TW200948760A - Process for producing isocyanate using diaryl carbonate - 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

200948760 IX. Description of the Invention: [Technical Field of the Invention] The present invention relates to a method for producing an isocyanate using a diaryl carbonate as a raw material. [Prior Art]

Isocyanates are widely used as raw materials for the production of polyamino phthalate foams, paints, and adhesives. The main industrial manufacturing process for isocyanic acid is to react an amine compound with phosgene (phosgene method), and almost all of the world's production is produced by the phosgene method. However, the phosgene method has many problems. First, a large amount of phosgene is used as a raw material. The phosgene is extremely toxic, and in order to prevent the practitioner from coming into contact with phosgenes, special care is required in its operation, and special equipment for removing waste is also required. In the second method, in the optical method, a large amount of highly corrosive hydrogen chloride is produced as a by-product, and a treatment for removing the hydrogen chloride is required, and the isocyanate produced in the day contains a hydrolyzable gas. In the case of the isocyanide SiL S produced by the phosgene method, the weather resistance and the heat recovery of the polyurethane vinegar product may be adversely affected. In such a background, a person who wants to use a phthalosene-free isocyanate compound is expected to be a method for producing a isocyanate compound which does not use phosgene, and an example of a method for producing an isocyanate compound which does not use phosgene is mentioned. The thermal decomposition of the amino phthalic acid ester has long been known to obtain an iso- and hydroxy compound by thermal decomposition of the retinoic acid ester (for example, ##甘丄refer to Non-Patent Document 1). It is exemplified by its basic anti-shoulder. 131505.doc 200948760 R (NHCOOR% - R(NCO)a + a R<〇H (1) (wherein R represents an organic residue of a valence, and R' represents a monovalent organic residue, a It is an integer of 1 or more.) Among the aminocarboxylic acid, the aromatic carboxylic acid aryl vinegar having an aromatic group has a thermal decomposition reaction as compared with the amino acid calcined g of the S group. The temperature of H is set to be low (refer to the patent document 丨). As a method for producing a urethane sulfonate, various methods have been described so far. According to the description of Patent Document 2, it is described by benzene, second reading, and fourth. In the presence of a solvent such as vaporized carbon, the mercapto monoamine is reacted with the diaryl carbonate to obtain a corresponding alkyl monoamine carbamate in a yield of 90 to 95%, which is further in Patent Document 3: A method for continuously producing methyl phenyl carbamate with methylamine and diphenyl carbonate. ❹ However, these methods use a lower alkyl monoamine as an amine, and a method for producing an alkyl aryl carbamate is not A method for producing an alkyl polyamino phthalic acid aryl ester, which is produced from an alkyl polyamine such as an alkyl diamine or an alkyl triamine. In the case of a polyalkyl aryl carbamate, there is a problem that is completely different from that in the case of using an alkylmonoamine. The reason is that, in the case of an alkyl monoamine, it is represented by the formula (2). In addition to the reaction, a urea compound which is a by-product is formed by a side reaction represented by the formula (3) and / (4), and a polyalkylamine such as an alkyl group is a diamine. For example, a very wide variety of urea compounds such as a compound represented by the formula (7) and/or the formula (6) and/or the formula (7) which are products of the sub-131505.doc 200948760 are produced.

R*nh2 + Ακ〇Λ〇.Αγ

RWHCOOAr + ArOH 2 R'NH2 A 人_ΑΓ (2) Ο R,, person..

R' + 2 ArOH R'NH2 + R'NHCOOAr

O h2n^r-nh4_nh^_r^nh2 (3) (4) (5)

O o o R'—NH-C-OAr (6)

Ar〇-C-HN+-R*~NH-^NH\ R,_ o II NH-C-OAr (7) (wherein R represents a monovalent alkyl or aromatic group,

