason for achieving such an effect is not clear, but the inventors of the present invention presumed that the aromatic hydroxy compound contained in the reaction mixture and the urethane are contained in the reaction for forming a urea bond represented by the above formula (2). The ester urethane bond (-NHCOO-) forms a hydrogen bond, thereby forming a state in which the urethane bonds are inaccessible to each other, and thus it is difficult to generate a reaction for forming a urea bond.

The transport of the reaction mixture is preferably carried out at a temperature ranging from 10 ° C to 180 ° C, more preferably from 30 ° C to 170 ° C, and further preferably from 50 ° C to 150 ° C.

The aryl urethane is supplied to the thermal decomposition reaction as a reaction mixture obtained by the reaction of a diaryl carbonate and an amine compound, and is supplied to the reaction mixture without performing a distillation separation operation or the like, thereby also having a simplification step. The advantages. Further, in the method of supplying a mixture of a part or all of the aromatic hydroxy compound from the reaction mixture, it is not necessary to carry out the operation of separating only the aryl carbamate from the reaction mixture, so that the procedure is simplified.

<Thermal decomposition reaction of aryl carbamate>

Next, an isocyanate is produced by thermal decomposition reaction of an aryl urethane.

The thermal decomposition reaction of the present embodiment is a reaction of producing an isocyanate and an aromatic hydroxy compound from an amino aryl carbamate.

The reaction temperature is usually in the range of from 100 ° C to 300 ° C, and is preferably a high temperature in order to increase the reaction rate. On the other hand, it may be caused by an aryl urethane and/or an isocyanate as a product at a high temperature. The side reaction is therefore preferably in the range of 150 ° C to 250 ° C. In order to fix the reaction temperature, a well-known cooling device and heating device can be provided in the above reactor. Further, the reaction pressure varies depending on the type of the compound to be used or the reaction temperature, and may be any of reduced pressure, normal pressure, and pressure, and is usually carried out in the range of 20 to 1 × 10 ⁶ Pa. The reaction time (the residence time in the case of the continuous method) is not particularly limited and is usually from 0.001 to 100 hours, preferably from 0.005 to 50 hours, more preferably from 0.01 to 10 hours.

In the present embodiment, it is preferred not to use a catalyst. The use of a catalyst promotes the thermal decomposition reaction, but it is often prone to cause side reactions caused by the above-described aryl urethane and/or isocyanate as a product, which is disadvantageous.

When the aryl carbamate is maintained at a high temperature for a long period of time, a side reaction as described above sometimes occurs. Further, the isocyanate formed by the thermal decomposition reaction sometimes causes a side reaction as described above. Therefore, the aryl carbamate and the isocyanate are preferably kept as short as possible at a high temperature, and the thermal decomposition reaction is preferably carried out in a continuous process. The continuous method refers to a method in which a mixture containing the aryl carbamate is continuously supplied to a reactor to be subjected to a thermal decomposition reaction, and the produced isocyanate and aromatic hydroxy compound are continuously discharged from the thermal decomposition reactor. . In the continuous process, the low-boiling component formed by the thermal decomposition reaction of the aryl carbamate is preferably recovered as a gas phase component from the upper portion of the thermal decomposition reactor, and the remainder is used as a liquid component from the heat. The bottom of the reactor is decomposed and recovered. Can also All of the compounds present in the thermal decomposition reactor are recovered as a gas phase component, but by the presence of a liquid phase component in the thermal decomposition reactor, a side reaction caused by an aryl carbamate and/or an isocyanate can be produced. The polymer compound is dissolved, and has an effect of preventing the polymer compound from adhering to and accumulating in the thermal decomposition reactor. The isocyanate and the aromatic hydroxy compound are formed by thermal decomposition reaction of an aryl urethane, and at least one of the compounds is recovered as a gas phase component. Which compound is recovered as a gas phase component depends on the thermal decomposition reaction conditions.

Here, the phrase "low-boiling component formed by thermal decomposition reaction of aryl carbamate" used in the present embodiment corresponds to an aromatic hydroxyl group formed by thermal decomposition reaction of the urethane. The compound and/or isocyanate means, in particular, a compound which can be present as a gas under the conditions under which the thermal decomposition reaction is carried out.

For example, a method in which an isocyanate produced by a thermal decomposition reaction and an aromatic hydroxy compound are recovered as a gas phase component, and a liquid phase component containing a diaryl carbonate and/or a urethane is recovered can be used. In this method, an isocyanate and an aromatic hydroxy compound can be separately recovered by a thermal decomposition reactor. The recovered gas phase component containing isocyanate is preferably supplied in a gas phase to a distillation apparatus for purifying the isocyanate. The recovered gas phase component containing isocyanate may be supplied to a distillation apparatus by a condenser or the like, and then supplied to a distillation apparatus. However, the apparatus is often complicated or the energy used is increased, which is disadvantageous. On the other hand, a liquid phase component containing a diaryl carbonate and/or an aryl carbamate is recovered from the bottom of the thermal decomposition reactor, and when the liquid component contains a diaryl carbonate, it is preferably That is, the diaryl carbonate is separated and recovered from the liquid phase component, and the diaryl carbonate is used. Further, when the liquid phase component contains an aryl carbamate, it is preferred to supply part or all of the liquid phase component to the upper portion of the thermal decomposition reactor to thermally decompose the aryl carbamate. reaction. Here, the upper part of the thermal decomposition reactor, for example, when the thermal decomposition reactor is a distillation column, refers to a section above the second stage which is upward from the bottom of the column by a theoretical number of stages, and the thermal decomposition reactor is a thin film distillation. In the case of a device, it refers to the upper portion of the heated surface portion. When a part or all of the liquid phase component is supplied to the upper portion of the thermal decomposition reactor, the liquid phase component is preferably from 50 ° C to 180 ° C, more preferably from 70 ° C to 170 ° C, and further preferably Shipped at 100 ° C ~ 150 ° C.

Further, for example, an isocyanate, an aromatic hydroxy compound, and a diaryl carbonate which are produced by a thermal decomposition reaction can be recovered as a gas phase component, and a liquid phase component containing an aryl carbamate aryl ester can be autothermally decomposed. The method of recycling at the bottom. In this method, the recovered isocyanate-containing gas component is preferably supplied in a gas phase to a distillation apparatus for purifying and separating the isocyanate. On the other hand, part or all of the liquid phase component containing the aryl carbamate is supplied to the upper portion of the thermal decomposition reactor, and the aryl carbamate is subjected to thermal decomposition reaction again. When a part or all of the liquid phase component is supplied to the upper portion of the thermal decomposition reactor, the liquid phase component is preferably from 50 ° C to 180 ° C, more preferably from 70 ° C to 170 ° C, and further preferably Shipped at 100 ° C ~ 150 ° C.

Further, for example, an isocyanate formed by a thermal decomposition reaction and an aromatic hydroxy compound may be used, and an aromatic hydroxy compound may be used as a gas phase component. The mixture containing the isocyanate is recovered as a liquid phase component from the bottom of the thermal decomposition reactor. In this case, the liquid phase component is supplied to a distillation apparatus, and the isocyanate is recovered. When the liquid phase component contains a diaryl carbonate, it is preferred to separate and recycle the diaryl carbonate. Further, in the case where the liquid phase component contains an aryl carbamate, it is preferred that a part or all of the mixture containing the aryl carbamate is supplied to the upper portion of the thermal decomposition reactor to form the amine group. The aryl formate is again subjected to a thermal decomposition reaction. When a part or all of the liquid phase component is supplied to the upper portion of the thermal decomposition reactor, the liquid phase component is preferably from 50 ° C to 180 ° C, more preferably from 70 ° C to 170 ° C, and further preferably Shipped at 100 ° C ~ 150 ° C.

As described above, it is preferred that the liquid phase component is recovered from the bottom of the thermal decomposition reactor in the thermal decomposition reaction. The reason for this is that a polymer-form by-product formed by a side reaction caused by an aryl carbamate aryl ester and/or an isocyanate can be dissolved by presenting a liquid phase component in the thermal decomposition reactor as a liquid phase component. Discharging in the thermal decomposition reactor has the effect of reducing the adhesion of the polymer-like compound and accumulating in the thermal decomposition reactor.

When the liquid phase component contains an aryl carbamate, part or all of the liquid phase component is supplied to the upper portion of the thermal decomposition reactor, and the aryl carbamate is subjected to thermal decomposition reaction again. Further, a polymer-like by-product may be accumulated in the liquid phase component. In this case, part or all of the liquid phase component may be removed from the reaction system to reduce the accumulation of polymerous by-products or may be maintained at a constant concentration.

a gas phase component and/or a liquid phase component obtained by the above thermal decomposition reaction The aromatic hydroxy compound and/or the diaryl carbonate contained in the mixture can be separately separated and recovered for reuse. Specifically, the aromatic hydroxy compound can be further used as a reaction solvent for the reaction of the diaryl carbonate with the amine compound, and/or the aromatic hydroxy compound A of the step (3) for producing the diaryl carbonate, and the diaryl carbonate can be used. It is used as a raw material for producing an aryl urethane.

The form of the thermal decomposition reactor is not particularly limited, and in order to efficiently recover the gas phase component, it is preferred to use a well-known distillation apparatus. For example, a distillation column, a multi-stage distillation column, a multi-tubular reactor, a continuous multi-stage distillation column, a packed column, a thin film evaporator, a reactor having a support inside, a forced circulation reactor, a falling film evaporator, and a falling can be used. Various methods such as a method of dropping a reactor of any one of the evaporators, and a method of combining the same. From the viewpoint of quickly removing low-boiling components from the reaction system, it is preferred to use a tubular reactor, preferably a tubular thin film evaporator, a tubular falling film evaporator or the like, preferably a reactor. The resulting low-boiling component is rapidly transferred to a structure in which the gas-liquid contact area of the gas phase is large.

If the aryl urethane or the aromatic hydroxy compound or isocyanate as a product is not adversely affected, the material of the thermal decomposition reactor and the line may be any known material, and SUS304, SUS316, SUS316L, etc. are relatively inexpensive. Therefore, it can be used well.

<Cleaning of Thermal Decomposition Reactor>

In the present embodiment, the reaction liquid containing the aryl carbamate obtained by reacting the diaryl carbonate with the amine compound contains, for example, the polymer represented by the above formula (5), formula (6), and formula (7). A side reaction product or the like. The side reaction Since most of the product is easily dissolved in the aromatic hydroxy compound, it is dissolved in the reaction liquid containing the aryl carbamate. However, in the thermal decomposition reactor, if most of the aromatic hydroxy compound is discharged as a gas phase component from the thermal decomposition reactor, the side reaction product is often precipitated and adhered to the thermal decomposition reactor. Further, with the thermal decomposition reaction of the aryl carbamate carboxylic acid, for example, a polymer by-product derived from a side reaction represented by the above formula (8), formula (9), formula (10) or the like is formed, and the thermal decomposition reaction is carried out. By-products are also often attached to the thermal decomposition reactor. When the compound adhering to the thermal decomposition reactor is accumulated to a certain extent, the operation of the thermal decomposition reactor is often hindered, and it is difficult to operate for a long period of time. Therefore, it is necessary to perform the operation of disassembling the thermal decomposition reactor for cleaning.

The inventors of the present invention were surprised to find that the compound attached to the thermal decomposition reactor was easily dissolved in an acid. Based on this knowledge, the following method is considered and completed: when the high-boiling substance is attached to the thermal decomposition reactor, the wall surface of the thermal decomposition reactor is washed with acid, and the high-boiling substances are dissolved and decomposed from the thermal decomposition. The reactor is removed, thereby keeping the inside of the thermal decomposition reactor (especially the wall) clean. According to this method, the thermal decomposition reactor can be separated and the wall surface of the thermal decomposition reactor can be cleaned, so that the operation stop time of the thermal decomposition reactor can be greatly shortened, and the isocyanate production efficiency is high.