Ar represents a monovalent aromatic group, and p, q, and Γ respectively represent an integer of 1 or more). That is, 'there is a problem that the yield of the alkyl polyamino carboxylate as the target compound is lowered due to the by-product reaction of the various urea compounds, etc.'; 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, there have been very few attempts to produce alkyl polyaminocarbamate from alkyl polyamines and diaryl carbonates, but several reports have been made. 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 amount of benzene 131505 is proposed. Doc 200948760; a solution in which 1 mol of 1,6-hexa-1f-diamine is dissolved in 5 times of benzene is added dropwise to the solution, and the reaction is carried out while stirring at 8 Torr. According to the patent specification, it is described that in order to carry out the reaction favorably, an important hydrazine can be used as a product, and hexamethylenediamine benzoate is not used; As the reaction solvent, as such a solvent, a hydrocarbon such as a benzene or a benzene is preferable. Ο Ο From this point of view, in Non-Patent Document 3, 0.01 mol of diphenyl carbonate and 〇〇〇5 mol of 1,6-hexa are used by using 4 lysine as the reaction solvent. The methyldiamine was reacted for up to 2 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 polyglycine 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 diamino phthalic acid vinegar 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. In the case of Patent Document 6, there is described a method in which a diaryl carbonate is reacted 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: an aromatic amine and a diaryl carbonate in the presence of a Lewis acid catalyst, 131505.doc 200948760 at a temperature of 14 (TC~23 (TC) In the 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. In Patent Document 8, 'the manufacturing method of the alkyl polyamino aryl ester is described'. In the case where the alkyl polyamine is reacted with a diaryl carbonate to produce an aromatic aryl carbamate, 1 to 3 equivalents of diaryl carbonate are used per 1 equivalent of the amine group of the polyamine. The aromatic hydroxy compound is used as a reaction solvent to carry out the reaction in a substantially homogeneous dissolved state. According to the patent document, it is usually 96% or more, and in a preferred embodiment, it is 98% or more. The rate is obtained as an alkyl aryl aryl ester. However, although it is a very small amount, it is confirmed that a urea compound is formed, so that the formation of a urea compound cannot be completely avoided. On the other hand, in the thermal decomposition reaction of the urethane, it is easy At the same time, various irreversible side reactions such as a thermal modification reaction of a urethane defect or a condensation reaction of an isocyanate produced by the thermal decomposition occur, and examples of the side reaction are represented by the following formula (8). The reaction for forming a urea bond, ❹ or a reaction for producing a carbodiimide represented by the following formula (9), or a reaction for producing an isocyanurate represented by the following formula (10), for example (refer to Non-patent literature 1, 2). [Chemical 3] || || ^| |_| || |_| || 卜NCO-R. + R*—OCN—R ^ R—NC—N—R + R .—〇-C—〇—R. ( 8 ) R~N=C=0 + 0=C=N—R —R—N=C=N—R + C〇2 (9) 1315〇5.{ J〇, •10· 200948760 (1 0) The reduction of these side reactions not only leads to a decrease in the yield or selectivity of the target lyophilic acid, but also makes it difficult to long-term occlusion of the reactor, especially in the manufacture of polyisocyanates. In the case of the operation, the method of producing a solid is used as a method for producing isocyanic acid based on amino carboxylic acid vinegar, and various methods have been proposed.

= Manufactured according to the special two, aromatic diisocyanate (tetra) and / or polyisocyanate Γ two steps. Specifically, in the first step, an aromatic amine and/or an aromatic-grade polyamine and a urethane amide are used in the presence or absence of a catalyst, and in the presence or absence of a knee and an alcohol. The hydrazine reaction is carried out to form an aryldiaminecarboxylic acid brewing and/or an arylpolyurethane carboxylic acid, 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 aryldiaminecarboxylic acid S and/or an arylpolyaminocarbazole.

There are several methods known for the production of relative isocyanide (tetra) and alcohol by thermal decomposition of (cyclic) aliphatic groups, and especially aromatic monocarbamates and diaminocarbamic acids. 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 of the compound produces, for example, the above-mentioned side reaction, forming a precipitate, a polymer-like substance and a plug in the reactor and the recovery device, or, in addition, the substance forms a fixing on the wall surface of the reactor. When the isocyanate is produced in a time, the economic efficiency is poor. 131505.doc 200948760 In this chemical method, the yield of thermal decomposition of carboxylic acid vinegar is described, for example, as (1) or as a catalyst (see Patent Document 12). / The catalyst of the composition of the chlorinating agent (refer to Patent Document 13 of the patent document , ,, as hexamethylene diisocyanate, the method of carrying the following method: dibenzyl toluene used as a solvent ???========================================================================================== The purification and random recovery of the solvent and the catalyst mixture are not described in any detail, so the economic efficiency of the method cannot be judged. According to the method described in Patent Document U, the aminocarboxylic acid can be used without a catalyst. It is easily decomposed into isocyanic acid and alcohol in a carbon-containing fluidized bed. Further, according to the description of Patent Document 15, the hexamethylene sulfonate-based urethane carboxylic acid can be contained, for example, in carbon, copper or yellow. In the presence or absence of copper, steel, rhetoric, m or quartz gas permeable packaging materials, it decomposes in the gas phase to produce hexamethylene diisocyanate at more than 3 Torr (: 2 temperature). Vinegar. According to Patent Document 14, the method is based on hydrogen autochemistry and/or This is carried out in the presence of a denture donor. However, this method cannot achieve a yield of hexamethylene diisocyanate of 9 % or more. The reason is that a part of the decomposition product is bonded again to form an amino phthalate bond. Further, it is necessary to further purify the hexamethylene diisocyanate by steaming, which often causes an increase in yield loss. Further, Patent Document 16 describes the case where the temperature is lower at 131505.doc -12- 200948760 The monocarbamate can be decomposed in a good yield without using a solvent under an advantageous reduced pressure in the presence or absence of a catalyst and/or a stabilizer. The decomposition product (monoisocyanate) And brewing alcohol, which is removed by steaming from the reaction mixture of the turpentine, and separately collected by condensation, respectively. It is described in a common form, in order to remove by-products formed in thermal decomposition. Partial removal of the reaction mixture. Therefore, by-products can be removed from the bottom of the reactor, but the problem of fixing to the wall of the reactor is still left, and it is not solved for long-term operation. Further, there is no description on the industrial application of the residual portion (containing a large amount of useful components). Patent Document 17, Aliphatic, Feed or Aromatic Polyurethane The thermal decomposition is carried out in the presence of an inert solvent in the presence of an inert solvent in the presence of an inert gas solvent, a gasification gas, an organic acid gasification, a hospitalization agent or The by-product produced in the presence or absence of the organotin vapor, for example, can be continuously Q removed from the reactor together with the reaction solution while adding a corresponding amount of new solvent or recovered solvent. The disadvantage of this method is that For example, due to the use of a reflux solvent, the space production of the polyiso-acid acid is reduced, and, for example, a large amount of energy is required to recover the solvent. Further, the auxiliary agent used is volatile under the reaction conditions, and can be decomposed and decomposed. Things. Further, there is a question about the economic efficiency and the reliability of the industrial method with respect to the amount of the residual portion of the produced polyacetoic acid vinegar. Patent Document 18 describes an amino carboxylic acid vinegar supplied from the inner surface of a tubular reactor in the presence of a high boiling point solvent, for example, an alicyclic carboxylic acid vinegar 5-(ethoxygalamino)-H ethoxy group Aminomethyl 131505.doc 13 200948760 t , 3 - dimethylcyclohexene - a method of continuous thermal decomposition. This method has the disadvantage of producing a lower yield of (cyclo)aliphatic diisocyanate and having a lower selectivity. Further, regarding the continuity of the recovery of the aminocarboxylic acid which has undergone re-bonding or partial decomposition, there is no description about the post-treatment with a solvent containing by-products and a catalyst. ❹ ❹ It is easy to imagine that the above-mentioned method for producing amino carboxylic acid aryl s and the method for producing isocyanate by thermal decomposition of amino carboxylic acid vinegar can be combined, and the diaryl carbonate and amine compound can be used as a raw material. Make isocyanate vinegar. However, in order to combine the above-described method for producing the aryl carbamate aryl ester with the method for producing an isocyanate by thermal decomposition reaction of an aryl carbamate aryl ester, any one of the methods such as τ 彳 is used: self-made diaryl vinegar a reaction solution obtained by reacting with an amine compound, separating an amino aryl decanoate, and performing a complicated operation of the thermal decomposition reaction of the amino carboxylic acid aryl vinegar; or directly preparing a reaction liquid obtained by producing an aryl urethane A method for thermal decomposition reaction. In this regard, Patent Document 19 describes a method of reacting an aromatic amine with a diaryl carbonate 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 this patent document, there is exemplified a method in which an amine-containing formic acid vinegar reaction liquid obtained by reacting an amine compound with diaryl carbonate in the presence of a Lewis acid catalyst is used for the synthesis of the aminocarboxylic acid g. The reactor was subjected to a thermal decomposition reaction to produce an isocyanate. [Patent Document 1] US Pat. No. 399,243, pp. [Patent Document 2] Japanese Patent Application Publication No. SHO-52-71443, No. s. [Patent Document 5] Japanese Patent Application Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. [Patent Document 8] Japanese Patent No. 4290970 (Patent Document 10) US Patent No. 2692275 (〇 Patent Document 11) US Patent [Patent Document 12] US Patent No. 4,081,472 [Patent Document 13] US Patent No. 43 88426 [Patent Document 14] US Patent No. 4482499 [Patent Document 15] US Patent No. 4,613,466 [ Patent Document 16] US Pat. No. 4,384,033 [Patent Document 17] US Patent No. 43 88246 [Patent Document 18] US Patent No. 4,692,550 [Patent Document 19] Japanese Laid-Open