As the acid for cleaning, If it is to dissolve the polymer-like by-product, There is no special limit. Organic acids can be used, Any of inorganic acids, It is preferred to use an organic acid. As an organic acid, Can be exemplified: carboxylic acid, Sulfonic acid, Sulfinic acid, Phenol, Enols, Thiophenols, Yttrium, Ape, Aromatic sulfonamide Class, etc. It is preferred to use a carboxylic acid, Phenols. As such a compound, Can be listed: Formic acid, Acetic acid, Propionic acid, Butyric acid, Isobutyric acid, Valeric acid, Isovaleric acid, 2-methylbutyric acid, Pivalic acid, Caproic acid, Isohexanoic acid, 2-ethylbutyric acid, 2, 2-dimethylbutyric acid, Heptanoic acid (each isomer), Octanoic acid (each isomer), Tannic acid (isomers), Tannic acid (isomers), Undecylic acid (isomers), Dodecanoic acid (isomers), Tetradecanic acid (isomeric), Hexadecaic acid (each isomer), acrylic acid, Butenoic acid, Methacrylic acid, Vinyl acetic acid, Methacrylate, Chalkic acid, Camomile acid, Allyl acetic acid, a saturated or unsaturated aliphatic monocarboxylic acid compound such as undecylenic acid (each isomer), Oxalic acid, Malonate, Succinic acid, Glutaric acid, Adipic acid, Pimelic acid (each isomer), Suberic acid (each isomer), Sebacic acid (each isomer), Sebacic acid (each isomer), Maleic acid, Fumaric acid, Methyl maleic acid, Methyl fumaric acid, Pentenoic acid (each isomer), Ikonic acid, a saturated or unsaturated aliphatic dicarboxylic acid such as allylmalonic acid, 1, 2, 3-propanetricarboxylic acid, 1, 2, 3-propene tricarboxylic acid, 2, 3-dimethylbutane-1, 2, a saturated or unsaturated aliphatic tricarboxylic acid compound such as 3-tricarboxylic acid, benzoic acid, Methyl benzoate (each isomer), Ethyl benzoate (each isomer), Propyl benzoate (isomeric), Dimethyl benzoate (each isomer), An aromatic monocarboxylic acid compound such as trimethyl benzoate (each isomer), Phthalate, Isophthalic acid, Terephthalic acid, An aromatic dicarboxylic acid compound such as methyl isophthalic acid (each isomer), 1, 2, 3-benzenetricarboxylic acid, 1, 2, 4-benzenetricarboxylic acid, 1, 3, An aromatic tricarboxylic acid compound such as 5-benzenetricarboxylic acid, phenol, Methyl-phenol (each isomer), Ethyl-phenol (each isomer), Propyl-phenol (each isomer), Butyl-phenol (each isomer), Pentyl-phenol (each isomer), Hexyl-phenol (each isomer), Heptyl-phenol (each isomer), Octyl-phenol (each isomer), Mercapto-phenol (each isomer), Mercapto-phenol (each isomer), Dodecyl-phenol (each isomer), Phenyl-phenol (each isomer), Phenoxyphenol (each isomer), Monosubstituted phenols such as cumyl-phenol (each isomer), Dimethyl-phenol (each isomer), Diethyl-phenol (each isomer), Dipropyl-phenol (each isomer), Dibutyl-phenol (each isomer), Dipentyl-phenol (each isomer), Dihexyl-phenol (each isomer), Diheptyl-phenol (each isomer), Dioctyl-phenol (each isomer), Dimercapto-phenol (each isomer), Dimercapto-phenol (each isomer), Di(dodecyl)-phenol (each isomer), Diphenyl-phenol (each isomer), Diphenoxyphenol (each isomer), Dicumyl-phenol (each isomer), Methyl-ethyl-phenol (each isomer), Methyl-propyl-phenol (each isomer), Methyl-butyl-phenol (each isomer), Methyl-pentyl-phenol (each isomer), Methyl-hexyl-phenol (each isomer), Methyl-heptyl-phenol (each isomer), Methyl-octyl-phenol (each isomer), Methyl-mercapto-phenol (each isomer), Methyl-mercapto-phenol (each isomer), Methyl-dodecyl-phenol (each isomer), Methyl-phenyl-phenol (each isomer), Methyl-phenoxyphenol (each isomer), Methyl-cumyl-phenol (each isomer), Ethyl-propyl-phenol (each isomer), Ethyl-butyl-phenol (each isomer), Ethyl-pentyl-phenol (each isomer), Ethyl-hexyl-phenol (each isomer), Ethyl-heptyl-phenol (each isomer), Ethyl-octyl-phenol (each isomer), Ethyl-mercapto-phenol (each isomer), Ethyl-mercapto-phenol (each isomer), Ethyl-dodecyl-phenol (each isomer), Ethyl-phenyl-phenol (each isomer), Ethyl-phenoxyphenol (each isomer), Ethyl-cumyl-phenol (each isomer), Propyl-butyl-phenol (each isomer), Propyl-pentyl-phenol (each isomer), Propyl- Hexyl-phenol (each isomer), Propyl-heptyl-phenol (each isomer), Propyl-octyl-phenol (each isomer), Propyl-mercapto-phenol (each isomer), Propyl-mercapto-phenol (each isomer), Propyl-dodecyl-phenol (each isomer), Propyl-phenyl-phenol (each isomer), Propyl-phenoxyphenol (each isomer), Propyl-cumyl-phenol (each isomer), Butyl-pentyl-phenol (each isomer), Butyl-hexyl-phenol (each isomer), Butyl-heptyl-phenol (each isomer), Butyl-octyl-phenol (each isomer), Butyl-mercapto-phenol (each isomer), Butyl-mercapto-phenol (each isomer), Butyl-dodecyl-phenol (each isomer), Butyl-phenyl-phenol (each isomer), Butyl-phenoxyphenol (each isomer), Butyl-cumyl-phenol (each isomer), Pentyl-hexyl-phenol (each isomer), Butyl-heptyl-phenol (each isomer), Butyl-octyl-phenol (each isomer), Amyl-decyl-phenol (each isomer), Amyl-decyl-phenol (each isomer), Amyl-dodecyl-phenol (each isomer), Pentyl-phenyl-phenol (each isomer), Pentyl-phenoxyphenol (each isomer), Amyl-cumyl-phenol (each isomer), Hexyl-heptyl-phenol (each isomer), Hexyl-octyl-phenol (each isomer), Hexyl-fluorenyl-phenol (each isomer), Hexyl-fluorenyl-phenol (each isomer), Hexyl-dodecyl-phenol (each isomer), Hexyl-phenyl-phenol (each isomer), Hexyl-phenoxyphenol (each isomer), Hexyl-isopropylphenyl-phenol (each isomer), Heptyl-octyl-phenol (each isomer), Heptyl-fluorenyl-phenol (each isomer), Heptyl-fluorenyl-phenol (each isomer), Heptyl-dodecyl-phenol (each isomer), Heptyl-phenyl-phenol (each isomer), Heptyl-phenoxyphenol (each isomer), Heptyl-cumyl-phenol (each isomer), Octyl-fluorenyl-phenol (each isomer), Octyl-fluorenyl-phenol (each isomer), Octyl-dodecyl-benzene Phenol (each isomer), Octyl-phenyl-phenol (each isomer), Octyl-phenoxyphenol (each isomer), Octyl-cumyl-phenol (each isomer), Mercapto-mercapto-phenol (each isomer), Mercapto-dodecyl-phenol (each isomer), Mercapto-phenyl-phenol (each isomer), Mercapto-phenoxyphenol (each isomer), Mercapto-cumyl-phenol (each isomer), Dodecyl-phenyl-phenol (each isomer), Dodecyl-phenoxyphenol (each isomer), Disubstituted phenols such as dodecyl-cumyl-phenol (each isomer), Trimethyl-phenol (each isomer), Triethyl-phenol (each isomer), Tripropyl-phenol (each isomer), Tributyl-phenol (each isomer), Tripentyl-phenol (each isomer), Trihexyl-phenol (each isomer), Triheptyl-phenol (each isomer), Trioctyl-phenol (each isomer), Triterpene-phenol (each isomer), Triterpene-phenol (each isomer), Tris(dodecyl)-phenol (each isomer), Triphenyl-phenol (each isomer), Triphenyloxyphenol (each isomer), Triisopropylphenyl-phenol (each isomer), Dimethyl-ethyl-phenol (each isomer), Dimethyl-propyl-phenol (each isomer), Dimethyl-butyl-phenol (each isomer), Dimethyl-pentyl-phenol (each isomer), Dimethyl-hexyl-phenol (each isomer), Dimethyl-heptyl-phenol (each isomer), Dimethyl-octyl-phenol (each isomer), Dimethyl-mercapto-phenol (each isomer), Dimethyl-mercapto-phenol (each isomer), Dimethyl-dodecyl-phenol (each isomer), Dimethyl-phenyl-phenol (each isomer), Dimethyl-phenoxyphenol (each isomer), Dimethyl-cumyl-phenol (each isomer), Diethyl-methyl-phenol (each isomer), Diethyl-propyl-phenol (each isomer), Diethyl-butyl-phenol (each isomer), Diethyl-pentyl-phenol (each isomer), Diethyl-hexyl-phenol (each isomer), Diethyl-heptyl-phenol (each isomer), Diethyl-octyl-phenol (each isomer), Diethyl-mercapto-phenol (each isomer), Diethyl-mercapto-phenol (each isomer), Diethyl-dodecyl-phenol (each isomer), Diethyl-phenyl-phenol (each isomer), Diethyl-phenoxyphenol (each isomer), Diethyl-isopropylphenyl-phenol (each isomer), Dipropyl-methyl-phenol (each isomer), Dipropyl-ethyl-phenol (each isomer), Dipropyl-butyl-phenol (each isomer), Dipropyl-pentyl-phenol (each isomer), Dipropyl-hexyl-phenol (each isomer), Dipropyl-heptyl-phenol (each isomer), Dipropyl-octyl-phenol (each isomer), Dipropyl-indenyl-phenol (each isomer), Dipropyl-indenyl-phenol (each isomer), Dipropyl-dodecyl-phenol (each isomer), Dipropyl-phenyl-phenol (each isomer), Dipropyl-phenoxyphenol (each isomer), Dipropyl-cumyl-phenol (each isomer), Dibutyl-methyl-phenol (each isomer), Dibutyl-ethyl-phenol (each isomer), Dibutyl-propyl-phenol (each isomer), Dibutyl-pentyl-phenol (each isomer), Dibutyl-hexyl-phenol (each isomer), Dibutyl-heptyl-phenol (each isomer), Dibutyl-octyl-phenol (each isomer), Dibutyl-mercapto-phenol (each isomer), Dibutyl-mercapto-phenol (each isomer), Dibutyl-dodecyl-phenol (each isomer), Dibutyl-phenyl-phenol (each isomer), Dibutyl-phenoxyphenol (each isomer), Dibutyl-cumyl-phenol (each isomer), Dipentyl-methyl-phenol (each isomer), Dipentyl-ethyl-phenol (each isomer), Dipentyl-propyl-phenol (each isomer), Dipentyl-butyl-phenol (each isomer), Dipentyl-hexyl-phenol (each isomer), Dipentyl-heptyl-phenol (each isomer), Dipentyl-octyl-phenol (each isomer), Dipentyl-indenyl-phenol (each isomer), Dipentyl-indenyl-phenol (each isomer), Dipentyl-dodecyl-phenol (isomeric Matter) Dipentyl-phenyl-phenol (each isomer), Dipentyl-phenoxyphenol (each isomer), Dipentyl-cumyl-phenol (each isomer), Dihexyl-methyl-phenol (each isomer), Dihexyl-ethyl-phenol (each isomer), Dihexyl-propyl-phenol (each isomer), Dihexyl-butyl-phenol (each isomer), Dihexyl-pentyl-phenol (each isomer), Dihexyl-heptyl-phenol (each isomer), Dihexyl-octyl-phenol (each isomer), Dihexyl-indenyl-phenol (each isomer), Dihexyl-indenyl-phenol (each isomer), Dihexyl-dodecyl-phenol (each isomer), Dihexyl-phenyl-phenol (each isomer), Dihexyl-phenoxyphenol (each isomer), Dihexyl-isopropylphenyl-phenol (each isomer), Diheptyl-methyl-phenol (each isomer), Diheptyl-ethyl-phenol (each isomer), Diheptyl-propyl-phenol (each isomer), Diheptyl-butyl-phenol (each isomer), Diheptyl-pentyl-phenol (each isomer), Diheptyl-hexyl-phenol (each isomer), Diheptyl-octyl-phenol (each isomer), Diheptyl-indenyl-phenol (each isomer), Diheptyl-indenyl-phenol (each isomer), Diheptyl-dodecyl-phenol (each isomer), Diheptyl-phenyl-phenol (each isomer), Diheptyl-phenoxyphenol (each isomer), Diheptyl-isopropylphenyl-phenol (each isomer), Dioctyl-methyl-phenol (each isomer), Dioctyl-ethyl-phenol (each isomer), Dioctyl-propyl-phenol (each isomer), Dioctyl-butyl-phenol (each isomer), Dioctyl-pentyl-phenol (each isomer), Dioctyl-hexyl-phenol (each isomer), Dioctyl-heptyl-phenol (each isomer), Dioctyl-decyl-phenol (each isomer), Dioctyl-decyl-phenol (each isomer), Dioctyl-dodecyl-phenol (each isomer), Dioctyl-phenyl-phenol (each isomer), Dioctyl-phenoxyphenol (each isomer), Dioctyl-isopropylphenyl-phenol (each isomer), Dimercapto-methyl-benzene Phenol (each isomer), Dimercapto-ethyl-phenol (each isomer), Dimercapto-propyl-phenol (each isomer), Dimercapto-butyl-phenol (each isomer), Dimercapto-pentyl-phenol (each isomer), Dimercapto-hexyl-phenol (each isomer), Dimercapto-heptyl-phenol (each isomer), Dimercapto-octyl-phenol (each isomer), Dimercapto-indenyl-phenol (each isomer), Dimercapto-dodecyl-phenol (each isomer), Dimercapto-phenyl-phenol (each isomer), Dimercapto-phenoxyphenol (each isomer), Dimercapto-isopropylphenyl-phenol (each isomer), Dimercapto-methyl-phenol (each isomer), Dimercapto-ethyl-phenol (each isomer), Dimercapto-propyl-phenol (each isomer), Dimercapto-butyl-phenol (each isomer), Dimercapto-pentyl-phenol (each isomer), Dimercapto-hexyl-phenol (each isomer), Dimercapto-heptyl-phenol (each isomer), Dimercapto-octyl-phenol (each isomer), Dimercapto-indenyl-phenol (each isomer), Dimercapto-dodecyl-phenol (each isomer), Dimercapto-phenyl-phenol (each isomer), Dimercapto-phenoxyphenol (each isomer), Dimercapto-isopropylphenyl-phenol (each isomer), Di(dodecyl)-methyl-phenol (each isomer), Di(dodecyl)-ethyl-phenol (each isomer), Di(dodecyl)-propyl-phenol (each isomer), Di(dodecyl)-butyl-phenol (each isomer), Di(dodecyl)-pentyl-phenol (each isomer), Di(dodecyl)-hexyl-phenol (each isomer), Di(dodecyl)-heptyl-phenol (each isomer), Di(dodecyl)-octyl-phenol (each isomer), Di(dodecyl)-fluorenyl-phenol (each isomer), Di(dodecyl)-fluorenyl-phenol (each isomer), Di(dodecyl)-dodecyl-phenol (each isomer), Di(dodecyl)-phenyl-phenol (each isomer), Di(dodecyl)-phenoxyphenol (each isomer), Di(dodecyl)-isopropylphenyl-phenyl (each isomer), Diphenyl-A Base-phenol (each isomer), Diphenyl-ethyl-phenol (each isomer), Diphenyl-propyl-phenol (each isomer), Diphenyl-butyl-phenol (each isomer), Diphenyl-pentyl-phenol (each isomer), Diphenyl-hexyl-phenol (each isomer), Diphenyl-heptyl-phenol (each isomer), Diphenyl-octyl-phenol (each isomer), Diphenyl-mercapto-phenol (each isomer), Diphenyl-mercapto-phenol (each isomer), Diphenyl-dodecyl-phenol (each isomer), Diphenyl-phenoxyphenol (each isomer), Diphenyl-isopropylphenyl-phenol (each isomer), Diphenoxymethyl-phenol (each isomer), Diphenoxyethyl-phenol (each isomer), Diphenoxypropyl-phenol (each isomer), Diphenoxybutyl-phenol (each isomer), Diphenoxypentyl-phenol (each isomer), Diphenoxyhexyl-phenol (each isomer), Diphenoxyheptyl-phenol (each isomer), Diphenoxyoctyl-phenol (each isomer), Diphenoxynonyl-phenol (each isomer), Diphenoxynonyl-phenol (each isomer), Diphenoxydodecyl-phenol (each isomer), Diphenoxyphenyl-phenol (each isomer), Diphenoxyisopropyl phenyl-phenol (each isomer), Dicumyl-methyl-phenol (each isomer), Dicumyl-ethyl-phenol (each isomer), Dicumyl-propyl-phenol (each isomer), Dicumyl-butyl-phenol (each isomer), Dicumyl-pentyl-phenol (each isomer), Dicumyl-hexyl-phenol (each isomer), Diisopropylphenyl-heptyl-phenol (each isomer), Dicumyl-octyl-phenol (each isomer), Dicumyl-mercapto-phenol (each isomer), Dicumyl-mercapto-phenol (each isomer), Dicumyl-dodecyl-phenol (each isomer), Dicumyl-phenyl-phenol (each isomer), Dicumyl-phenoxyphenol (each isomer), Methyl-ethyl-propyl-phenol (each isomer), Methyl-ethyl-butyl-phenol (each isomer), Methyl-ethyl-pentyl-phenol (each isomer), Methyl-ethyl-hexyl-phenol (each isomer), Methyl-ethyl-heptyl-phenol (each isomer), Methyl-ethyl-octyl-phenol (each isomer), Methyl-ethyl-fluorenyl-phenol (each isomer), Methyl-ethyl-fluorenyl-phenol (each isomer), Methyl-ethyl-dodecyl-phenol (each isomer), Methyl-ethyl-phenyl-phenol (each isomer), Methyl-ethyl-phenoxyphenol (each isomer), Methyl-ethyl-isopropylphenyl-phenol (each isomer), Methyl-propyl-methyl-propyl-butyl-phenol (each isomer), Methyl-propyl-pentyl-phenol (each isomer), Methyl-propyl-hexyl-phenol (each isomer), Methyl-propyl-heptyl-phenol (each isomer), Methyl-propyl-octyl-phenol (each isomer), Methyl-propyl-indenyl-phenol (each isomer), Methyl-propyl-indenyl-phenol (each isomer), Methyl-propyl-dodecyl-phenol (each isomer), Methyl-propyl-phenyl-phenol (each isomer), Methyl-propyl-phenoxyphenol (each isomer), Methyl-propyl-isopropylphenyl-phenol (each isomer), Methyl-butyl-pentyl-phenol (each isomer), Methyl-butyl-hexyl-phenol (each isomer), Methyl-butyl-heptyl-phenol (each isomer), Methyl-butyl-octyl-phenol (each isomer), Methyl-butyl-mercapto-phenol (each isomer), Methyl-butyl-mercapto-phenol (each isomer), Methyl-butyl-dodecyl-phenol (each isomer), Methyl-butyl-phenyl-phenol (each isomer), Methyl-butyl-phenoxyphenol (each isomer), Methyl-butyl-cumyl-phenol (each isomer), Methyl-pentyl-hexyl-phenol (each isomer), Methyl-pentyl-heptyl-phenol (each isomer), Methyl-pentyl-octyl-phenol (each isomer), Methyl-pentyl-indolyl-phenol (each isomer), Methyl-pentyl-indolyl-phenol (each isomer), Methyl-pentyl-dodecyl-phenol (each isomer), Methyl-pentyl-phenyl-phenol (each isomer), Methyl-pentyl-benzene Oxyphenol (each isomer), Methyl-pentyl-cumyl-phenol (each isomer), Methyl-hexyl-heptyl-phenol (each isomer), Methyl-hexyl-octyl-phenol (each isomer), Methyl-hexyl-indolyl-phenol (each isomer), Methyl-hexyl-indolyl-phenol (each isomer), Methyl-hexyl-dodecyl-phenol (each isomer), Methyl-hexyl-phenyl-phenol (each isomer), Methyl-hexyl-phenoxyphenol (each isomer), Methyl-hexyl-cumyl-phenol (each isomer), Ethyl-propyl-butyl-phenol (each isomer), Ethyl-propyl-pentyl-phenol (each isomer), Ethyl-propyl-hexyl-phenol (each isomer), Ethyl-propyl-heptyl-phenol (each isomer), Ethyl-propyl-octyl-phenol (each isomer), Ethyl-propyl-indenyl-phenol (each isomer), Ethyl-propyl-indenyl-phenol (each isomer), Ethyl-propyl-dodecyl-phenol (each isomer), Ethyl-propyl-phenyl-phenol (each isomer), Ethyl-propyl-phenoxyphenol (each isomer), Ethyl-propyl-isopropylphenyl-phenol (each isomer), Ethyl-butyl-phenol (each isomer), Ethyl-butyl-pentyl-phenol (each isomer), Ethyl-butyl-hexyl-phenol (each isomer), Ethyl-butyl-heptyl-phenol (each isomer), Ethyl-butyl-octyl-phenol (each isomer), Ethyl-butyl-mercapto-phenol (each isomer), Ethyl-butyl-mercapto-phenol (each isomer), Ethyl-butyl-dodecyl-phenol (each isomer), Ethyl-butyl-phenyl-phenol (each isomer), Ethyl-butyl-phenoxyphenol (each isomer), Ethyl-butyl-cumyl-phenol (each isomer), Ethyl-pentyl-hexyl-phenol (each isomer), Ethyl-pentyl-heptyl-phenol (each isomer), Ethyl-pentyl-octyl-phenol (each isomer), Ethyl-pentyl-indolyl-phenol (each isomer), Ethyl-pentyl-indolyl-phenol (each isomer), Ethyl-pentyl-dodecyl-phenol (each isomer), Ethyl-pentyl-phenyl-phenol (each isomer), B Keto-pentyl-phenoxyphenol (each isomer), Ethyl-pentyl-cumyl-phenol (each isomer), Ethyl-hexyl-heptyl-phenol (each isomer), Ethyl-hexyl-octyl-phenol (each isomer), Ethyl-hexyl-indolyl-phenol (each isomer), Ethyl-hexyl-indolyl-phenol (each isomer), Ethyl-hexyl-dodecyl-phenol (each isomer), Ethyl-hexyl-phenyl-phenol (each isomer), Ethyl-hexyl-phenoxyphenol (each isomer), Ethyl-hexyl-cumyl-phenol (each isomer), Ethyl-heptyl-octyl-phenol (each isomer), Ethyl-heptyl-indenyl-phenol (each isomer), Ethyl-heptyl-indenyl-phenol (each isomer), Ethyl-heptyl-dodecyl-phenol (each isomer), Ethyl-heptyl-phenyl-phenol (each isomer), Ethyl-heptyl-phenoxyphenol (each isomer), Ethyl-heptyl-isopropylphenyl-phenol (each isomer), Ethyl-octyl-phenol (each isomer), Ethyl-octyl-indenyl-phenol (each isomer), Ethyl-octyl-indenyl-phenol (each isomer), Ethyl-octyl-dodecyl-phenol (each isomer), Ethyl-octyl-phenyl-phenol (each isomer), Ethyl-octyl-phenoxyphenol (each isomer), Ethyl-octyl-isopropylphenyl-phenol (each isomer), Ethyl-fluorenyl-fluorenyl-phenol (each isomer), Ethyl-indenyl-dodecyl-phenol (each isomer), Ethyl-indenyl-phenyl-phenol (each isomer), Ethyl-mercapto-phenoxyphenol (each isomer), Ethyl-indenyl-cumyl-phenol (each isomer), Ethyl-indenyl-dodecyl-phenol (each isomer), Ethyl-indenyl-phenyl-phenol (each isomer), Ethyl-mercapto-phenoxyphenol (each isomer), Ethyl-indenyl-cumyl-phenol (each isomer), Ethyl-dodecyl-phenyl-phenol (each isomer), Ethyl-dodecyl-phenoxyphenol (each isomer), Ethyl-dodecyl-cumyl-phenol (each isomer), Ethyl-phenyl-phenoxyphenol (each isomer), Ethyl-phenyl-cumyl-benzene Phenol (each isomer), Propyl-butyl-phenol (each isomer), Propyl-butyl-pentyl-phenol (each isomer), Propyl-butyl-hexyl-phenol (each isomer), Propyl-butyl-heptyl-phenol (each isomer), Propyl-butyl-octyl-phenol (each isomer), Propyl-butyl-mercapto-phenol (each isomer), Propyl-butyl-mercapto-phenol (each isomer), Propyl-butyl-dodecyl-phenol (each isomer), Propyl-butyl-phenyl-phenol (each isomer), Propyl-butyl-phenoxyphenol (each isomer), Propyl-butyl-cumyl-phenol (each isomer), Propyl-pentyl-phenol (each isomer), Propyl-pentyl-hexyl-phenol (each isomer), Propyl-pentyl-heptyl-phenol (each isomer), Propyl-pentyl-octyl-phenol (each isomer), Propyl-pentyl-indolyl-phenol (each isomer), Propyl-pentyl-indolyl-phenol (each isomer), Propyl-pentyl-dodecyl-phenol (each isomer), Propyl-pentyl-phenyl-phenol (each isomer), Propyl-pentyl-phenoxyphenol (each isomer), Propyl-pentyl-cumyl-phenol (each isomer), Propyl-hexyl-phenol (each isomer), Propyl-hexyl-heptyl-phenol (each isomer), Propyl-hexyl-octyl-phenol (each isomer), Propyl-hexyl-decyl-phenol (each isomer), Propyl-hexyl-decyl-phenol (each isomer), Propyl-hexyl-dodecyl-phenol (each isomer), Propyl-hexyl-phenyl-phenol (each isomer), Propyl-hexyl-phenoxyphenol (each isomer), Propyl-hexyl-cumyl-phenol (each isomer), Propyl-heptyl-octyl-phenol (each isomer), Propyl-heptyl-fluorenyl-phenol (each isomer), Propyl-heptyl-fluorenyl-phenol (each isomer), Propyl-heptyl-dodecyl-phenol (each isomer), Propyl-heptyl-phenyl-phenol (each isomer), Propyl-heptyl-phenoxyphenol (each isomer), Propyl-heptyl-cumyl-phenol (each isomer), Propyl-octyl-fluorenyl-phenol (each isomer), Propyl-octyl-fluorenyl- Phenol (each isomer), Propyl-octyl-dodecyl-phenol (each isomer), Propyl-octyl-phenyl-phenol (each isomer), Propyl-octyl-phenoxyphenol (each isomer), Propyl-octyl-isopropylphenyl-phenol (each isomer), Propyl-mercapto-mercapto-phenol (each isomer), Propyl-mercapto-dodecyl-phenol (each isomer), Propyl-mercapto-phenyl-phenol (each isomer), Propyl-mercapto-phenoxyphenol (each isomer), Propyl-mercapto-isopropylphenyl-phenol (each isomer), Propyl-mercapto-dodecyl-phenol (each isomer), Propyl-mercapto-phenyl-phenol (each isomer), Propyl-mercapto-phenoxyphenol (each isomer), Propyl-mercapto-isopropylphenyl-phenol (each isomer), Propyl-dodecyl-phenyl-phenol (each isomer), Propyl-dodecyl-phenoxyphenol (each isomer), Propyl-dodecyl-cumylphenol-phenol (each isomer), Methyl-phenol (each isomer), Ethyl-phenol (each isomer), Propyl-phenol (each isomer), Butyl-phenol (each isomer), Pentyl-phenol (each isomer), Hexyl-phenol (each isomer), Heptyl-phenol (each isomer), Octyl-phenol (each isomer), Mercapto-phenol (each isomer), Mercapto-phenol (each isomer), Dodecyl-phenol (each isomer), Phenyl-phenol (each isomer), Phenoxyphenol (each isomer), Propiyl-phenol (each isomer), Propyl-phenyl-phenoxyphenol (each isomer), Propyl-phenyl-isopropylphenyl-phenol (each isomer), Propyl-phenoxyisopropylphenyl-phenol (each isomer), Propyl-butyl-pentyl-phenol (each isomer), Propyl-butyl-hexyl-phenol (each isomer), Propyl-butyl-heptyl-phenol (each isomer), Propyl-butyl-octyl-phenol (each isomer), Propyl-butyl-mercapto-phenol (each isomer), Propyl-butyl-mercapto-phenol (each isomer), Propyl-butyl-dodecyl-phenol (each isomer), Propyl-butyl-phenyl-phenol (each isomer), Propyl-butyl-phenoxy Phenol (each isomer), Propyl-butyl-cumyl-phenol (each isomer), Propyl-pentyl-phenol (each isomer), Propyl-pentyl-hexyl-phenol (each isomer), Propyl-pentyl-heptyl-phenol (each isomer), Propyl-pentyl-octyl-phenol (each isomer), Propyl-pentyl-indolyl-phenol (each isomer), Propyl-pentyl-indolyl-phenol (each isomer), Propyl-pentyl-dodecyl-phenol (each isomer), Propyl-pentyl-phenyl-phenol (each isomer), Propyl-pentyl-phenoxyphenol (each isomer), Propyl-pentyl-cumyl-phenol (each isomer), Propyl-hexyl-heptyl-phenol (each isomer), Propyl-hexyl-octyl-phenol (each isomer), Propyl-hexyl-decyl-phenol (each isomer), Propyl-hexyl-decyl-phenol (each isomer), Propyl-hexyl-dodecyl-phenol (each isomer), Propyl-hexyl-phenyl-phenol (each isomer), Propyl-hexyl-phenoxyphenol (each isomer), Propyl-hexyl-cumyl-phenol (each isomer), Propyl-heptyl-octyl-phenol (each isomer), Propyl-heptyl-fluorenyl-phenol (each isomer), Propyl-heptyl-fluorenyl-phenol (each isomer), Propyl-heptyl-dodecyl-phenol (each isomer), Propyl-heptyl-phenyl-phenol (each isomer), Propyl-heptyl-phenoxyphenol (each isomer), Propyl-heptyl-cumyl-phenol (each isomer), Propyl-octyl-fluorenyl-phenol (each isomer), Propyl-octyl-fluorenyl-phenol (each isomer), Propyl-octyl-dodecyl-phenol (each isomer), Propyl-octyl-phenyl-phenol (each isomer), Propyl-octyl-phenoxyphenol (each isomer), Propyl-octyl-isopropylphenyl-phenol (each isomer), Propyl-mercapto-mercapto-phenol (each isomer), Propyl-mercapto-dodecyl-phenol (each isomer), Propyl-mercapto-phenyl-phenol (each isomer), Propyl-mercapto-phenoxyphenol (each isomer), Propyl-mercapto-isopropylphenyl-phenol (each isomer), Propyl-mercapto-dodecane Base-phenol (each isomer), Propyl-mercapto-phenyl-phenol (each isomer), Propyl-mercapto-phenoxyphenol (each isomer), Propyl-mercapto-isopropylphenyl-phenol (each isomer), Propyl-dodecyl-phenyl-phenol (each isomer), Propyl-dodecyl-phenoxyphenol (each isomer), Propiyl-phenol (each isomer), Propyl-phenyl-phenoxyphenol (each isomer), Propyl-phenyl-isopropylphenyl-phenol (each isomer), Butyl-pentyl-hexyl-phenol (each isomer), Butyl-pentyl-heptyl-phenol (each isomer), Butyl-pentyl-octyl-phenol (each isomer), Butyl-pentyl-indolyl-phenol (each isomer), Butyl-pentyl-indolyl-phenol (each isomer), Butyl-pentyl-dodecyl-phenol (each isomer), Butyl-pentyl-phenyl-phenol (each isomer), Butyl-pentyl-phenoxyphenol (each isomer), Butyl-pentyl-cumyl-phenol (each isomer), Butyl-hexyl-heptyl-phenol (each isomer), Butyl-hexyl-octyl-phenol (each isomer), Butyl-hexyl-indolyl-phenol (each isomer), Butyl-hexyl-indolyl-phenol (each isomer), Butyl-hexyl-dodecyl-phenol (each isomer), Butyl-hexyl-phenyl-phenol (each isomer), Butyl-hexyl-phenoxyphenol (each isomer), Butyl-hexyl-cumyl-phenol (each isomer), Butyl-heptyl-octyl-phenol (each isomer), Butyl-heptyl-indolyl-phenol (each isomer), Butyl-heptyl-indolyl-phenol (each isomer), Butyl-heptyl-dodecyl-phenol (each isomer), Butyl-heptyl-phenyl-phenol (each isomer), Butyl-heptyl-phenoxyphenol (each isomer), Butyl-heptyl-cumyl-phenol (each isomer), Butyl-octyl-fluorenyl-phenol (each isomer), Butyl-octyl-fluorenyl-phenol (each isomer), Butyl-octyl-dodecyl-phenol (each isomer), Butyl-octyl-phenyl-phenol (each isomer), Butyl-octyl-phenoxyphenol (each isomer), Butyl-octyl-isopropylphenyl-benzene Phenol (each isomer), Butyl-mercapto-fluorenyl-phenol (each isomer), Butyl-mercapto-dodecyl-phenol (each isomer), Butyl-mercapto-phenyl-phenol (each isomer), Butyl-mercapto-phenoxyphenol (each isomer), Butyl-mercapto-isopropylphenyl-phenol (each isomer), Butyl-mercapto-dodecyl-phenol (each isomer), Butyl-mercapto-phenyl-phenol (each isomer), Butyl-mercapto-phenoxyphenol (each isomer), Butyl-mercapto-isopropylphenyl-phenol (each isomer), Butyl-dodecyl-phenol (each isomer), Butyl-dodecyl-phenyl-phenol (each isomer), Butyl-dodecyl-phenoxyphenol (each isomer), Butyl-dodecyl-cumylphenol-phenol (each isomer), Butyl-phenyl-phenol (each isomer), Butyl-phenyl-phenoxyphenol (each isomer), Butyl-phenyl-isopropylphenyl-phenol (each isomer), Pentyl-hexyl-heptyl-phenol (each isomer), Pentyl-hexyl-octyl-phenol (each isomer), Pentyl-hexyl-indolyl-phenol (each isomer), Pentyl-hexyl-indolyl-phenol (each isomer), Pentyl-hexyl-dodecyl-phenol (each isomer), Pentyl-hexyl-phenyl-phenol (each isomer), Amyl-hexyl-phenoxyphenol (each isomer), Amyl-hexyl-cumyl-phenol (each isomer), Pentyl-heptyl-octyl-phenol (each isomer), Pentyl-heptyl-fluorenyl-phenol (each isomer), Pentyl-heptyl-fluorenyl-phenol (each isomer), Pentyl-heptyl-dodecyl-phenol (each isomer), Butyl-heptyl-phenyl-phenol (each isomer), Butyl-heptyl-phenoxyphenol (each isomer), Butyl-heptyl-cumyl-phenol (each isomer), Pentyl-octyl-decyl-phenol (each isomer), Pentyl-octyl-decyl-phenol (each isomer), Amyl-octyl-dodecyl-phenol (each isomer), Butyl-octyl-phenyl-phenol (each isomer), Amyl-octyl-phenoxyphenol (each isomer), Amyl-octyl-isopropylphenyl-phenol (each isomer), 戊基- Mercapto-mercapto-phenol (each isomer), Amyl-decyl-dodecyl-phenol (each isomer), Amyl-decyl-phenyl-phenol (each isomer), Amyl-decyl-phenoxyphenol (each isomer), Amyl-decyl-cumyl-phenol (each isomer), Amyl-decyl-dodecyl-phenol (each isomer), Amyl-decyl-phenyl-phenol (each isomer), Amyl-decyl-phenoxyphenol (each isomer), Amyl-decyl-cumyl-phenol (each isomer), Amyl-decyl-dodecyl-phenol (each isomer), Amyl-decyl-phenyl-phenol (each isomer), Amyl-decyl-phenoxyphenol (each isomer), Amyl-decyl-cumyl-phenol (each isomer), Pentyl-dodecyl-phenyl-phenol (each isomer), Amyl-dodecyl-phenoxyphenol (each isomer), Amyl-dodecyl-cumyl-phenol (each isomer), Butyl-phenyl-phenoxyphenol (each isomer), Butyl-phenyl-cumylphenol-phenol (each isomer), Hexyl-heptyl-octyl-phenol (each isomer), Hexyl-heptyl-fluorenyl-phenol (each isomer), Hexyl-heptyl-fluorenyl-phenol (each isomer), Hexyl-heptyl-dodecyl-phenol (each isomer), Hexyl-heptyl-phenyl-phenol (each isomer), Hexyl-heptyl-phenoxyphenol (each isomer), Hexyl-heptyl-isopropylphenyl-phenol (each isomer), Hexyl-octyl-fluorenyl-phenol (each isomer), Hexyl-octyl-fluorenyl-phenol (each isomer), Hexyl-octyl-dodecyl-phenol (each isomer), Hexyl-octyl-phenyl-phenol (each isomer), Hexyl-octyl-phenoxyphenol (each isomer), Hexyl-octyl-isopropylphenyl-phenol (each isomer), Hexyl-indenyl-fluorenyl-phenol (each isomer), Hexyl-fluorenyl-dodecyl-phenol (each isomer), Hexyl-fluorenyl-phenyl-phenol (each isomer), Hexyl-fluorenyl-phenoxyhexyl-fluorenyl-dodecyl-phenol (each isomer), Hexyl-fluorenyl-phenyl-phenol (each isomer), Hexyl-fluorenyl-phenoxyphenol (isomeric Matter) Hexyl-indenyl-cumyl-phenol (each isomer), Hexyl-dodecyl-phenyl-phenol (each isomer), Hexyl-dodecyl-phenoxyphenol (each isomer), Hexyl-dodecyl-cumylphenol-phenol (each isomer), Hexyl-phenyl-phenoxyphenol (each isomer), Hexyl-phenyl-isopropylphenyl-phenol (each isomer), Heptyl-octyl-fluorenyl-phenol (each isomer), Heptyl-octyl-fluorenyl-phenol (each isomer), Heptyl-octyl-dodecyl-phenol (each isomer), Heptyl-octyl-phenyl-phenol (each isomer), Heptyl-octyl-phenoxyphenol (each isomer), Heptyl-octyl-isopropylphenyl-phenol (each isomer), Heptyl-fluorenyl-fluorenyl-phenol (each isomer), Heptyl-fluorenyl-dodecyl-phenol (each isomer), Heptyl-fluorenyl-phenyl-phenol (each isomer), Heptyl-fluorenyl-phenoxyphenol (each isomer), Heptyl-fluorenyl-cumyl-phenol (each isomer), Heptyl-fluorenyl-dodecyl-phenol (each isomer), Heptyl-fluorenyl-phenyl-phenol (each isomer), Heptyl-fluorenyl-phenoxyphenol (each isomer), Heptyl-fluorenyl-cumyl-phenol (each isomer), Heptyl-dodecyl-phenyl-phenol (each isomer), Heptyl-dodecyl-phenoxyphenol (each isomer), Heptyl-dodecyl-cumyl-phenol (each isomer), Heptyl-phenyl-phenoxyphenol (each isomer), Heptyl-phenyl-isopropylphenyl-phenol (each isomer), Octyl-fluorenyl-fluorenyl-phenol (each isomer), Octyl-decyl-dodecyl-phenol (each isomer), Octyl-fluorenyl-phenyl-phenol (each isomer), Octyl-nonyl-phenoxyphenol (each isomer), Octyl-decyl-isopropylphenyl-phenol (each isomer), Octyl-decyl-dodecyl-phenol (each isomer), Octyl-fluorenyl-phenyl-phenol (each isomer), Octyl-nonyl-phenoxyphenol (each isomer), Octyl-decyl-isopropylphenyl-phenol (each isomer), Octyl-dodecyl-phenyl-phenol (each isomer), Octyl-dodecane Base-phenoxyphenol (each isomer), Octyl-dodecyl-cumyl-phenol (each isomer), Octyl-dodecyl-phenyl-phenol (each isomer), Octyl-dodecyl-phenoxyphenol (each isomer), Octyl-dodecyl-cumyl-phenol (each isomer), Octyl-phenyl-phenoxyphenol (each isomer), Octyl-phenyl-isopropylphenyl-phenol (each isomer), Mercapto-mercapto-dodecyl-phenol (isomers), Mercapto-mercapto-phenyl-phenol (each isomer), Mercapto-mercapto-phenoxyphenol (each isomer), Mercapto-mercapto-isopropylphenyl-phenol (each isomer), Mercapto-dodecyl-phenyl-phenol (each isomer), Mercapto-dodecyl-phenoxyphenol (each isomer), Mercapto-dodecyl-cumylphenol-phenol (each isomer), Mercapto-phenyl-phenoxyphenol (each isomer), Mercapto-phenyl-isopropylphenyl-phenol (each isomer), Mercapto-dodecyl-phenyl-phenol (each isomer), Mercapto-dodecyl-phenoxyphenol (each isomer), Mercapto-dodecyl-cumylphenol-phenol (each isomer), Mercapto-phenyl-phenoxyphenol (each isomer), Mercapto-phenyl-isopropylphenyl-phenol (each isomer), Dodecyl-phenyl-phenoxyphenol (each isomer), Dodecyl-phenyl-cumylphenyl-phenol (each isomer), Phenyl-phenoxyisopropylphenyl-phenol (each isomer) and the like. Among these organic acids, Considering the effect of the cleaning solvent remaining after the cleaning operation of the thermal decomposition reactor, More preferred is an aromatic hydroxy compound, Further preferably, the aromatic hydroxy compound used in the reaction with the diaryl carbonate and the amine compound is the same compound.

Further, when an aromatic hydroxy compound is used as the acid for cleaning, the standard boiling point of the aromatic hydroxy compound is preferably from the thermal decomposition of the above-mentioned aryl carboxylic acid aryl ester from the viewpoint of the cleaning effect. a compound of an isocyanate formed by the reaction, or a heat of the aryl carbamate The standard boiling point of the aromatic hydroxy compound formed by the decomposition reaction has a difference in boiling point of 10 ° C or more.

As a method of washing the thermal decomposition reactor by using the above-described cleaning solvent, a method of washing the thermal decomposition reactor by introducing a cleaning solvent from an upper portion of the thermal decomposition reactor may be used; and a cleaning solvent is introduced to the bottom of the thermal decomposition reactor to make the Various methods such as a method in which the cleaning solvent is boiled upward in the thermal decomposition reactor to clean the inside.

This cleaning operation is not required to be carried out every time the thermal decomposition reaction is carried out, and can be arbitrarily determined depending on the compound to be used, the operation speed, etc., and it is preferably carried out once every one hour to 20,000 hours, preferably at an operation time. The operation time is once every one day to one year, and it is better that the operation time is performed once every one month to one year. The thermal decomposition reactor may be provided with a line for introducing a cleaning solvent in the thermal decomposition reactor.

Further, when the thermal decomposition reaction of the aryl carbamate is carried out for the purpose of washing the thermal decomposition reactor, the cleaning solvent may be allowed to coexist under the conditions of the thermal decomposition reaction. It is different from the inert solvent of the prior art (for example, see U.S. Patent No. 4,081,472). For example, according to this patent document, an inert solvent means a compound which does not react with an isocyanate formed by thermal decomposition of a urethane, and, for example, the literature (Journal of the American Chemical Society, Vol. 64, 2229, 1942) describes the reaction of an aromatic hydroxy compound with phenyl isocyanate to form a urethane, and the aromatic hydroxy compound can be reacted with an isocyanate. The aromatic hydroxy compound can be added to the thermal decomposition reactor when the reaction mixture obtained by reacting the diaryl carbonate with the amine compound is transported to the thermal decomposition reactor. The mixture is supplied to the thermal decomposition reactor in a mixed manner, or may be supplied separately from the line to which the reaction mixture is supplied, and a line for supplying the aromatic hydroxy compound may be provided.

The isocyanate obtained by the production method of the present embodiment can be preferably used as a raw material for producing a polyurethane foam, a coating material, an adhesive, or the like. According to the production method of the present embodiment, the isocyanate can be produced with good yield without using highly toxic phosgene. Therefore, the present invention is extremely important in the industry.

[Examples]

Hereinafter, the present invention will be specifically described based on examples, but the scope of the present invention is not limited to the examples.

<Analysis method>

1) NMR analysis method

Device: JNM-A400 FT-NMR system manufactured by Japan Electronics Co., Ltd.

(1) Preparation of ¹ H and ¹³ C-NMR analysis samples

About 0.3 g of the sample solution was weighed, and about 0.7 g of deuterated chloroform (manufactured by Aldrich Co., Ltd., 99.8%) and 0.05 g of tetramethyltin as an internal standard substance (manufactured by Wako Pure Chemical Industries, Ltd., Japan) were added to the solution. And light level), uniformly mixed, and the resulting solution was analyzed as a sample by NMR.

(2) Quantitative analysis

A quantitative analysis of the analytical sample solution was carried out based on a calibration curve prepared by performing analysis on each of the reference materials.

2) Liquid chromatography method

Device: LC-10AT system manufactured by Shimadzu Corporation, Japan Pipe column: Japan, Tosoh company's Silica-60 column 2 series connection connection development solvent: hexane / tetrahydrofuran = 80 / 20 (volume ratio) mixture solvent flow rate: 2 mL / min column temperature: 35 ° C Detector: RI (refractive index meter)

(1) Analysis of samples by liquid chromatography

Approximately 0.1 g of the sample was weighed, and about 1 g of tetrahydrofuran (manufactured by Wako Pure Chemical Industries, Ltd., Japan) and about 0.02 g of bisphenol A as an internal standard substance (manufactured by Wako Pure Chemical Industries, Ltd., Japan) were added thereto. The mixture was uniformly mixed, and the resulting solution was used as a sample for liquid chromatography analysis.

(2) Quantitative analysis

A quantitative analysis of the analytical sample solution was carried out based on a calibration curve prepared by performing analysis on each of the reference materials.

3) Gas chromatography analysis method

Device: GC-2010 column manufactured by Shimadzu Corporation, Japan: DB-1, manufactured by Agilent Technologies, USA, has a length of 30 m, an inner diameter of 0.250 mm, and a film thickness of 1.00 μm. Column temperature: 5 at 50 °C After a minute, the temperature was raised to 200 ° C at a temperature increase rate of 10 ° C / min for 5 minutes at 200 ° C, and then raised to 300 ° C at a temperature increase rate of 10 ° C / min. Detector: FID

(1) Analysis of samples by gas chromatography

Weigh about 0.05 g of sample and add about 1 g of acetone to it (Japan, and light) Manufactured by Pure Chemical Industries, Ltd., dehydrated) and about 0.02 g of toluene (manufactured by Wako Pure Chemical Industries, Ltd., Japan), uniformly mixed, and the obtained solution was sampled by gas chromatography.

(2) Quantitative analysis

A quantitative analysis of the analytical sample solution was carried out based on a calibration curve prepared by performing analysis on each of the reference materials.

4) Inductively coupled plasma mass analysis method

Device: Japan, manufactured by Seiko Instruments, SPQ-8000

(1) Inductively coupled plasma quality analysis samples

After about 0.15 g of the sample was ashed with dilute sulfuric acid, it was dissolved in dilute nitric acid.

(2) Quantitative analysis

A quantitative analysis of the analytical sample solution was carried out based on a calibration curve prepared by performing analysis on each of the reference materials.

[Reference Example 1] Production of diphenyl carbonate

. Step (I-1): Manufacture of dialkyl tin catalyst

Into an eggplant type flask having a volume of 3000 mL, 692 g (2.78 mol) of di-n-butyltin oxide and 2000 g (27 mol) of 1-butanol (manufactured by Wako Pure Chemical Industries, Ltd., Japan) were added. A flask to which the mixture was added in the form of a white slurry was attached to an evaporator which was connected to an oil bath with a temperature regulator and a vacuum pump and a vacuum controller. The vent valve outlet of the evaporator is connected to a line that flows nitrogen at atmospheric pressure. Close the vent valve of the evaporator, and after decompressing the system, slowly open the vent valve to allow nitrogen to flow into the system and return to normal pressure. The oil bath temperature was set to 126 ° C, and the flask was immersed in the oil bath to start the rotation of the evaporator. After the aeration valve of the evaporator was opened and stirred under normal pressure for about 30 minutes and heated, the mixture was boiled to start distillation of the low boiling component. After maintaining this state for 8 hours, the vent valve was closed, the inside of the system was gradually decompressed, and the residual low boiling component was distilled in a state where the system pressure was 76 to 54 kPa. After the low boiling component did not occur, the flask was taken out of the oil bath. The reaction solution is a transparent liquid. Thereafter, the flask was taken out of the oil bath and the vent valve was slowly opened to restore the pressure in the system to normal pressure. 952 g of the reaction liquid was obtained in the flask. According to the analysis results of ¹¹⁹ Sn, ¹ H, and ¹³ C-NMR, it was confirmed that the product 1,1,3,3-tetra-n-butyl-1,3 was obtained in a yield of 99% based on di-n-butyltin oxide. - bis(n-butoxy)-distannoxane. The same operation was repeated 12 times to obtain a total of 11480 g of 1,1,3,3-tetra-n-butyl-1,3-di(n-butoxy)-distannoxane.

. Step (I-2): Production of dibutyl carbonate

In a continuous manufacturing apparatus as shown in Fig. 1, a carbonate is produced. 1,1,3,3-tetra-n-butyl-1,3-di(n-butoxy)-distannoxane produced by the step (I-1) from line 4 at 4201 g/hr, and The 1-butanol purified in the distillation column 101 was supplied to the filled mellapak 750Y (manufactured by Sulzer Chemtech Ltd., Switzerland) from line 2 at 24517 g/hr, and the inner diameter was 151 mm, and the effective length was 5040. In the tower type reactor 102 of mm. The reactor was conditioned by a heater and reboiler 112 to bring the liquid temperature to 160 ° C and adjusted with a pressure regulating valve to bring the pressure to about 150 kPa-G. The residence time in the reactor was about 10 minutes. The aqueous 1-butanol was fed from the upper part of the reactor via line 6 at 24,715 g/hr and the 1-butanol was fed via line 1 at 824 g/hr to the filled Metal Gauze CY (Sulzer Chemtech Ltd., Switzerland). The distillation column 101 of the reboiler 111 and the condenser 121 is manufactured by the company, and is subjected to distillation purification. The fraction containing the high-concentration water is condensed by the condenser 121 in the upper portion of the distillation column 101, and is recovered by the line 3. Purified 1-butanol is delivered via line 2 below the distillation column 101. From the lower part of the column reactor 102, it is obtained to contain di-n-butyltin-di-n-butyl oxide and 1,1,3,3-tetra-n-butyl-1,3-di(n-butoxy)-distannoxane. The alkyl tin alkoxide catalyst composition is supplied to the thin film evaporation apparatus 103 via line 5 (manufactured by Kobelco eco-solutions, Japan). 1-butanol is distilled off in the thin film evaporation apparatus 103, and returned to the column reactor 102 via the condenser 123, the line 8 and the line 4. The alkyltin alkoxide catalyst composition is delivered from the lower portion of the thin film evaporation device 103 via line 7, and dibutyltin dibutoxide is combined with 1,1,3,3-tetra-n-butyl-1,3-di(positive) The flow rate of the active ingredient of butoxy)-distannoxane was adjusted to about 4812 g/hr and supplied to the autoclave 104. Carbon dioxide was supplied to the autoclave at 973 g/hr via line 9, and the internal pressure of the autoclave was maintained at 4 MPa-G. The temperature in the autoclave was set to 120 ° C, and the residence time was adjusted to about 4 hours to carry out a reaction of carbon dioxide with an alkyl tin alkoxide catalyst composition to obtain a reaction liquid containing dibutyl carbonate. The reaction liquid is transported to the carbon removal tank 105 via the line 10 and the regulating valve to remove residual carbon dioxide, and the carbon dioxide is recovered by the line 11. Thereafter, the reaction liquid was transported via line 12 to a thin film evaporation apparatus 106 (manufactured by Kobelco eco-solutions, Japan) of about 140 ° C and about 1.4 kPa, and 1,1,3,3-tetra-n-butyl The flow rate of the base-1,3-bis(n-butoxy)-distannoxane is adjusted to be about 4,201 g/hr to obtain a fraction containing dibutyl carbonate, and on the other hand, the evaporation residue is passed through the line 13 and Line 4, the 1,1,3,3-tetra-n-butyl-1,3-di(n-butoxy)-distannoxane flow rate was adjusted to about 4,201 g/hr, and recycled to the column reactor 102. The fraction containing dibutyl carbonate was supplied to the filled Metal Gauze CY (manufactured by Sulzer Chemtech Ltd., Switzerland) via a condenser 126 and a line 14 at 830 g/hr, and was equipped with a reboiler 117 and a condenser. In the distillation column 107 of 127, after distillation purification, 99 wt% of dibutyl carbonate was obtained from line 15 at 814 g/hr. The alkyltin alkoxide catalyst composition of line 13 was analyzed by ¹¹⁹ Sn, ¹ H, ¹³ C-NMR, and the result contained 1,1,3,3-tetra-n-butyl-1,3-di(positive). Butoxy)-distannoxane does not contain di-n-butyltin-di-n-butyl oxide. After the above continuous operation was carried out for about 600 hours, the alkyltin alkoxide catalyst composition was supplied from the line 16 at 16 g/hr, and on the other hand, the line 17 was supplied in the step (I-1) at 16 g/hr. 1,1,3,3-tetra-n-butyl-1,3-di(n-butoxy)-distannoxane.

. Step (I-3): Production of aromatic carbonate

[Preparation of catalyst]

79 g of phenol and 32 g of lead monoxide were heated at 180 ° C for 10 hours, and the produced water was distilled off together with phenol. About 2.5 g of water was discharged in 10 hours. Thereafter, phenol was distilled off from the upper portion of the reactor to prepare a catalyst.

[Manufacture of aromatic carbonates]

Use the device shown in Figure 2.

To the middle of the continuous multi-stage distillation column 202 filled with Dixon packing (6 mm Φ) having an inner diameter of about 5 cm and a column length of 2 m, via the preheater 201, from the line 21 at about 270 g/hr, The liquid continuous feed comprises a mixture of dibutyl carbonate, phenol, and a catalyst prepared as described above in the step (I-2) (the weight ratio of dibutyl carbonate to phenol in the mixture is about 65/ 35, lead concentration The reaction was prepared by preparing about 1% by weight. The heat necessary for the reaction and distillation is supplied by circulating the liquid in the lower portion of the column via the line 23 and the reboiler 204. The liquid temperature at the bottom of the continuous multi-stage distillation column 202 is 238 ° C, the overhead pressure is about 250 kPa, and the reflux ratio is about 2. The gas distilled from the top of the continuous multi-stage distillation column 202 is discharged from the line 22, and continuously discharged to the storage tank 205 by the line 24 at about 67 g/hr via the condenser 203. From the bottom of the column, it is continuously discharged into the sump 206 via line 23 at about 204 g/hr.

The composition of the liquid discharged from line 24 is about 13% by weight of 1-butanol, about 65% by weight of phenol, and about 2% by weight of dibutyl carbonate. The liquid composition discharged to the storage tank 206 is about 11% by weight of phenol, about 60% by weight of dibutyl carbonate, about 26% by weight of butyl phenyl carbonate, about 1.6% by weight of diphenyl carbonate, and about lead concentration. It is 1% by weight.

Next, a device as shown in Fig. 3 is used.

To the middle of the continuous multi-stage distillation column 302 filled with Dixon packing (6 mm Φ) having an inner diameter of 5 cm and a column length of 2 m, via the preheater 301, from the line 31 at about 203 g/hr, The liquid continuous feed is discharged to the liquid in the sump 206. The heat necessary for the reaction and distillation is supplied by circulating the lower portion of the liquid through the line 33 and the reboiler 304. The liquid temperature at the bottom of the continuous multi-stage distillation column 302 is 240 ° C, the top pressure is about 27 kPa, and the reflux ratio is about 2. The gas distilled from the top of the continuous multi-stage distillation column 302 was condensed in the condenser 303 via line 32, and continuously discharged into the storage tank 305 by line 34 at about 165 g/hr. From the bottom of the column, it is continuously discharged into the sump 306 via line 33 at about 39 g/hr.

The composition of the liquid discharged from line 34 is that 1-butanol is about 500 ppm. The phenol is about 13% by weight, the dibutyl carbonate is about 85% by weight, and the butyl phenyl carbonate is about 2% by weight. The composition of the liquid discharged to the storage tank 306 was about 0.3% by weight of dibutyl carbonate, about 32% by weight of butyl phenyl carbonate, about 61% by weight of diphenyl carbonate, and about 7% by weight of lead.

[Reuse of alcohol]

Alcohol reuse was carried out using a device as shown in FIG.

The continuous multi-stage distillation column 402 filled with Dixon packing (6 mm Φ) having an inner diameter of about 5 cm and a column length of 2 m is about 0.7 m from the lowermost portion of the column, and the line 41 is passed through the preheater 401. The liquid continuously discharged to the storage tank 205 in the above step was continuously fed at about 201 g/hr, and distillation separation was carried out. The heat necessary for the distillation separation is supplied by circulating the lower portion of the liquid through the line 43 and the reboiler 404. The liquid temperature at the bottom of the continuous multi-stage distillation column 402 was 145 ° C, the overhead pressure was about 13 kPa, and the reflux ratio was about 0.3. The gas distilled from the continuous multi-stage distillation column 402 is condensed in the condenser 403 via line 42, and discharged to the storage tank 405 by line 44 at about 68 g/hr. From the bottom of the column via line 43, it is continuously discharged to the sump 406 at about 133 g/hr.

The composition of the liquid discharged from line 44 is about 99% by weight of 1-butanol and about 100 ppm of phenol. The composition of the liquid discharged to the storage tank 406 is about 2% by weight of dibutyl carbonate and about 98% by weight of phenol.

[Purification of diaryl carbonate]

Purification of the diaryl carbonate was carried out using the apparatus shown in Figures 5 and 6.

To the middle of a continuous multi-stage distillation column 502 filled with Dixon packing (6 mm Φ) having an inner diameter of about 5 cm and a column length of 2 m, from line 51 via preheater 501, at about 195 g/hr. The feed is discharged to the liquid in the sump 306. Distillation The heat necessary for the separation is supplied by circulating the lower portion of the liquid through the line 53 and the reboiler 504. The liquid temperature at the bottom of the continuous multi-stage distillation column 502 is 210 ° C, the pressure at the top of the column is about 1.5 kPa, and the reflux ratio is about 1. The gas distilled from the top of the continuous multi-stage distillation column 502 is condensed in the condenser 503 via line 52, and continuously discharged from the line 54. From the bottom of the column, it is discharged to the sump 506 via line 53 at about 14 g/hr.

The composition of the liquid discharged from line 54 is about 0.3% by weight of dibutyl carbonate, about 34% by weight of butyl phenyl carbonate, and about 66% by weight of diphenyl carbonate.

The middle portion of the continuous multi-stage distillation column 602 filled with Dixon packing (6 mm Φ) having an inner diameter of about 5 cm and a column length of 2 m was continuously continuous by the line 61 via the preheater 601 at about 181 g/hr. The liquid discharged by line 54 is fed. The heat necessary for the distillation separation is supplied by circulating the lower portion of the liquid through the line 63 and the reboiler 604. The liquid temperature at the bottom of the continuous multi-stage distillation column 602 is 232 ° C, the pressure at the top of the column is about 15 kPa, and the reflux ratio is about 2. The gas distilled from the top of the continuous multi-stage distillation column 602 is condensed in the condenser 603 via line 62 and continuously discharged by line 64. From the bottom of the column, it is discharged to the sump 606 via line 63 at about 119 g/hr.