Patent Publication No. 2004-262835 [Non-Patent Document 1] Berchte der Deutechen Chemischen Gesellschaft, Vol. 3, 653, 1 870 [Non-Patent Document 2] Journal of American Chemical Society, Vol. 81, p. 2138, 1959 [Introduction to 1J Literature 3] Journal of Polymer Science Polymer Chemistry Edition, Vol. 17, 835, 1979 [Invention] 131505.doc -15- 200948760 [Problems to be solved by the invention] However, due to the amine group Since the synthesis reaction and the thermal decomposition reaction of the formate compound are carried out in the same reactor, it is not possible to select a reactor or a reaction condition corresponding to the synthesis reaction and the thermal decomposition reaction of the urethane compound, respectively. Actually, according to the exemplification of Patent Document 丨 9, the yield of isocyanate is low. Further, in Patent Document 19, there is no detailed description relating to the method of continuously producing isocyanate, and it is not satisfactory from the viewpoint of industrially producing isocyanate efficiently. As described above, the present invention is a method for producing an aryl urethane by using a diaryl carbonate and an amine compound as a raw material to produce an isocyanate via the urethane urethane. The problems to be solved are numerous, and industrialization has not yet been achieved. 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 any problems encountered in the prior art. [Means for Solving the Problem] The inventors of the present invention have conducted intensive studies on the above problems, and as a result, have found a method for producing isocyanic acid vinegar which is obtained by reacting a diaryl carbonate with an amine compound under specific conditions. The mixture is transported to a thermal decomposition reactor under specific conditions to thermally decompose the guanidinium aminoformate contained in the mixture to produce an isocyanate, thereby completing the present invention. That is, the present invention provides, [1] a method for producing isocyanic acid vinegar, comprising the steps of: reacting a diaryl carbonate with an amine compound in a reactor for performing a reaction of a diaryl carbonate with an amine compound; Obtaining a reaction mixture comprising an aryl carbamate having an aryl group 131505.doc -16·200948760 from a diaryl carbonate, an aromatic hydroxy compound derived from a diaryl carbonate, and a diaryl carbonate; transporting the reaction mixture In the thermal decomposition reactor, wherein the thermal decomposition reactor is connected to the reactor for carrying out the reaction of the diaryl carbonate with the amine compound by a pipe; and by thermally decomposing the amino aryl phthalate And isocyanate si is obtained. [2] The method of producing the item [1], further comprising the step of acid-cleaning the high-boiling by-product attached to the thermal decomposition reactor. [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 Ar〇H, and the compound Αγ〇η is formed to constitute the diaryl carbonate Ar〇CO〇 Ar (Ar is an aromatic group, a non-oxygen atom of a quinone) is a structure in which a hydrogen atom is added to ArO. [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 1 Torr to 180 °C. [8] The production method according to any one of [1] to [7] wherein the 131505.doc 200948760 reaction mixture is continuously supplied to the thermal decomposition reactor. [9] The production method according to any one of [1] to [8] wherein the low-boiling component formed in the thermal decomposition reaction is recovered as a gas phase component from a thermal decomposition reactor, and the liquid phase component is obtained. It is recovered from the bottom of the reactor. [10] The production method according to the above [9], wherein the recovery of the gas phase component and the recovery of the liquid phase component are continuously performed. [11] The production method according to the above [9] or [10], wherein the isocyanate vinegar autothermal decomposition reactor obtained by the thermal decomposition reaction of the amino phthalic acid vinegar is used as a gas phase component It is recovered and the liquid phase component containing the diaryl carbonate is recovered from the bottom of the reactor. [12] The 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 the distillation column to recover the isocyanic acid S, and the autothermal decomposition reaction The gas phase component containing the isocyanate recovered by the reactor is supplied to the distillation column in the gas phase. [13] The method according to the above [11] or [12] wherein the liquid phase component containing a diaryl carbonate contains a mixture of an 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 amino aryl phthalate is recovered as a liquid phase component from the bottom of the reactor subjected to the thermal decomposition reaction. . [15] The production method according to [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, and one or both of the remaining components are left. It is supplied to the upper part of the reactor. [16] The method of manufacturing according to [14] or [15], wherein the isocyanate-containing mixture recovered from the thermal decomposition reactor is distilled and the isocyanate is recovered. [1] The production method according to any one of [1] to [16] wherein the type of the reactor for performing the reaction of the diaryl carbonate with the amine compound is the same as the type of the thermal decomposition reactor. The reactor in which the reaction between the diaryl carbonate and the amine compound is carried out differently, and the thermal decomposition reactor is selected from at least one of the group consisting of a column reactor and a tank reactor. [18] The method of manufacturing according to [17], wherein the thermal decomposition reactor is 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. Composition. [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): [Chemical 4] r'〇A〇*r1 ( Id (wherein R1 represents an aromatic group having a carbon number of 6 to 12). The method according to the above [21], wherein the diaryl carbonate contains a metal atom of 〇〇〇1 ppm to 10%. [23] The method according to the above [22], wherein the metal atom is selected from the group consisting of 131505.doc 19-200948760 iron, nickel, cobalt, zinc, tin, copper species 0, titanium, or a plurality [ [24] The production method according to any one of [1] to [23], which comprises the steps of the following steps (1) to (3), wherein the diaryl carbonate is produced by the manufacturer: Step (1) : reacting an organotin compound having a tin-oxygen-carbon bond with carbon dioxide to obtain a reaction mixture containing dialkyl carbonate. Step (2): separating the reaction mixture to obtain carbonic acid _ 咴 咴 文 文 烷And residual hydrazine; Step (3): reacting the dialkyl carbonate separated in the step (2) with the aromatic sulfhydryl compound to obtain a recovery of the diaryl vinegar The product I is an alcohol. [25] The aromatic hydroxy compound a in the production method of the above [24] is an aromatic hydroxy compound having a carbon number of 6 to 12. [26] as in the above [24] or [25] Manufacturing method, wherein

The diaryl carbonate is produced by further comprising the steps of the following steps (4) and (7): Step W: reacting the residual liquid obtained in the step (7) with an alcohol to form a tin-oxygen-carbon bond. The organotin compound and water are removed from the reaction system; Step (5): the organotin compound obtained in the step (4) and obtained by the right sister #丹有锡虱-carbon bond is used as the step (1) The tin-oxygen-carbon bond is hard <organic tin compound and reused. [27] The production method according to the above [26] wherein the alcohol recovered in the step (3), 131505.doc -20-200948760, is used as a part or all of the alcohol of the 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 autothermal decomposition reactor. The aryl ester is reused as a starting material. [29] The method of producing [A] or [24], wherein the aromatic hydroxy compound is separated and recovered from a liquid phase component or a gas phase component recovered from the thermal decomposition reactor, and the aromatic hydroxy compound is used as the The aromatic hydroxy compound A of 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): R 2 (nH 2 ) n (12) (wherein R represents a selected from the group consisting of One of a group consisting of an aliphatic group of carbon (4) and an aromatic group having a carbon number of 6 to 20, which has an atomic valence equal to η; 'η is 2 to 10 The integer). [32] The production method according to the above [31], which is a diamine compound of 2. The method of producing the η mesh according to any one of the above items (1) to [32], wherein the amination is carried out to a state in which the carbonate is reacted with the amine compound. In the reactor in which the reaction is carried out, it is a method for producing a cup according to the above [1] to [33], wherein the amination of the σ substance to the reaction of reacting the analytic acid with the amine compound for 8 days is carried out. (4) It is carried out in a state of being mixed with alcohol, water, or carbonic acid. [Effect of the Invention] By the method of the present invention, an isocyanate can be produced continuously for a long period of time and in a good yield with a diaryl carbonate and an amine compound as a raw material. [Embodiment] 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 following embodiments, 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 vinegar carbonate. a step of reacting an aryl carbamate, a reaction mixture of an aromatic hydroxy compound 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 a compound represented by the following formula 131505.doc -22- 200948760 (13). [Chemical 6]