The composition of the liquid discharged from line 64 is about 0.6% by weight of dibutyl carbonate, about 99% by weight of butyl phenyl carbonate, and about 0.4% by weight of diphenyl carbonate. The composition of the liquid discharged to the storage tank 606 was 0.1% by weight of butyl phenyl carbonate and about 99.9% by weight of diphenyl carbonate. The diphenyl carbonate contained 22 ppm of iron as a metal component.

[Example 1]

. Step (1-1): Manufacture of N,N' -hexanediyl-bis-carbamic acid diphenyl ester

The reaction was carried out using the apparatus shown in FIG.

1350 g (6.3 mol) of diphenyl carbonate of Reference Example 1 was supplied from the storage tank 701 via the line 71 to the SUS reaction vessel 704 with the inner volume of 5 L. The storage tank 702 supplied 987 g (10.5 mol) of phenol (manufactured by Aldrich Co., Ltd.) to the SUS reactor via a line 72. The temperature of the liquid in the reactor 704 was adjusted to about 50 ° C, and 244 g (2.1 mol) of hexamethylenediamine (manufactured by Aldrich Co., Ltd.) was supplied from the storage tank 703 via line 73 to the solution at about 200 g/hr. In reactor 704.

The solution after the reaction was analyzed by liquid chromatography, and as a result , N,N' -hexanediyl-bis-carbamic acid diphenyl ester was formed in a yield of 99.5%.

Line 74 is opened and the reaction liquid is conveyed via line 74 to storage tank 705.

. Step (1-2): Production of isocyanate by thermal decomposition of N,N' -hexanediyl-bis-carbamic acid diphenyl ester

The reaction was carried out using a device as shown in FIG.

A thin film distillation apparatus 801 (manufactured by Kobelco Eco-solutions Co., Ltd., Japan) having a heat transfer area of 0.1 m ² was heated to 220 ° C to have an internal pressure of about 13 kPa. The mixture recovered in the storage tank 705 in the step (1-1) was heated to 150 ° C, and supplied to the upper portion of the thin film distillation apparatus 801 via line 81 at about 800 g/hr. From the bottom of the thin film distillation apparatus 801, the liquid phase component is discharged from the line 83, and is circulated to the upper portion of the thin film distillation apparatus 801 via the line 84 and the line 81. The gas phase components are discharged from line 82.

The gas phase component discharged from the thin film distillation apparatus 801 via line 82 is continuously fed to a middle portion of a continuous multi-stage distillation column 802 filled with a Dixon packing (6 mm Φ) having an inner diameter of about 5 cm and a column length of 2 m. Distillation separation of the gas phase component is carried out. The heat necessary for the distillation separation is supplied by circulating the lower portion of the liquid through the line 86 and the reboiler 804. The liquid temperature at the bottom of the continuous multi-stage distillation column 802 is 150 ° C and the overhead pressure is about 15 kPa. The gas distilled from the top of the continuous multi-stage distillation column 802 is condensed in the condenser 803 via the line 85, and is continuously discharged by the line 87. From the line 89 of the continuous multi-stage distillation column 802 below the line 82, the liquid phase components are discharged.

The liquid phase component discharged from the line 89 is continuously fed to the middle portion of the continuous multi-stage distillation column 805 filled with Dixon packing (6 mm Φ) and having an inner diameter of about 5 cm and a column length of 2 m, and the liquid phase is carried out. Distillation separation of the ingredients. The heat necessary for the distillation separation is supplied by circulating the lower portion of the liquid through the line 91 and the reboiler 807. The liquid temperature at the bottom of the continuous multi-stage distillation column 805 is 150 ° C, and the pressure at the top of the column is about 1.5 kPa. The gas distilled from the top of the continuous multi-stage distillation column 805 is condensed in the condenser 806 via the line 90, and continuously discharged to the storage tank 809 via the line 92. The steady state discharge is about 104 g/hr.

In a steady state, the liquid phase component is discharged from line 94 to storage tank 810 at about 140 g/hr. The liquid phase component contained about 97% by weight of diphenyl carbonate.

The liquid system discharged from line 92 contained a solution of about 99.8% by weight of hexamethylene diisocyanate. The yield based on hexamethylenediamine was 95.3%.

. Step (1-3): Reuse of diaryl carbonate

The reuse of the diaryl carbonate was carried out using the apparatus shown in Figs.

The liquid discharged from line 94 in step (1-2) is continuously fed from line 95 via preheater 901 at about 195 g/hr to an inner diameter filled with a Dixon packing (6 mm Φ). The middle section of a continuous multi-stage distillation column 902 having a length of 5 cm and a length of 2 m. The heat necessary for the distillation separation is supplied by circulating the lower portion of the liquid through the line 97 and the reboiler 904. The liquid temperature at the bottom of the continuous multi-stage distillation column 902 is 210 ° C, the pressure at the top of the column is about 1.5 kPa, and the reflux ratio is about 1. The gas distilled from the top of the continuous multi-stage distillation column 902 is condensed in the condenser 903 via line 96, and continuously discharged from the line 99. From the bottom of the column, it is discharged to the sump 906 via line 97 at about 14 g/hr.

The middle section of a continuous multi-stage distillation column 1002 filled with a Dixon packing (6 mm Φ) having an inner diameter of about 5 cm and a column length of 2 m is continuously continuous by the line A1 via the preheater 1001 at about 181 g/hr. Feed the liquid discharged by line 99. The heat necessary for the distillation separation is supplied by circulating the lower portion of the liquid through the line A3 and the reboiler 1004. The liquid temperature at the bottom of the continuous multi-stage distillation column 1002 is 232 ° C, the pressure at the top of the column is about 15 kPa, and the reflux ratio is about 2. The gas distilled from the top of the continuous multi-stage distillation column 1002 is condensed in the condenser 1003 via the line A2, and continuously discharged from the line A4. From the bottom of the column, it was discharged to the storage tank 1006 via line A3 at about 119 g/hr. The liquid discharged to the storage tank 1006 contained about 99.9% by weight of diphenyl carbonate.

. Step (1-4): Reuse of phenol

The reuse of phenol was carried out using a device as shown in FIG.

The liquid discharged from line 87 in step (1-2) is continuously fed from line B1 via preheater 1101 at about 200 g/hr to an inner diameter filled with a Dixon packing (6 mm Φ). Continuous multi-stage distillation column 1102 with a length of 5 cm and a length of 2 m Mid section. The heat necessary for the distillation separation is supplied by circulating the lower portion of the liquid through the line B3 and the reboiler 1104. The liquid temperature at the bottom of the continuous multi-stage distillation column 1102 is 230 ° C, the pressure at the top of the column is atmospheric pressure, and the reflux ratio is about 1. The gas distilled from the top of the continuous multi-stage distillation column 1102 is condensed in the condenser 1103 via the line B2, and continuously discharged to the storage tank 1105 by the line A4. The liquid discharged to the storage tank 1105 contained about 99.9% by weight of phenol. The continuous operation was carried out for 10 days, and no deposit was observed in the wall area of the thin film distillation apparatus 801. Further, after 300 days of continuous operation, it was found that deposits were deposited in the wall area of the thin film distillation apparatus 801.

[Embodiment 2]

. Step (2-1): Production of phenyl 3-(phenoxycarbonylamino-methyl)-3,5,5-trimethylcyclohexylaminocarboxylate

The reaction was carried out using the apparatus shown in FIG.

In the state where the line 74 was closed, 1992 g (9.3 mol) of diphenyl carbonate of Reference Example 1 was supplied from the storage tank 701 via the line 71 to a SUS reaction vessel 704 with a baffle having an internal volume of 5 L. 1311 g (14.0 mol) of phenol was supplied from the storage tank 702 via line 72 to the SUS reactor. The temperature of the liquid in the reactor 704 was adjusted to about 50 ° C, and 528 g (3.1 mol) of 3-aminomethyl-3,5,5-trimethyl ring was transferred from the storage tank 703 via line 73 at about 250 g/hr. Hexylamine (manufactured by Aldrich, USA) is supplied to the reactor 704.

The solution after the reaction was analyzed by liquid chromatography to give 3-(phenoxycarbonylamino-methyl)-3,5,5-trimethylcyclohexylaminocarboxylic acid benzene in a yield of 99.3%. ester.

Line 74 is opened and the reaction liquid is transported via line 74 to storage tank 705.

. Step (2-2): Production of isocyanate by thermal decomposition of phenyl 3-(phenoxycarbonylamino-methyl)-3,5,5-trimethylcyclohexylaminocarboxylate

The reaction was carried out using a device as shown in FIG.

A thin film distillation apparatus 801 (manufactured by Kobelco Eco-solutions Co., Ltd., Japan) having a heat transfer area of 0.1 m ² was heated to 220 ° C to have an internal pressure of about 13 kPa. The mixture recovered in the storage tank 705 in the step (2-1) was heated to 150 ° C, and supplied to the upper portion of the thin film distillation apparatus 801 via line 81 at about 780 g/hr. From the bottom of the thin film distillation apparatus 801, the liquid phase component is discharged from the line 83, and is circulated to the upper portion of the thin film distillation apparatus 801 via the line 84 and the line 81. The gas phase components are discharged from line 82.

The gas phase component discharged from the thin film distillation apparatus 801 via line 82 is continuously fed to a middle portion of a continuous multi-stage distillation column 802 filled with a Dixon packing (6 mm Φ) having an inner diameter of about 5 cm and a column length of 2 m. Distillation separation of the gas phase component is carried out. The heat necessary for the distillation separation is supplied by circulating the lower portion of the liquid through the line 86 and the reboiler 804. The liquid temperature at the bottom of the continuous multi-stage distillation column 802 is 150 ° C, and the pressure at the top of the column is about 15 kPa. The gas distilled from the top of the continuous multi-stage distillation column 802 is condensed in the condenser 803 via line 85, and is continuously discharged by line 87. The liquid phase component is discharged from line 89 of the continuous multi-stage distillation column 802 below the line 82.

The liquid phase component discharged from the line 89 is continuously fed to the middle of the continuous multi-stage distillation column 805 filled with Dixon packing (6 mm Φ) and having an inner diameter of about 5 cm and a column length of 2 m, and the liquid phase is carried out. Distillation separation of the ingredients. The heat necessary for the distillation separation is to circulate the liquid in the lower part of the column via line 91 and reboiler 807. And supply. The liquid temperature at the bottom of the continuous multi-stage distillation column 805 is 150 ° C, and the pressure at the top of the column is about 1.3 kPa. The gas distilled from the top of continuous multistage distillation column 805 is condensed in condenser 806 via line 90 and continuously discharged to storage tank 809 via line 92 at about 134 g/hr.

The liquid system discharged from line 92 contained a solution of about 99.8% by weight of isophorone diisocyanate. The yield based on 3-aminomethyl-3,5,5-trimethylcyclohexylamine was 95.0%. The continuous operation was carried out for 10 days, and no deposit was observed in the wall area of the thin film distillation apparatus 801.

[Example 3]

. Step (3-1): Production of diphenyl-4,4'-methylene-dicyclohexylcarbamate

To the diphenyl carbonate of Reference Example 1, iron (II) acetonitrile was added to prepare diphenyl carbonate containing 2.3% of iron as a metal atom.

The reaction was carried out using the apparatus shown in FIG.

1577 g (7.4 mol) of diphenyl carbonate was supplied from the storage tank 701 via line 71 to a SUS reaction vessel 704 with a baffle of 5 L, which was 1189 g (12.7). Mol) phenol is supplied from the storage tank 702 to the SUS reactor via line 72. The temperature of the liquid in the reactor 704 was adjusted to about 50 ° C, and 484 g (2.3 mol) of 4,4'-methylenebis(cyclohexylamine) was charged from the storage tank 703 via line 73 at about 250 g/hr. The Aldrich Company, USA, is supplied to the reactor 704.

The solution after the reaction was analyzed by liquid chromatography to give diphenyl-4,4'-methylene-dicyclohexylcarbamate in a yield of 99.1%.

Line 74 is opened and the reaction liquid is transported via line 74 to storage tank 705.

. Step (3-2): using diphenyl-4,4'-methylene-dicyclohexylcarbamate Isocyanate produced by thermal decomposition

The reaction was carried out using a device as shown in FIG.

A thin film distillation apparatus 1201 (manufactured by Kobelco Eco-solutions Co., Ltd., Japan) having a heat transfer area of 0.1 m ² was heated to 250 ° C so that the internal pressure was about 1.3 kPa. The mixture recovered from the storage tank 705 in the step (3-1) was heated to 170 ° C, and supplied to the upper portion of the thin film distillation apparatus 1201 at about 650 g/hr via the line C1. From the bottom of the thin film distillation apparatus 1201, the liquid phase component is discharged from the line C3, and is circulated to the upper portion of the thin film distillation apparatus 1201 via the line C4 and the line C1. The gas phase component is discharged from line C2.

The gas phase component discharged from the thin film distillation apparatus 1201 via the line C2 is continuously fed to a middle portion of a continuous multi-stage distillation column 1202 filled with a Dixon packing (6 mm Φ) having an inner diameter of about 5 cm and a column length of 2 m. Distillation separation of the gas phase component is carried out. The heat necessary for the distillation separation is supplied by circulating the lower portion of the liquid through the line C6 and the reboiler 1204. The liquid temperature at the bottom of the continuous multi-stage distillation column 1201 is 210 ° C, and the pressure at the top of the column is atmospheric pressure. The gas distilled from the top of the continuous multi-stage distillation column 1201 is condensed in the condenser 1203 via the line C5, and continuously discharged from the line C7. The liquid phase component is discharged from line C8.

The liquid phase component discharged from the line C8 is continuously fed to the middle section of the continuous multi-stage distillation column 1205 filled with Dixon packing (6 mm Φ) and having an inner diameter of about 5 cm and a column length of 2 m, and the liquid phase is carried out. Distillation separation of the ingredients. The heat necessary for the distillation separation is supplied by circulating the lower portion of the liquid through the line C11 and the reboiler 1207. The liquid temperature at the bottom of the continuous multi-stage distillation column 1205 is 210 ° C, and the pressure at the top of the column is about 2.5 kPa. Self-continuous multi-stage distillation column 1205 The gas distilled from the top of the column is condensed in the condenser 1206 via the line C10, and continuously discharged through the line C12. The liquid phase component is discharged from line C14.

The liquid phase component discharged from the line C14 is continuously fed to the middle portion of the continuous multi-stage distillation column 1208 filled with Dixon packing (6 mm Φ) and having an inner diameter of about 5 cm and a column length of 2 m, and the liquid phase is carried out. Distillation separation of the ingredients. The heat necessary for the distillation separation is supplied by circulating the lower portion of the liquid through the line C16 and the reboiler 1210. The liquid temperature at the bottom of the continuous multi-stage distillation column 1208 is 220 ° C, and the pressure at the top of the column is about 0.5 kPa. The gas distilled from the top of the continuous multi-stage distillation column 1205 was condensed in the condenser 1209 via line C15, and continuously discharged at about 113 g/hr via line C17. The liquid discharged from C17 contained about 99.9% by weight of 4,4'-methylene-bis(cyclohexyl isocyanate). The yield relative to 4,4'-methylenebis(cyclohexylamine) was 93.2%. The continuous operation was carried out for 10 days, and no deposit was observed in the wall area of the thin film distillation apparatus 1202.

[Example 4]

. Step (4-1): Production of diphenyl-4,4'-methylene-dicyclohexylcarbamate

In addition to supplying 1650 g (7.7 mol) of diphenyl carbonate of Reference Example 1, 1344 g (11.0 mol) of 2,6-dimethylphenol (manufactured by Aldrich, USA) in place of phenol, and 463 g (2.2 mol) of 4, The same procedure as in the step (3-1) of Example 3 was carried out, except for 4'-methylenebis(cyclohexylamine). The solution after the reaction was analyzed by liquid chromatography to give diphenyl-4,4'-methylene-dicyclohexylcarbamate in a yield of 99.3%.

. Step (4-2): Production of isocyanate by thermal decomposition of diphenyl-4,4'-methylene-dicyclohexylaminocarboxylic acid

The same procedure as in the step (3-2) of Example 3 was carried out except that the mixture obtained in the step (4-1) was used instead of the mixture obtained in the step (3-1), and the mixture was heated to 140 °C. A mixture of phenol and 2,6-dimethylphenol is discharged from C7. The liquid discharged from C17 contained about 99.9% by weight of 4,4'-methylene-bis(cyclohexyl isocyanate). The yield relative to 4,4'-methylenebis(cyclohexylamine) was 92.3%. The continuous operation was carried out for 10 days, and no deposit was observed in the wall area of the thin film distillation apparatus 1202.

[Example 5]

. Step (5-1): Production of N,N'-hexanediyl-bis-carbamic acid diphenyl ester

The procedure of Example 1 was carried out except that 1874 g (8.8 mol) of diphenyl carbonate of Reference Example 1, 1246 (13.3 mol) of phenol, and 291 g (2.5 mol) of hexamethylenediamine were supplied. The same method.

The solution after the reaction was analyzed by liquid chromatography, and as a result , N,N '-hexanediyl-bis-carbamic acid diphenyl ester was formed in a yield of 99.4%.

. Step (5-2): Production of isocyanate by thermal decomposition of N,N '-hexanediyl-bis-carbamic acid diphenyl ester

The mixture obtained in the step (1-1) was used in place of the mixture obtained in the step (1-1), and the mixture was heated to 190 ° C and supplied to the outside of the thin film distillation apparatus 801, and the procedure of Example 1 was carried out. -2) The same method. The liquid was continuously discharged to the sump 809 by line 92 at 76.5 g/hr. The liquid system discharged from line 92 contained a solution of about 99.8% by weight of hexamethylene diisocyanate. The yield based on hexamethylenediamine was 77.5%. The continuous operation was carried out for 10 days, and no deposit was observed in the wall area of the thin film distillation apparatus 801.

[Embodiment 6]

. Step (6-1): Manufacture of N,N' -hexanediyl-bis-carbamic acid diphenyl ester

The procedure of Example 1 was carried out except that 2056 g (9.6 mol) of diphenyl carbonate of Reference Example 1, 1504 g (16.0 mol) of phenol, and 372 g (3.2 mol) of hexamethylenediamine were supplied. 1) The same method.