(13) (wherein R1 represents an aromatic group having a carbon number of 6 to 20).

❹ As Ri of the above formula (13), an aromatic hydrocarbon group having a carbon number of 6 to 2 Å is preferable, and a material (4) having a Wei of 6 to U is more preferable. It is considered that the carbonic acid diaryl vinegar having an aromatic hydrocarbon group having a carbon number of 2 UX is considered to be better from the viewpoint of separation of isocyanic acid vinegar which is formed by thermal decomposition reaction of amino carboxylic acid vinegar as follows. The carbon number constituting R1 is 2 Å or less. Examples of such R1 include a phenyl group, a methylphenyl group (each isomer), an ethylphenyl group (each isomer), a propylphenyl group (each isomer), and a butylphenyl group. (each isomer), pentylphenyl (each isomer), hexylphenyl (each structure), dimethylphenyl (each isomer), mercaptoethyl stupyl (isoisomer) Methyl propyl phenyl (each isomer), methyl butyl phenyl (each isomer, decylpentyl phenyl (each isomer), diethyl phenyl (each isomer), ethyl Propyl phenyl (each isomer), ethyl butyl phenyl (each isomer), dipropyl phenyl (each isomer), tridecyl phenyl (each isomer), triethyl Phenylphenyl group (each isomer), naphthyl group (each isomer), etc. Among these divalent carbonic acid, one of the S days, the preferred 疋R is %I number is ό~8 The nicotinyl carbonate--anthracene ester, as such a diaryl carbonate, may be exemplified by diphenyl carbonate and di(methylphenyl vinegar) (each isomer (mercaptoethylphenyl) ester (each Isomers, etc. 131505.doc -23- 200948760 It is better to be such The acid diaryl ester contains a metal atom in a range of preferably 0.001 ppm to 10%, more preferably 0.001 ρ ρηι 5%, and further preferably 0.002 ppm to 3%. Further, the metal The atom may exist as a metal ion or as a metal atom. As the metal atom, it is preferably a metal atom which may be a divalent or tetravalent atom, wherein 'better is selected from iron, cobalt, One of or a plurality of metals such as nickel, zinc, tin, copper, and titanium. The inventors of the present invention were surprised to find that if a diaryl carbonate containing a metal atom in a concentration within the above range is used, carbonation is suppressed. The effect of the modification reaction of the aryl urethane formed by the reaction of the diarylate with the amine compound. The mechanism for achieving such an effect is not clear, but the inventors have speculated that 'the metal atoms are coordinated to the reaction. The urethane bond (_nhcoo-) of the amino phthalate ester formed in the above stabilizes the urethane bond, thereby inhibiting, for example, the above formula (4), formula (8), and the like Side reaction. Also 'delivered with amine groups as described below In the case of the reaction solution of the acid aryl ester, the effect of suppressing the modification reaction of the aryl carbamate aryl ester by the metal atom is also determined. The mechanism is also different from the above. ❹ It is expected to be produced by mixing a diaryl carbonate with an amine compound. When the mixture is further added to the above-mentioned range of the above-exemplified metal atoms in the above range, the same effect can be obtained, but the inventors of the present invention conducted an effort to find out that it is only in the mixture of the diaryl carbonate and the amine compound. When the metal atom is added, it is difficult to obtain the above effects. The reason for this is not clear, but the inventors of the present invention presume that when the diaryl carbonate contains a metal atom, the diaryl carbonate is coordinated to the metal atom, as opposed to Therefore, when a metal atom is added to a mixture of a diaryl carbonate and an amine compound, the metal atom and the amine compound interact more strongly than the 131505.doc •24·200948760 metal atom interacts with the amine compound. Therefore, the metal humiliation and the substance are firmly coordinated to the amine compound, and it is difficult to match the amino carboxylic acid vinegar bond of the formed amino carboxylic acid aryl vinegar.The acid-breaking g of the present embodiment is preferably produced by the method described below, and in the case where the metal anaerobic diaryl vinegar of the method is contained in the above preferred range, if the metal atom is not included in the above preferred range, The diaryl carbonate can be used directly. When the amount of the metal atom contained in the cesium carbonate is less than the above range, the metal atom may be added in other manners, for example, as an organic acid cesium such as an acetate or a guanidinium sulphate, and a sputum I vapor, B. Add the hydrazine acetone complex. Moreover, when it is more than the above range, for example, the amount of the metal atom can be reduced to the above range by a method such as solvent cleaning, vapor purification, crystallization, removal by ion exchange resin, or removal by an integrated resin. And use. Further, in the case of the metal atom contained in the above range in the diaryl vinegar, it is basically determined that it does not have the catalytic action of the reaction of the diaryl aryl carbonate with the amine compound, and therefore, it should be combined with the following aminocarboxylic acid. 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. 131505. doc - 25 - 200948760 Preferably, 'the following method is employed: a compound having a tin-oxygen-carbon bond is reacted with carbon dioxide to produce a carbonate. A diaryl carbonate is produced from the carbonate and an aromatic mercapto compound. Namely, 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) Alkyl ester separation step) a step of separating the mono-carbonic acid monoester from the reaction mixture and obtaining a residual liquid; Step (3): (diaryl carbonate production step) to separate the monoalkyl carbonate in the step (2) The reaction with the aromatic hydroxy compound A is carried out to obtain a step of recovering the alcohol formed as a by-product from the diaryl sulfonium carbonate. 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 same from the reaction system Step of water; Step (5) · (Reuse step) The organotin compound having a tin-oxygen-carbon bond obtained in the step (4) is used as a step 〇) having a tin-oxygen-carbon bond The step of recycling the organotin compound. As the organotin compound used in the step (1), a dialkyltin compound is preferably used. The dialkyltin compound refers to an organotin compound having two substituents bonded to a tin atom. Examples of the dialkyltin compound include a dialkyltin compound selected from the group consisting of the following formula 131505.doc •26·200948760 (14) and a tetraalkyl group represented by the following formula (15). At least one selected compound of the group consisting of a stannous oxide compound. % [Chemical Formula 7] R3a-Sn--χ2^ (1 4 ) (wherein R and R are independently represented by a linear or branched alkyl group having 1 to 12 carbon atoms; X1 and X2 are independent Representing at least one substituent selected from the group consisting of an alkoxy group, a decyloxy group, and a pixel atom; a and b are integers of 〇~2, respectively, a+b=2; c and d are respectively 〇~2 Integer, c+d=2). [化8]

(15) (wherein R, R, R7 and R8 each independently represent a linear or branched alkyl group having 1 to 12 carbon atoms; X and X are not selected from alkoxy groups, decyloxy groups and At least one substituent in the group consisting of halogen atoms; e, f, g, h are integers of 〇~2, respectively, e+f=2, g+h=2). 131505.doc •27-200948760 R5 and R4 as a dialkyltin catalyst represented by the above formula (14), and R5 and R6 of a tetraalkyldistannoxane compound represented by the above formula (15) Examples of R7 and R8 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), dodecyl (each isomer), etc. The number of carbon atoms in the group is an alkyl group as an aliphatic hydrocarbon group selected from an integer of from 1 to 12. More preferably, the number of carbon atoms constituting the group is a linear or branched alkyl group selected from an integer selected from the group, and the number of carbon atoms constituting the group may be a range other than the range shown above. The second is a base-tin compound, 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. The oxime and X2 of the dialkyltin compound represented by the above formula (14) and the & and χ4 of the tetraalkyldistannoxane compound represented by the formula (15) represent an alkoxy group selected from When at least the hydrazine substituent in the group consisting of a decyloxy group and a halogen atom is in the case of an alkoxy group and/or a methoxy group, it is preferred that the number of carbon atoms constituting the group is selected from hydrazine. ~! The base of an integer of 2. As such an example, an oximeoxy group, an ethoxy group, a propoxy group (each isomer) 'butoxy group (each isomer), a pentyloxy group (each isomer), a hexyloxy group ( 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 constitute a methoxy group, a gas group, a bromine group and the like dentate element 131505.doc -28- 200948760. In consideration of fluidity or solubility, it is considered to be used as a catalyst for producing carbonated vinegar, and as a further preferred example, an alkoxy group having a carbon number of 4 to 6 is used. ❹ Ο As an example of the dialkyl tin compound represented by the formula (14), dimethyl-dimethoxy tin, didecyl-diethoxy tin, dimethyl tin (isomeric , dimethyl-dibutoxytin (each isomer), dimethyl-dipentyloxytin (each isomer), dimethyl.dihexyloxytin (each isomer) Dimercapto-diheptyloxytin (each isomer), dimethyldioctyloxytin (each isomer), dimethyl-dimethoxytin (each isomer), dimethyl Base-dimethoxytin (each isomer), dibutyl-dimethoxy tin (each isomer), dibutyl'-di-diethoxytin (isomeric), dibutyl Dipropoxytin (each isomer), = butyl-dibutoxytin (each isomer), dibutyl-dipentyloxytin (isomeric oxime) iso-dihexyloxy Base tin (each isomer), dibutyl bis heptyl tin oxide oxime), dibutyl _ dioctyl tin (each isomer), dibutyl dimethoxy tin (each Isomer), dibutyl-dimethoxytin (each isomer), dioctyl-dimethoxytin (isomeric), dioctyl-di-B Base tin (each), dioctyl-dipropoxytin (each isomer), dioctyl-dibutoxytin (each isomer), dioctyl-dipentyloxytin (each Isomers), dioctyl bis-yltin (each isomer), dioctyl-diheptyloxy tin (each isomer), = octyloxy tin (isomeric), two辛基_二壬物), - 辛八土土 tin (isomeric) monooctyl-monodecyloxy tin (each isomer) and other two-form base lock, dimethyl-diethyl oxy tin , dimethyl dipropylene oxide 2), dimethyl-butadienyl tin oxide (isomeric /, tin (each isomer), dimethyl-di (twelbic oxygen 2) tin ^ Base-brewed oxybutyl-diethyloxy kick (each isomer), dibutyl-dipropene on 131505.doc -29- 200948760 isomer), dibutyl·dibutyl Oxytin (each isomer), dibutyl-dioxanyloxy; (: isomer), dibutyl-bis(dodecanoxy) tin (isoisomer)-octyl-di Ethyl tin oxide (each isomer), 2 octyl-dipropane tin oxide (iso-isomer), dioctyl-dibutyl