The solution after the reaction was analyzed by liquid chromatography, and as a result , N,N' -hexanediyl-bis-carbamic acid diphenyl ester was formed in a yield of 99.4%.

. Step (6-2): Production of isocyanate by thermal decomposition of N,N '-hexanediyl-bis-carbamic acid diphenyl ester

The reaction was carried out using a device as shown in FIG.

The thin film distillation apparatus 801 having a heat transfer area of 0.1 m ² was heated to 220 ° C so that the internal pressure was about 0.13 kPa. The mixture recovered in the storage tank 705 in the step (6-1) was heated to 100 ° C, and supplied to the upper portion of the thin film distillation apparatus 801 via line 81 at about 800 g/hr. The gas phase component is discharged through the line 82 by the thin film distillation apparatus 801. From the line 83 provided at the bottom of the thin film distillation apparatus 801, almost no liquid phase component was recovered.

The gas phase component discharged from the thin film distillation apparatus 801 via line 82 is continuously fed to the middle section of the continuous multi-stage distillation column 802 filled with Dixon packing (6 mm Φ) and having an inner diameter of about 5 cm and a column length of 2 m. Distillation separation of the gas phase component is carried out. The heat necessary for the distillation separation is supplied by circulating the lower portion of the liquid through the line 86 and the reboiler 804. The liquid temperature at the bottom of the continuous multi-stage distillation column 802 is 150 ° C, and the pressure at the top of the column is about 8 kPa. The gas distilled from the top of the continuous multi-stage distillation column 802 is condensed in the condenser 803 via line 85, and is continuously discharged by line 87. The liquid phase component is withdrawn from line 89 of the continuous multi-stage distillation column 802 below the line 82.

The liquid phase component discharged from the line 89 is continuously fed to the middle section of the continuous multi-stage distillation column 805 filled with Dixon packing (6 mm Φ) and having an inner diameter of about 5 cm and a column length of 2 m, and the liquid is discharged. Distillation separation of phase components. The heat necessary for the distillation separation is supplied by circulating the lower portion of the liquid through the line 91 and the reboiler 807. The liquid temperature at the bottom of the continuous multi-stage distillation column 805 is 150 ° C, and the pressure at the top of the column is about 1.5 kPa. The gas distilled from the top of the continuous multi-stage distillation column 805 is condensed in the condenser 806 via line 90, and continuously discharged to the storage tank 809 via line 92. The steady state discharge is about 104 g/hr.

The liquid system discharged from line 92 contained a solution of about 99.9% by weight of hexamethylene diisocyanate. The yield based on hexamethylenediamine was 95.4%. After continuous operation for 10 days, it was found that deposits were deposited in the wall area of the thin film distillation apparatus 801.

[Embodiment 7]

. Step (7-1): Production of diphenyl-4,4'-methylene-dicyclohexylcarbamate

Except using 1874 g (8.8 mol) of diphenyl carbonate of Reference Example 1, 1175 g (12.5 mol) of phenol, and 526 g (2.5 mol) of 4,4'-methylenebis(cyclohexylamine), The same procedure as in the step (3-1) of Example 3.

The solution after the reaction was analyzed by liquid chromatography to give diphenyl-4,4'-methylene-dicyclohexylcarbamate in a yield of 99.2%.

. Step (7-2): Production of isocyanate by thermal decomposition of diphenyl-4,4'-methylene-dicyclohexylcarbamate

The reaction was carried out using a device as shown in FIG.

The mixture recovered from the storage tank 705 in the step (7-1) was heated to 150 ° C, fed via line D1 at about 510 g / hr to the filled with Dixon filler (6 mm). The middle portion of the continuous multi-stage distillation column 1301 having an inner diameter of about 5 cm and a column length of 2 m is subjected to a thermal decomposition reaction. The heat necessary for the thermal decomposition reaction is supplied by circulating the lower portion of the liquid through the line D3 and the reboiler 1303. The liquid temperature at the bottom of the column of the continuous multi-stage distillation column 1301 was 220 ° C, and the pressure at the top of the column was about 15 kPa. The gas distilled from the top of the continuous multi-stage distillation column 1301 is condensed in the condenser 1302 via the line D2, and continuously discharged from the line D4. From the bottom of the continuous multi-stage distillation column 1301, the liquid phase component is recovered via line D3.

The liquid phase component discharged through the line D6 is continuously fed to the middle section of the continuous multi-stage distillation column 1304 filled with Dixon packing (6 mm Φ) and having an inner diameter of about 5 cm and a column length of 2 m, and the liquid is discharged. Distillation separation of phase components. The heat necessary for the distillation separation is supplied by circulating the lower portion of the liquid through the line D8 and the reboiler 1306. The liquid temperature at the bottom of the continuous multi-stage distillation column 1304 is 220 ° C, and the pressure at the top of the column is about 5.2 kPa. The gas distilled from the top of the continuous multi-stage distillation column 1304 is condensed in the condenser 1305 via the line D7, and continuously discharged from the line D9. From the bottom of the continuous multi-stage distillation column 1304, the liquid phase component is recovered via line D8 and line D11.

The liquid phase component discharged from the line D8 is continuously fed to the middle section of the continuous multi-stage distillation column 1307 filled with Dixon packing (6 mm Φ) and having an inner diameter of about 5 cm and a column length of 2 m, and the liquid is continuously supplied. Distillation separation of phase components. The heat necessary for the distillation separation is supplied by circulating the lower portion of the liquid through the line D14 and the reboiler 1309. The liquid temperature at the bottom of the continuous multi-stage distillation column 1307 is 220 ° C, and the pressure at the top of the column is about 0.40 kPa. The gas distilled from the top of the continuous multi-stage distillation column 1307 is condensed in the condenser 1308 via line D12. It is continuously discharged via the line D13. The steady state discharge is about 75 g/hr.

The liquid system discharged from line D13 contained about 99.8% by weight of a solution of 4,4'-methylene-bis(cyclohexyl isocyanate). The yield relative to 4,4'-methylenebis(cyclohexylamine) was 80.4%. When the continuous operation was carried out for 10 days, no deposit was accumulated in the inside of the continuous multi-stage distillation column 1301.

[Embodiment 8]

. Step (8-1): Manufacture of N,N' -hexanediyl-bis-carbamic acid diphenyl ester

In addition to 1350 g (6.3 mol) of diphenyl carbonate of Reference Example 1, 2204 g (8.4 mol) of 4-dodecylphenol (manufactured by Aldrich, USA) instead of phenol, and 244 g (2.1 mol) of hexamethylene The same method as the step (1-1) of Example 1 was carried out, except for the bis-diamine.

The solution after the reaction was analyzed by liquid chromatography, and as a result , N,N' -hexanediyl-bis-carbamic acid diphenyl ester was formed in a yield of 99.0%.

. Step (8-2): Production of isocyanate by thermal decomposition of N,N' -hexanediyl-bis-carbamic acid diphenyl ester

The reaction was carried out using a device as shown in FIG.

The thin film distillation apparatus 801 having a heat transfer area of 0.1 m ² was heated to 220 ° C so that the internal pressure was about 5.2 kPa. The mixture recovered in the storage tank 705 in the step (8-1) was heated to 150 ° C, and supplied to the upper portion of the thin film distillation apparatus 801 via the line 81 at about 1200 g/hr. From the bottom of the thin film distillation apparatus 801, the liquid phase component is discharged from the line 83, and is circulated to the upper portion of the thin film distillation apparatus 801 via the line 84 and the line 81. The gas phase components are discharged from line 82.

Filled with Dixon packing (6 mm) The middle section of the continuous multi-stage distillation column 802 having an inner diameter of about 5 cm and a column length of 2 m is continuously fed to the vapor phase component discharged from the thin film distillation apparatus 801 via the line 82, and the vapor phase component is subjected to distillation separation. The heat necessary for the distillation separation is supplied by circulating the lower portion of the liquid through the line 86 and the reboiler 804. The liquid temperature at the bottom of the continuous multi-stage distillation column 802 is 150 ° C, and the pressure at the top of the column is about 4.0 kPa. The gas distilled from the top of the continuous multi-stage distillation column 802 is condensed in the condenser 803 via line 85, and is continuously discharged by line 87. The liquid phase component is withdrawn from line 89 of the continuous multi-stage distillation column 802 below the line 82.

Filled with Dixon packing (6 mm) The middle section of the continuous multi-stage distillation column 805 having an inner diameter of about 5 cm and a column length of 2 m continuously feeds the liquid phase component discharged from the line 89 to carry out distillation separation of the liquid phase component. The heat necessary for the distillation separation is supplied by circulating the lower portion of the liquid through the line 91 and the reboiler 807. The liquid temperature at the bottom of the continuous multi-stage distillation column 805 is 150 ° C, and the pressure at the top of the column is about 0.8 kPa. The gas distilled from the top of the continuous multi-stage distillation column 805 is condensed in the condenser 806 via line 90, and continuously discharged to the storage tank 809 via line 92. The steady state discharge is about 104 g/hr.

In a steady state, the liquid phase component is discharged to the storage tank 810 by line 94 at about 690 g/hr. The liquid phase component contains about 97% by weight of 4-dodecylphenol.

The liquid system discharged from line 92 contained a solution of about 99.8% by weight of hexamethylene diisocyanate. The yield based on hexamethylenediamine was 93.1%. The continuous operation was carried out for 10 days, and no deposit was observed in the wall area of the thin film distillation apparatus 801.

[Embodiment 9]

. Step (9-1): 3-(phenoxycarbonylamino-methyl)-3,5,5-trimethylcyclohexane Manufacture of phenyl carbamic acid

In addition to 1028 g (4.8 mol) of diphenyl carbonate of Reference Example 1, 2643 g (8.0 mol) of 2,4-(α,α-dimethylbenzyl)phenol (manufactured by Tokyo Chemical Industry Co., Ltd.), instead of phenol, The same procedure as in the step (2-1) of Example 2 was carried out, except that 273 g (1.6 mol) of 3-aminomethyl-3,5,5-trimethylcyclohexylamine was used.

The solution after the reaction was analyzed by liquid chromatography to give 3-(phenoxycarbonylamino-methyl)-3,5,5-trimethylcyclohexylaminocarbamate benzene in a yield of 99.0%. ester.

. Step (9-2): Production of isocyanate by thermal decomposition of phenyl 3-(phenoxycarbonylamino-methyl)-3,5,5-trimethylcyclohexylaminocarboxylate

The procedure of Example 8 was carried out except that the mixture obtained in the step (9-2) was used instead of the mixture obtained in the step (8-1), and the mixture was heated to 150 ° C and supplied at about 1310 g/hr. 8-2) The same method.

The gas distilled from the top of the continuous multi-stage distillation column 805 is condensed in the condenser 806 via line 90, and continuously discharged to the storage tank 809 via line 92 at about 112 g/hr.

The liquid system discharged from line 92 contained a solution of about 99.8% by weight of isophorone diisocyanate. The yield based on 3-aminomethyl-3,5,5-trimethylcyclohexylamine was 94.5%. The continuous operation was carried out for 10 days, and no deposit was observed in the wall area of the thin film distillation apparatus 801.

[Embodiment 10]

. Step (10-1): Manufacture of N,N' -(4,4'-methylene-diphenyl)-diphenyl diphenyl carbamate

The reaction was carried out using the apparatus shown in FIG.

In the state where the line 74 is closed, 1478 g (6.9 mol) of diphenyl carbonate of Reference Example 1 and 50.5 g (0.2 mol) of zinc acetate dihydrate (manufactured by Aldrich Co., Ltd.) are supplied from the storage tank 701 via the line 71. The mixed solution was supplied to a SUS reaction vessel 704 equipped with a baffle having an internal volume of 5 L, and 1297 g (13.8 mol) of phenol was supplied from the storage tank 702 via line 72 to the SUS reactor. The temperature of the liquid in the reactor 704 was adjusted to about 50 ° C, and 456 g (2.3 mol) of 4,4'-methylene diphenylamine (manufactured by Aldrich, USA) was passed from the storage tank 703 via line 73 at about 200 g/hr. ) is supplied to the reactor 704.

The solution after the reaction was analyzed by liquid chromatography to give N,N' -(4,4'-methylene-diphenyl)-dicarbamic acid diphenyl ester in a yield of 98.8%.

Line 74 is opened and the reaction liquid is transported via line 74 to storage tank 705.

. Step (10-2): Production of isocyanate by thermal decomposition of N,N' -(4,4'-methylene-diphenyl)-dicarbamic acid diphenyl ester

The reaction was carried out using a device as shown in FIG.

The thin film distillation apparatus 1201 having a heat transfer area of 0.1 m ² was heated to 230 ° C so that the internal pressure was about 1.3 kPa. The mixture recovered in the storage tank 705 in the step (10-1) was heated to 130 ° C, and supplied to the upper portion of the thin film distillation apparatus 1201 via the line C1 at about 690 g/hr. From the bottom of the thin film distillation apparatus 1201, the liquid phase component is discharged from the line C3, and is circulated to the upper portion of the thin film distillation apparatus 1201 via the line C4 and the line C1. The gas phase component is discharged from line C2.

The middle portion of the continuous multi-stage distillation column 1202 filled with Dixon packing (6 mm Φ) having an inner diameter of about 5 cm and a column length of 2 m is continuously fed into the gas phase discharged from the thin film distillation apparatus 1201 via the line C2. The component is subjected to distillation separation of the gas phase component. The heat necessary for distillation separation is via line C6 and again The boiler 1204 circulates and supplies the liquid in the lower portion of the tower. The liquid temperature at the bottom of the continuous multi-stage distillation column 1201 is 200 ° C, and the pressure at the top of the column is 60 kPa. The gas distilled from the top of the continuous multi-stage distillation column 1201 is condensed in the condenser 1203 via the line C5, and continuously discharged from the line C7. The liquid phase component is discharged from line C8.

The liquid phase component discharged from the line C8 is continuously fed to the middle section of the continuous multi-stage distillation column 1205 filled with Dixon packing (6 mm Φ) and having an inner diameter of about 5 cm and a column length of 2 m, and the liquid phase is carried out. Distillation separation of the ingredients. The heat necessary for the distillation separation is supplied by circulating the lower portion of the liquid through the line C11 and the reboiler 1207. The liquid temperature at the bottom of the continuous multi-stage distillation column 1205 is 210 ° C, and the pressure at the top of the column is about 2.5 kPa. The gas distilled from the top of the continuous multi-stage distillation column 1205 is condensed in the condenser 1206 via the line C10, and continuously discharged through the line C12. The liquid phase component is discharged from line C14.

The liquid phase component discharged from the line C14 is continuously fed to the middle section of the continuous multi-stage distillation column 1208 filled with Dixon packing (6 mm Φ) and having an inner diameter of about 5 cm and a column length of 2 m, and the liquid is continuously supplied. Distillation separation of phase components. The heat necessary for the distillation separation is supplied by circulating the lower portion of the liquid through the line C16 and the reboiler 1210. The liquid temperature at the bottom of the continuous multi-stage distillation column 1208 is 220 ° C, and the pressure at the top of the column is about 0.5 kPa. The gas distilled from the top of the continuous multi-stage distillation column 1205 was condensed in the condenser 1209 via line C15, and continuously discharged via line C17 at about 99.6 g/hr. The liquid discharged from C17 contained about 99.9% by weight of 4,4'-diphenylmethane diisocyanate. The yield relative to 4,4'-methylenediphenylamine was 82.3%. The continuous operation was carried out for 10 days, and no deposit was observed in the wall area of the thin film distillation apparatus 1202.

[Example 11]

. Step (11-1): Production of diphenyl toluene-2,4-dicarbamate

The reaction was carried out using the apparatus shown in FIG.

In the state where the line 74 is closed, a mixture of 2125 g (9.9 mol) of diphenyl carbonate of Reference Example 1 and 35.1 g (0.2 mol) of zinc acetate dihydrate is supplied from the storage tank 701 via line 71 to the internal volume. In a 5 L SUS reaction vessel 704 equipped with a baffle, 1534 g (16.3 mol) of phenol was supplied from the storage tank 702 via the line 72 to the SUS reactor. The temperature of the liquid in the reactor 704 was adjusted to about 50 ° C, and 391 g (3.2 mol) of 2,4-toluenediamine (manufactured by Aldrich Co., Ltd.) was supplied from the storage tank 703 via line 73 to about 230 g/hr. In the reactor 704.

The solution after the reaction was analyzed by liquid chromatography, and as a result, toluene-2,4-dicarbamic acid diphenyl ester was formed in a yield of 98.1%.

Line 74 is opened and the reaction liquid is transported via line 74 to storage tank 705.

. Step (11-2): Production of isocyanate by thermal decomposition of toluene-2,4-dicarbamic acid diphenyl ester

The reaction was carried out using a device as shown in FIG.

The thin film distillation apparatus 801 having a heat transfer area of 0.1 m ² was heated to 220 ° C so that the internal pressure was about 13 kPa. The mixture recovered in the storage tank 705 in the step (11-1) was heated to 130 ° C, and supplied to the upper portion of the thin film distillation apparatus 801 via line 81 at about 820 g/hr. From the bottom of the thin film distillation apparatus 801, the liquid phase component is discharged from the line 83, and is circulated to the upper portion of the thin film distillation apparatus 801 via the line 84 and the line 81. The gas phase components are discharged from line 82.

The inside diameter is about 5 cm and the length of the tower is 2 filled with Dixon packing (6 mm Φ). In the middle of the continuous multi-stage distillation column 802 of m, the gas phase component discharged from the thin film distillation apparatus 801 via the line 82 is continuously fed, and the vapor phase component is subjected to distillation separation. The heat necessary for the distillation separation is supplied by circulating the lower portion of the liquid through the line 86 and the reboiler 804. The liquid temperature at the bottom of the continuous multi-stage distillation column 802 is 150 ° C, and the pressure at the top of the column is about 15 kPa. The gas distilled from the top of the continuous multi-stage distillation column 802 is condensed in the condenser 803 via line 85, and continuously discharged from the line 87. The liquid phase component is discharged from line 89 of the continuous multi-stage distillation column 802 below the line 82.

The liquid phase component discharged from the line 89 is continuously fed to the middle section of the continuous multi-stage distillation column 805 filled with Dixon packing (6 mm Φ) and having an inner diameter of about 5 cm and a column length of 2 m, and the liquid is discharged. Distillation separation of phase components. The heat necessary for the distillation separation is supplied by circulating the lower portion of the liquid through the line 91 and the reboiler 807. The liquid temperature at the bottom of the continuous multi-stage distillation column 805 is 150 ° C, and the pressure at the top of the column is about 1.3 kPa. The gas distilled from the top of the continuous multi-stage distillation column 805 is condensed in the condenser 806 via line 90, and continuously discharged to the storage tank 809 via line 92 at about 93 g/hr.

The liquid system discharged from line 92 contains a solution of about 99.7% by weight of 2,4-toluene diisocyanate. The yield based on 2,4-toluenediamine was 83.4%. The continuous operation was carried out for 10 days, and no deposit was observed in the wall area of the thin film distillation apparatus 801.

[Embodiment 12]

. Step (12-1): Production of N,N' -(4,4'-methylene-diphenyl)-diphenyl diphenyl carbamate

Except using 2055 g (9.5 mol) of diphenyl carbonate of Reference Example 1 with 54.9 The procedure of Example 10 was carried out in addition to a mixture of g (0.3 mol) zinc acetate dihydrate, 1293 g (13.8 mol) phenol and 496 g (2.5 mol) 4,4'-methylenediphenylamine. -1) The same method.

The solution after the reaction was analyzed by liquid chromatography to give N,N' -(4,4'-methylene-diphenyl)-dicarbamic acid diphenyl ester in a yield of 98.6%.

. Step (12-2): Production of isocyanate by thermal decomposition of N,N' -(4,4'-methylene-diphenyl)-dicarbamic acid diphenyl ester

The mixture obtained in the step (11-1) was used instead of the mixture obtained in the step (7-1), and the mixture was heated to 130 ° C, and subjected to a thermal decomposition reaction via a line D1 at a feed of about 700 g / hr. The heat necessary for the thermal decomposition reaction is supplied by circulating the lower portion of the liquid through the line D3 and the reboiler 1303. The liquid temperature at the bottom of the continuous multi-stage distillation column 1301 is 220 ° C, and the pressure at the top of the column is about 15 kPa. The gas distilled from the top of the continuous multi-stage distillation column 1301 is condensed in the condenser 1302 via the line D2, and continuously discharged from the line D4. The liquid phase component is recovered from the bottom of the continuous multi-stage distillation column 1301 via line D3.

The liquid phase component discharged through the line D6 is continuously fed to the middle section of the continuous multi-stage distillation column 1304 filled with Dixon packing (6 mm Φ) and having an inner diameter of about 5 cm and a column length of 2 m, and the liquid is discharged. Distillation separation of phase components. The heat necessary for the distillation separation is supplied by circulating the lower portion of the liquid through the line D8 and the reboiler 1306. The liquid temperature at the bottom of the continuous multi-stage distillation column 1304 is 220 ° C, and the pressure at the top of the column is about 5.2 kPa. The gas distilled from the top of the continuous multi-stage distillation column 1304 is condensed in the condenser 1305 via the line D7, and continuously discharged from the line D9. From the bottom of the continuous multi-stage distillation column 1304, the liquid phase The components are recovered via line D8 and line D11.

The liquid phase component discharged from the line D8 is continuously fed to the middle section of the continuous multi-stage distillation column 1307 filled with Dixon packing (6 mm Φ) and having an inner diameter of about 5 cm and a column length of 2 m, and the liquid is continuously supplied. Distillation separation of phase components. The heat necessary for the distillation separation is supplied by circulating the lower portion of the liquid through the line D14 and the reboiler 1309. The liquid temperature at the bottom of the continuous multi-stage distillation column 1307 is 220 ° C, and the pressure at the top of the column is about 0.40 kPa. The gas distilled from the top of the continuous multi-stage distillation column 1307 is condensed in the condenser 1308 via the line D12, and continuously discharged through the line D13. The steady state discharge is about 92 g/hr.

The liquid system discharged from line D13 contained a solution of about 99.8% by weight of 4,4'-diphenylmethane diisocyanate. The yield relative to 4,4'-methylenediphenylamine was 76.9%. When the continuous operation was carried out for 10 days, no deposit was accumulated in the inside of the continuous multi-stage distillation column 1301.

[Example 13]

. Step (13-1): Manufacture of N,N' -hexanediyl-bis-carbamic acid diphenyl ester

The diphenyl carbonate of Reference Example 1 was placed in an eggplant type flask having an internal volume of 10 L, and a three-way cock was attached to the eggplant type flask, and a distillation column filled with the spiral filler No. 3 was attached and accepted with the distillate. A fractionation column and a thermometer of a reflux condenser connected to the reactor were subjected to vacuum-nitrogen replacement in the system, and diphenyl carbonate was distilled and purified. The distilled purified product was subjected to ¹ H-NMR measurement, and found to contain about 99.9% by weight of diphenyl carbonate. Further, it contains 0.002 ppm of iron as a metal atom.

Example 1 was carried out except that 1414 g (6.6 mol) of the diphenyl carbonate, 1034 g (11.0 mol) of phenol and 256 g (2.2 mol) of hexamethylenediamine were supplied. The same method as step (1-1).

The solution after the reaction was analyzed by liquid chromatography, and as a result , N,N' -hexanediyl-bis-carbamic acid diphenyl ester was formed in a yield of 99.0%.

. Step (13-2): Production of isocyanate by thermal decomposition of N,N' -hexanediyl-bis-carbamic acid diphenyl ester

The same procedure as in the step (1-2) of Example 1 was carried out except that the mixture obtained in the step (13-1) was used instead of the mixture obtained in the step (1-1). It is continuously discharged to the sump 809 by line 92 at about 104 g/hr. The liquid system discharged from line 92 contained a solution of about 99.8% by weight of hexamethylene diisocyanate. The yield based on hexamethylenediamine was 95.0%. The continuous operation was carried out for 10 days, and no deposit was observed in the wall area of the thin film distillation apparatus 801.

[Embodiment 14]

. Step (14-1): Manufacture of N,N' -hexanediyl-bis-carbamic acid diphenyl ester

To the diphenyl carbonate of Reference Example 1, iron (II) acetate was added to prepare diphenyl carbonate containing 8% of iron as a metal atom. The same procedure as in the step (1-1) of Example 1 was carried out except that 1371 g (6.4 mol) of the diphenyl carbonate, 940 g (10.0 mol) of phenol and 232 g (2.0 mol) of hexamethylenediamine were supplied. Methods.

The solution after the reaction was analyzed by liquid chromatography, and as a result , N,N' -hexanediyl-bis-carbamic acid diphenyl ester was formed in a yield of 98.9%.

. Step (14-2): Production of isocyanate by thermal decomposition of N,N' -hexanediyl-bis-carbamic acid diphenyl ester

The same procedure as in the step (1-2) of Example 1 was carried out except that the mixture obtained in the step (14-1) was used instead of the mixture obtained in the step (1-1). It is continuously discharged to the sump 809 by line 92 at about 101 g/hr. The liquid system discharged from line 92 contained a solution of about 99.8% by weight of hexamethylene diisocyanate. The yield based on hexamethylenediamine was 95.2%. The continuous operation was carried out for 10 days, and no deposit was observed in the wall area of the thin film distillation apparatus 801.

[Example 15]

. Step (15-1): Manufacture of N,N' -hexanediyl-bis-carbamic acid diphenyl ester

The diphenyl carbonate of Reference Example 1 was placed in an eggplant type flask having an internal volume of 10 L, and a three-way cock was attached to the eggplant type flask, and a distillation column filled with the spiral filler No. 3 was attached and accepted with the distillate. A fractionation column and a thermometer of a reflux condenser connected to the reactor were subjected to vacuum-nitrogen replacement in the system, and diphenyl carbonate was distilled and purified. When a distillate having an addition amount of about 1/4 was obtained, the flask was cooled to complete distillation purification. The distillate was subjected to ¹ H-NMR measurement, and as a result, the distillate contained about 99.9% by weight of diphenyl carbonate. Further, the metal atom contained in the distillate is not less than the lower limit of detection (0.001 ppm) in terms of iron, cobalt, nickel, zinc, tin, copper, and titanium.

The same procedure as in the first step (1-1) of Example 1 was carried out except that 1553 g (7.3 mol) of the diphenyl carbonate, 1175 g (12.5 mol) of phenol and 291 g (2.5 mol) of hexamethylenediamine were supplied. Methods.

The solution after the reaction was analyzed by liquid chromatography to give N,N' -hexanediyl-bis-carbamic acid diphenyl ester in a yield of 95.6%.

. Step (15-2): Production of isocyanate by thermal decomposition of N,N' -hexanediyl-bis-carbamic acid diphenyl ester

The same procedure as in the step (1-2) of Example 1 was carried out except that the mixture obtained in the step (15-1) was used instead of the mixture obtained in the step (1-1). The liquid is continuously discharged to the sump 809 by line 92 at about 99.1 g/hr. The liquid system discharged from line 92 contained a solution of about 99.8% by weight of hexamethylene diisocyanate. The yield based on hexamethylenediamine was 88.9%. The continuous operation was carried out for 10 days, and no deposit was observed in the wall area of the thin film distillation apparatus 801.

[Example 16]

. Step (16-1): Manufacture of N,N' -hexanediyl-bis-carbamic acid diphenyl ester

To the diphenyl carbonate of Reference Example 1, iron (II) acetonitrile was added to prepare diphenyl carbonate containing 13% of iron as a metal atom. The same procedure as in the first step (1-1) of Example 1 was carried out except that 1527 g (7.1 mol) of the diphenyl carbonate, 1081 g (11.5 mol) of phenol and 267 g (2.3 mol) of hexamethylenediamine were supplied. Methods.

The solution after the reaction was analyzed by liquid chromatography, and as a result , N,N' -hexanediyl-bis-carbamic acid diphenyl ester was formed in a yield of 94.5%.

. Step (16-2): Production of isocyanate by thermal decomposition of N,N' -hexanediyl-bis-carbamic acid diphenyl ester

The same procedure as in the step (1-2) of Example 1 was carried out except that the mixture obtained in the step (16-1) was used instead of the mixture obtained in the step (1-1). The liquid is continuously discharged to the sump 809 by line 92 at about 95.1 g/hr. The liquid system discharged from line 92 contained a solution of about 99.8% by weight of hexamethylene diisocyanate. The yield based on hexamethylenediamine was 88.0%. When the operation was continued for 10 days, no deposit was observed in the wall area of the thin film distillation apparatus 801.

[Example 17]

. Step (17-1): Manufacture of N,N' -hexanediyl-bis-carbamic acid diphenyl ester

In addition to supplying 1350 g (6.3 mol) of diphenyl carbonate and 790 g (8.4 mol) of phenol, a mixture of 244 g (2.1 mol) of hexamethylenediamine and 197 g (2.1 mol) of phenol was supplied instead of hexamethylene. The same method as the step (1-1) of Example 1 was carried out, except for the diamine.

The solution after the reaction was analyzed by liquid chromatography, and as a result , N,N' -hexanediyl-bis-carbamic acid diphenyl ester was formed in a yield of 99.0%.

. Step (17-2): Production of isocyanate by thermal decomposition of N,N' -hexanediyl-bis-carbamic acid diphenyl ester

The same procedure as in the step (1-2) of Example 1 was carried out except that the mixture obtained in the step (17-1) was used instead of the mixture obtained in the step (1-1). The liquid is continuously discharged to the sump 809 by line 92 at about 106 g/hr. The liquid system discharged from line 92 contained a solution of about 99.8% by weight of hexamethylene diisocyanate. The yield based on hexamethylenediamine was 97.0%. The continuous operation was carried out for 10 days, and no deposit was observed in the wall area of the thin film distillation apparatus 801.

[Embodiment 18]

. Step (18-1): Manufacture of N,N' -hexanediyl-bis-aminocarbamic acid bis(3-methylbutyl) ester

A device as shown in Fig. 16 was used.

In a state where the line G4 is closed, 1660 g (7.8 mol) of diphenyl carbonate is supplied from the storage tank 1601 via the line G1 to a SUS reaction vessel 1604 with a baffle having an internal volume of 5 L, and is passed through the storage tank 1602 via the storage tank 1602. On line G2, 1175 g (12.5 mol) of phenol was supplied to the reactor made of SUS. The reaction The temperature of the liquid in the vessel 1604 was adjusted to about 50 ° C, and a mixture of 291 g (2.5 mol) of hexamethylenediamine and water was supplied to the reactor 1604 from the storage tank 1603 via line G3 at about 200 g/hr.

After completion of the reaction, the inside of the reactor 1604 was depressurized to 10 kPa, and water was distilled off. The water is condensed in condenser 1607 and discharged via line G6.

The solution after the reaction was analyzed by liquid chromatography, and as a result , N,N' -hexanediyl-bis-carbamic acid diphenyl ester was formed in a yield of 99.0%.

The line G4 is opened, and the reaction liquid is transported to the storage tank 1605 via the line G4.

. Step (18-2): Production of isocyanate by thermal decomposition of N,N' -hexanediyl-bis-carbamic acid diphenyl ester

The same procedure as in the step (1-2) of Example 1 was carried out except that the mixture obtained in the step (18-1) was used instead of the mixture obtained in the step (1-1). The heating area of the thin film distillation apparatus 801 with respect to the reactor capacity is larger than the reactor 1604 of FIG. The liquid is continuously discharged to the sump 809 by line 92 at about 104 g/hr. The liquid system discharged from line 92 contained a solution of about 99.8% by weight of hexamethylene diisocyanate. The yield relative to hexamethylenediamine was 96.5%. The continuous operation was carried out for 10 days, and no deposit was observed in the wall area of the thin film distillation apparatus 801.

[Example 19] Reactor cleaning

In the sixth embodiment, the cleaning operation of the thin film distillation apparatus 801 in which the deposits are accumulated is carried out. The thin film distillation apparatus 801 was heated to 180 ° C so that the inside of the thin film distillation apparatus 801 was an atmospheric nitrogen atmosphere. Phenol is supplied from line 81 at about 1200 g/hr, discharged from line 83, and the liquid phase components are recovered via line 94 to the storage tank. 810. When this operation was performed for 1 hour, no deposit was found inside the thin film distillation apparatus 801.

[Example 20] ~ [Example 27]

The operation of Example 6 was carried out continuously, and various washing solvents were used every 10 days, and the washing operation was carried out in the same manner as in Example 19, and the results are shown in Table 1.

[Comparative Example 1]

. Step (A-1): N, N '- dihexyl - bis - manufacture of amino carboxylic acid, diphenyl

The reaction was carried out using a device as shown in FIG.

In the state where the line E4 is closed, 1979 g (9.2 mol) of diphenyl carbonate is supplied from the storage tank 1401 via the line E1 to the SUS reaction vessel 1404 with a baffle having an internal volume of 5 L, and the tank 1402 is passed through the line. E2 1316 g (14.0 mol) of phenol was supplied to the reactor made of SUS. The temperature of the liquid in the reactor 1404 was adjusted to about 50 ° C, and 325 g (2.8 mol) of hexamethylenediamine was supplied to the reactor 1404 from the storage tank 1403 via line E3 at about 190 g/hr.

The solution after the reaction was analyzed by liquid chromatography, and as a result , N,N' -hexanediyl-bis-carbamic acid diphenyl ester was formed in a yield of 99.3%.

. Step (A-2): Production of isocyanate by thermal decomposition of N,N' -hexanediyl-bis-carbamic acid diphenyl ester

The reaction was then carried out using a device as shown in FIG.

The reactor 1404 made of SUS was heated to 220 ° C, and the pressure inside the reactor was reduced to 1.3 kPa. The gas phase component is discharged from the line E4, and the gas phase component is continuously fed to the middle section of the continuous multi-stage distillation column 1405 having an inner diameter of about 5 cm and a column length of 2 m filled with a Dixon packing (6 mm Φ). Steaming the gas phase component Distillation separation. The heat necessary for the distillation separation is supplied by circulating the lower portion of the liquid through the line E6 and the reboiler 1408. The liquid temperature at the bottom of the continuous multi-stage distillation column 1405 is 150 ° C, and the pressure at the top of the column is about 15 kPa. The gas distilled from the top of the continuous multi-stage distillation column 802 is condensed in the condenser 1407 via the line E5, and continuously discharged from the line E7. The liquid phase component is discharged from the line E9 of the continuous multi-stage distillation column 1405 at a position lower than the line E4.

The liquid phase component discharged from the line E9 is continuously fed to the middle section of the continuous multi-stage distillation column 1406 filled with Dixon packing (6 mm Φ) and having an inner diameter of about 5 cm and a column length of 2 m, and the liquid is continuously supplied. Distillation separation of phase components. The heat necessary for the distillation separation is supplied by circulating the lower portion of the liquid through the line E11 and the reboiler 1412. The liquid temperature at the bottom of the continuous multi-stage distillation column 1406 is 150 ° C and the overhead pressure is about 1.5 kPa. The gas distilled from the top of the continuous multi-stage distillation column 1406 is condensed in the condenser 1410 via the line E10, and continuously discharged to the storage tank 1411 via the line E12. The liquid recovered from storage tank 1411 is approximately 304 g. The liquid system contained a solution of about 99.8% by weight of hexamethylene diisocyanate. The yield based on hexamethylenediamine was 64.5%.

[Comparative Example 2]

. Step (B-1): Production of N,N' -(4,4'-methylene-diphenyl)-diphenyl diphenyl carbamate

The reaction was carried out using a device as shown in FIG.

In the state where the line F4 is closed, a mixture of 1527 g (7.1 mol) of diphenyl carbonate and 50.5 g (0.2 mol) of zinc acetate dihydrate is supplied from the storage tank 1501 via the line F1 to an internal volume of 5 L. In the SUS reaction vessel 1504 of the plate, 1146 g (1.2 mol) of phenol was supplied from the storage tank 1502 via the line F2. It was supplied to the reactor made of SUS. The liquid temperature in the reactor 1504 was adjusted to about 50 ° C, and 456 g (2.3 mol) of 4,4'-methylene diphenylamine was supplied to the reactor 1504 from the storage tank 1503 via line F3 at about 200 g/hr. in.

The solution after the reaction was analyzed by liquid chromatography to give N,N' -(4,4'-methylene-diphenyl)-dicarbamic acid diphenyl ester in a yield of 98.3%.

. Step (B-2): Production of isocyanate by thermal decomposition of N,N' -(4,4'-methylene-diphenyl)-dicarbamic acid diphenyl ester

The reaction was then carried out using a device as shown in FIG.

The SUS reactor 1504 was heated to 220 ° C to reduce the pressure in the reactor to 1.3 kPa. The gas phase component is discharged from the line F4, and the gas phase component is continuously fed to the middle section of the continuous multi-stage distillation column 1506 filled with a Dixon packing (6 mm Φ) having an inner diameter of about 5 cm and a column length of 2 m. Distillation separation of the gas phase component is carried out. The heat necessary for the distillation separation is supplied by circulating the lower portion of the liquid through the line F6 and the reboiler 1507. The bottom of the continuous multi-stage distillation column 1506 has a liquid temperature of 200 ° C and a column top pressure of 60 kPa. The gas distilled from the top of the continuous multi-stage distillation column 1506 is condensed in the condenser 1505 via the line F5, and continuously discharged from the line F7. The liquid phase component is discharged from line F6.

The liquid phase component discharged from the line F6 is continuously fed to the middle section of the continuous multi-stage distillation column 1509 filled with Dixon packing (6 mm Φ) and having an inner diameter of about 5 cm and a column length of 2 m, and the liquid is continuously supplied. Distillation separation of phase components. The heat necessary for the distillation separation is supplied by circulating the lower portion of the liquid through the line F11 and the reboiler 1510. Liquid temperature at the bottom of the continuous multi-stage distillation column 1509 At 210 ° C, the top pressure is approximately 2.5 kPa. The gas distilled from the top of the continuous multi-stage distillation column 1509 is condensed in the condenser 1508 via the line F10, and continuously discharged through the line F12. The liquid phase component is discharged from the line F11.

The liquid phase component discharged from the line F14 is continuously fed to the middle portion of the continuous multi-stage distillation column 1512 filled with Dixon packing (6 mm Φ) and having an inner diameter of about 5 cm and a column length of 2 m, and the liquid is continuously supplied. Distillation separation of phase components. The heat necessary for the distillation separation is supplied by circulating the lower portion of the liquid through the line F16 and the reboiler 1513. The liquid temperature at the bottom of the continuous multi-stage distillation column 1512 is 220 ° C, and the pressure at the top of the column is about 0.5 kPa. The gas distilled from the top of the continuous multi-stage distillation column 1512 is condensed in the condenser 1511 via the line F15, and is discharged through the line F17. The liquid discharged from F17 was about 70 g and contained about 99.9% by weight of 4,4'-diphenylmethane diisocyanate. The yield relative to 4,4'-methylenediphenylamine was 56.0%.

[Comparative Example 3]

. Step (C-1): Manufacture of N,N' -hexanediyl-bis-carbamic acid diphenyl ester

The reaction was carried out using the apparatus shown in FIG.

In the state where the line 74 was closed, 2454 g (11.5 mol) of diphenyl carbonate was supplied from the storage tank 701 via the line 71 to a SUS reaction vessel 704 equipped with a baffle having an internal volume of 5 L. The temperature of the liquid in the reactor 704 was adjusted to about 80 ° C, molten diphenyl carbonate, and 372 g (3.2 mol) of hexamethylenediamine was supplied from the storage tank 703 via line 73 to the reactor at about 100 g/hr. 704.

The solution after the reaction was analyzed by liquid chromatography, and as a result , N,N' -hexanediyl-bis-carbamic acid diphenyl ester was formed in a yield of 77.5%.

Line 74 is opened and the reaction liquid is transported via line 74 to storage tank 705.

. Step (C-2): Production of isocyanate by thermal decomposition of N,N' -hexanediyl-bis-carbamic acid diphenyl ester

The reaction was carried out using a device as shown in FIG.

The same procedure as in the step (1-2) of Example 1 was carried out except that the mixture obtained in the step (C-1) was used instead of the mixture obtained in the step (1-1).

The liquid is continuously discharged to the sump 809 via line 92 at about 113 g/hr.

The liquid system discharged from line 92 contained a solution of about 99.8% by weight of hexamethylene diisocyanate. The yield relative to hexamethylenediamine was 74.4%.

[Comparative Example 4] ~ [Comparative Example 6]

The operation of Example 6 was carried out continuously, and various washing solvents were used every 10 days, and the washing operation was carried out in the same manner as in Example 13, and the results are shown in Table 1.

[Industrial availability]

The method for producing an isocyanate of the present invention can efficiently produce an isocyanate without using highly toxic phosgene. Therefore, the production method of the present invention is industrially useful and has high commercial value.

(figure 1)

1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17‧‧ line

101, 107‧‧‧ distillation tower

102‧‧‧ tower reactor

103, 106‧‧‧film distillation unit

104‧‧‧ autoclave

105‧‧‧In addition to carbon tank

111, 112, 117‧‧ ‧ reboiler

121, 123, 126, 127‧‧ ‧ condenser

(figure 2)

21, 22, 23, 24, 25‧‧‧ lines

201‧‧‧Preheater

202‧‧‧Continuous multi-stage distillation tower

203‧‧‧Condenser

204‧‧‧ reboiler

205, 206‧‧‧ storage tank

(image 3)

31, 32, 33, 34, 35‧‧‧ lines

301‧‧‧Preheater

302‧‧‧Continuous multi-stage distillation tower

303‧‧‧Condenser

304‧‧‧ reboiler

305, 306‧‧ ‧ storage tank

(Figure 4)

41, 42, 43, 44, 45‧‧‧ lines

401‧‧‧Preheater

402‧‧‧Continuous multi-stage distillation tower

403‧‧‧Condenser

404‧‧‧ reboiler

405, 406‧‧ ‧ storage tank

(Figure 5)

51, 52, 53, 54, 55‧ ‧ lines

501‧‧‧Preheater

502‧‧‧Continuous multi-stage distillation tower

503‧‧‧Condenser

504‧‧‧ reboiler

505, 506‧‧‧ storage tank

(Figure 6)

61, 62, 63, 64, 65‧‧‧ lines

601‧‧‧Preheater

602‧‧‧Continuous multi-stage distillation tower

603‧‧‧Condenser

604‧‧‧ reboiler

605, 606‧‧ ‧ storage tank

(Figure 7)

71, 72, 73, 74‧‧‧ lines

701, 702, 703, 705‧‧ ‧ storage tank

704‧‧‧Stirring tank

(Figure 8)

81, 82, 83, 84, 85, 86, 87, 88, 89‧‧ line

801‧‧‧film distillation unit

802, 803‧‧‧ continuous multi-stage distillation tower

808, 809, 810 ‧ ‧ storage tank

803, 806‧‧ ‧ condenser

804, 807‧‧ ‧ reboiler

(Figure 9)

90, 91, 92, 93 94, 95, 96, 97, 98, 99‧‧ line

901‧‧‧Preheater

902‧‧‧Continuous multi-stage distillation tower

903‧‧‧Condenser

904‧‧‧ reboiler

905, 906‧‧ ‧ storage tank

(Figure 10)

1001‧‧‧Preheater

1002‧‧‧Continuous multi-stage distillation tower

1003‧‧‧Condenser

1004‧‧‧ reboiler

1005, 1006‧‧‧ storage tank

A1, A2, A3, A4, A5‧‧ line

(Figure 11)

1101‧‧‧Preheater

1102‧‧‧Continuous multi-stage distillation tower

1103‧‧‧Condenser

1104‧‧‧Reboiler

1105, 1106‧‧‧ storage tank

B1, B2, B3, B4, B5‧‧ line

(Figure 12)

1201‧‧‧film distillation unit

1202, 1205, 1208‧‧‧ continuous multi-stage distillation tower

1203, 1206, 1209‧‧ ‧ condenser

1204, 1207, 1210‧‧‧ reboiler

C1, C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17, C18‧‧ line

(Figure 13)

1301, 1304, 1307‧‧‧ continuous multi-stage distillation tower

1302, 1305, 1308‧‧ ‧ condenser

1303, 1306, 1309‧‧‧ reboiler

D1, D2, D3, D4, D5, D6, D7, D8, D9, D10, D11, D12, D13, D14, D15‧‧ line

(Figure 14)

1401, 1402, 1403, 1409, 1410‧‧ Storage tank

1404‧‧‧Stirring tank

1405, 1406‧‧‧Continuous multi-stage distillation tower

1407, 1410‧‧ ‧ condenser

1408, 1412‧‧‧ reboiler

E1, E2, E3, E4, E5, E6, E7, E8, E9, E10, E11, E12, E13‧‧ line

(Figure 15)

1501, 1502, 1503‧‧‧ storage tank

1504‧‧‧Stirring tank

1506, 1509, 1512‧‧‧Continuous multi-stage distillation tower

1505, 1508, 1511‧‧ ‧ condenser

1507, 15I0, 1513‧‧‧ reboiler

F1, F2, F3, F4, F5, F6, F7, F8, F9, F10, F11, F12, F13, F14, F15, F16, F17, F18‧‧ line

(Figure 16)

1601, 1602, 16031606‧‧ Storage tank

1604‧‧‧Stirring tank

1605‧‧‧ column

1607‧‧‧Condenser

G1, G2, G3, G4, G5, G6‧‧ line

Fig. 1 is a conceptual diagram showing a continuous production apparatus of a carbonate according to an embodiment of the present invention.

Fig. 2 is a conceptual view showing an aromatic carbonate production apparatus according to an embodiment of the present invention.

Fig. 3 is a conceptual diagram showing an apparatus for producing an aromatic carbonate according to an embodiment of the present invention.

Fig. 4 is a conceptual view showing an alcohol purifying apparatus of an embodiment of the present invention.

Fig. 5 is a conceptual diagram showing a diaryl carbonate purification apparatus according to an embodiment of the present invention.

Fig. 6 is a conceptual diagram showing a diaryl carbonate purification apparatus according to an embodiment of the present invention.

Fig. 7 is a conceptual view showing an apparatus for producing an urethane urethane according to an embodiment of the present invention.

Fig. 8 is a conceptual view showing an apparatus for producing an isocyanate according to an embodiment of the present invention.

Fig. 9 is a conceptual view showing an apparatus for producing an isocyanate according to an embodiment of the present invention.

Fig. 10 is a conceptual view showing an apparatus for producing an isocyanate according to an embodiment of the present invention.

Fig. 11 is a conceptual view showing an apparatus for producing an isocyanate according to an embodiment of the present invention.

Fig. 12 is a conceptual view showing an apparatus for producing an isocyanate according to an embodiment of the present invention.

Fig. 13 is a conceptual view showing an apparatus for producing an isocyanate according to an embodiment of the present invention.

Fig. 14 is a conceptual view showing an apparatus for producing an isocyanate according to an embodiment of the present invention.

Fig. 15 is a conceptual view showing an apparatus for producing an isocyanate according to an embodiment of the present invention.

Fig. 16 is a conceptual view showing an apparatus for producing an urethane urethane according to an embodiment of the present invention.

81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94‧‧ line

705, 808, 809‧‧ ‧ storage tank

801‧‧‧film distillation unit

802, 805‧‧‧ continuous multi-stage distillation tower

803, 806‧‧ ‧ condenser

804, 807‧‧ ‧ reboiler

Claims (28)

A method for producing an isocyanate, comprising the steps of: reacting a diaryl carbonate with an amine compound to obtain a reaction mixture in a reactor for carrying out a reaction of a diaryl carbonate with an amine compound, the reaction mixture containing An aryl carbamate of an aryl ester, an aromatic hydroxy compound derived from a diaryl carbonate, and a diaryl carbonate; the reaction mixture is transported to the reactor for carrying out a reaction of a diaryl carbonate with an amine compound a thermal decomposition reactor connected by a pipe; obtaining an isocyanate by subjecting the aryl carbamate to a thermal decomposition reaction; and washing the high-boiling by-product attached to the thermal decomposition reactor with an acid; the amine compound is a polyamine compound The reaction of the diaryl carbonate with the amine compound is carried out under the condition that the stoichiometric ratio of the diaryl carbonate to the amine group constituting the amine compound is 1 or more; the diaryl carbonate is represented by the following formula (1) ) the compound represented: (wherein R ¹ represents an aromatic group having a carbon number of 6 to 12); and the amine compound is represented by the following formula (2): (wherein R ² represents one selected from the group consisting of an aliphatic group having a carbon number of 1 to 20 containing an atom selected from carbon and oxygen, and an aromatic group having a carbon number of 6 to 20, which has n equal atomic valence; n is an integer from 2 to 10); and the low boiling component formed in the thermal decomposition reaction is recovered from the thermal decomposition reactor as a gas phase component, and the liquid phase component is supplied from the bottom of the reactor Recycling. The production method of claim 1, wherein the diaryl carbonate and the amine compound are reacted in the presence of an aromatic hydroxy compound as a reaction solvent. The method of claim 2, wherein the aromatic hydroxy compound as a reaction solvent has a hydrogen atom added to the group ArO having the diaryl carbonate ArOCOOAr (Ar represents an aromatic group and O represents an oxygen atom). The structure of the compound ArOH is the same species. The production method of claim 1, wherein the reaction mixture is supplied as a liquid to the thermal decomposition reactor. The production method of claim 4, wherein the reaction mixture is supplied to the thermal decomposition reactor while maintaining the temperature in the range of 10 ° C to 180 ° C. The production method of claim 1, wherein the reaction mixture is continuously supplied to the thermal decomposition reactor. The production method of claim 1, wherein the recovery of the gas phase component and the recovery of the liquid phase component are continuously performed. The method of claim 1, wherein the isocyanate autothermal decomposition reactor obtained by the thermal decomposition reaction of the aryl carbamate is recovered as a gas phase component, and the liquid phase component containing the diaryl carbonate is supplied thereto. The bottom of the reactor is recycled. The method of claim 8, further comprising the step of recovering the isocyanate by distillation distillation separation of the gas phase component containing isocyanate recovered from the thermal decomposition reactor; and recovering the isocyanate-containing gas recovered from the thermal decomposition reactor The phase components are supplied to the distillation column in the gas phase. The method of claim 8, wherein the liquid phase component containing the diaryl carbonate is a mixture containing an aryl carbamate, and a part or all of the mixture is supplied to the upper portion of the reactor. The production method of claim 1, wherein the isocyanate obtained by the thermal decomposition reaction of the aryl carbamate is recovered from the bottom of the reactor subjected to the thermal decomposition reaction as a liquid phase component. The method of claim 11, wherein the liquid phase component recovered from the bottom of the reactor contains an isocyanate and an aryl carbamate, and a part or all of the isocyanate is separated from the liquid phase component, and a part or all of the remaining is supplied to the reaction. Above the device. The production method of claim 11, wherein the isocyanate-containing mixture recovered from the thermal decomposition reactor is distilled and separated, and the isocyanate is recovered. The production method of claim 1, wherein the type of the reactor for performing the reaction of the diaryl carbonate with the amine compound may be the same as or different from the type of the thermal decomposition reactor, and the reaction of the reaction of the diaryl carbonate with the amine compound may be carried out. The thermal decomposition reactor and the thermal decomposition reactor are selected from at least one of the group consisting of a column reactor and a tank reactor. The method of claim 14, wherein the thermal decomposition reactor is selected from the group consisting of an evaporation can, a continuous multi-stage distillation column, a packed column, a thin film evaporator, and a lowering At least one of the group consisting of membrane evaporators is constructed. The production method of claim 1, wherein the reaction of the diaryl carbonate with the amine compound is carried out in the presence of a catalyst. The production method of claim 1, wherein the thermal decomposition reaction is carried out in a liquid phase. The method of claim 1, wherein the diaryl carbonate contains 0.001 ppm to 10% of a metal atom. The method of claim 18, wherein the metal atom is selected from one or more of the group consisting of iron, nickel, cobalt, zinc, tin, copper, and titanium. The method of claim 1, wherein the diaryl carbonate is produced by the steps comprising the following steps (1) to (3): Step (1): organically having a tin-oxygen-carbon bond The tin compound is reacted with carbon dioxide to obtain a reaction mixture containing dialkyl carbonate; the step (2): separating the reaction mixture to obtain a dialkyl carbonate and a residual liquid; and the step (3): separating the carbonic acid in the step (2) The dialkyl ester is reacted with an aromatic hydroxy compound A to obtain a diaryl carbonate, and an alcohol produced as a by-product is recovered. The method of claim 20, wherein the aromatic hydroxy compound A is an aromatic hydroxy compound having 6 to 12 carbon atoms. The method of claim 20, wherein the diaryl carbonate is produced by further comprising the steps of the following steps (4) and (5): Step (4): reacting the residual liquid obtained in the step (2) with an alcohol to form an organotin compound having a tin-oxygen-carbon bond and water, and removing the water from the reaction system; and step (5): the step The organotin compound having a tin-oxygen-carbon bond obtained in (4) is reused as an organotin compound having a tin-oxygen-carbon bond in the step (1). The method of claim 20, wherein the alcohol recovered in the step (3) is used as part or all of the alcohol of the step (4). The production method of claim 1, wherein the diaryl carbonate is separated and recovered from the liquid phase component or the gas phase component recovered from the thermal decomposition reactor, and the diaryl carbonate is reused as a starting material. The production method according to claim 1 or 20, wherein the aromatic hydroxy compound is separated and recovered from the liquid phase component or the gas phase component recovered from the thermal decomposition reactor, and the aromatic hydroxy compound is used as the aroma of the step (3). The group hydroxy compound A or the aromatic hydroxy compound as the reaction solvent is reused. The production method of claim 1, wherein the amine compound is a diamine compound wherein n is 2 in the formula (2). The production method of claim 1, wherein the amine compound is supplied to the reactor for reacting the carbonate with the amine compound, and is carried out in a liquid state. The production method of claim 1, wherein the amine compound is supplied to a reactor for reacting the carbonate with the amine compound, and is carried out in a state of being a mixture with an alcohol, water, or a carbonate.