oxy tin (iso-isomer), dioctyl-pentyl Tin oxytin (each isomer) ), dioctyl. II (tweldium isomer), etc., diterpene-di-oxytin, dimethyl-di-sulphide, di-basic-tin-tin, di-butyl-di-gasification Tin (each isomer), dibutyl Ο ❹ ❹ tin (each isomer), dioctyl-tin dichloride (each isomer), dioctyl-dibromide (isoisomer) Dialkyl, bidentate, etc. Among these, preferred are dimethyl-dimethoxy tin, dimethyl-diethoxytin-methyl-dipropoxytin (each isomer), and dimethyl-dibutyltin. (each isomer), dimethyl-dipentyloxytin (each isomer), xylylene dihexyltin (each isomer), dimethyl diheptyloxy tin (isomeric Physicochemical, bis-octyloxytin (each isomer), dimethyl-dimethoxy tin (each isomer), monomethyl-dimethoxy tin (each isomer), two Butyl-ditin (each isomer), dibutyl-diethoxytin (each isomer), dibutyldipropoxide (each isomer), dibutyl-dibutoxide Base tin (each isomer II:) base tin (each isomer), dibutyl·dihexyloxytin (isomeric aw-heptyloxytin (isomeric), dibutyl _Dioctyloxytin (widely isomer), dibutyl-dimethoxytin (each isomer), dibutyl-dioctadecyltin (each isomer) 'dioctyl-dimethoxy Base tin (each isomer), two: = diethoxy tin (each isomer), dioctyl-dipropoxy tin (isomeric (different:: tin oxide (each isomer) ), dioctyl-two Pentyl pentoxide (each isomer), dioctyl-dihexyloxytin (each isomer), dioctyl-di-g-goxide 131505.doc 200948760 tin oxytin (isomeric), dioctyl -Dioctyl-dioctyltin (each isomer), dioctyl-dimethoxytin (each isomer), dioctyl-dimethoxytin (each isomer) Alkoxytin, among which, more preferred are dibutyl-dipropoxytin (each isomer), dibutyl-dibutoxytin (each isomer), dibutyl-dipentyloxy Base tin (each isomer), dibutyl-dihexyl tin (each isomer), dibutyl-monoheptyl tin (each isomer), dioctyl-dipropoxy tin (each isomer), dioctyl-dibutoxytin (each isomer), dioctyl-dipentyloxytin (each isomer), dioctyl-dihexyloxytin (each a dialkyl-dialkyloxy tin such as an isomer) or a dioctyl-diheptyloxytin (each isomer), and further preferably a dibutyl decyl-dibutoxy tin (isomeric , dibutyl-dipentyloxytin (each isomer), monobutyl-dihexyloxytin (each isomer), dibutyl- Heptyltin (each isomer), dibutyl-dioctyl tin (each isomer), dioctyl-dibutoxytin (each isomer), dioctyl-dipentoxide Base tin (each isomer), dioctyl-dihexyl tin (each isomer), dioctyl-diheptyl tin (each isomer), dioctyl-dioctyl tin (Dimers) The dialkyl tin compound represented by the above formula (14) exhibits a monomer structure 'but may also be a multimeric structure or an association. As the four represented by the formula (15) Examples of the alkyl dialkoxy distannoxane include 1,1,3,3-tetradecyldidecyloxydistannoxane, and u,3,3_tetramethyl-1,3-di Ethoxy distannoxane, ^, 弘 曱 ^ ^, 夂 dipropoxy distannoxane (each isomer), 1,1,3,3-tetramethyl-1,3-di Butyryl distannoxane (each isomer), M,3,3-tetramethyl-1,3·dipentyloxydistannoxane (each isomer), μ, 3,3-tetramethyl _丨, 3_dihexyloxystannane (each isomer), 1,1,3,3-tetramethyl-pyridyldiheptyloxydistannoxane (isomeric 131505.doc • 31 - 200948760 , 1,1,3,3-tetramethyl-1,3-dioctoxydistannoxane (each isomer), 1,1,3,3-tetradecyl-1,3- Dimethoxy distannoxane (each isomer), 1,1,3,3-tetramethyl-I,3-didecyloxydistannoxane (isomeric), 1.1.3.3- Tetrabutyl-1,3-dimethoxydistannoxane (each isomer), 1,1,3,3-tetrabutyl-1,3-diethoxydistannoxane Structure), 1,1,3,3-tetrabutyl-1,3-dipropoxydistannoxane (each isomer), 1.1.3.3-tetrabutyl-1,3-dibutoxy 1, octane oxane (each isomer), 1.1.3.3-tetrabutyl-1,3-dipentyloxystannane (each isomer), Ο 1,1,3,3-tetrazide -1,3-dihexyloxystannane (each isomer), 1,1,3,3-tetrabutyl-1,3-diheptyloxydistannoxane (isoisomers) , 1,1,3,3-tetrabutyl-1,3-dioctoxydistannoxane (each isomer), 1,1,3,3-tetrabutyl-1,3-di Decyloxystannane (each isomer), 1,1,3,3-tetrabutyl-1,3-didecyloxystannane (each isomer), 1,1,3 ,3-tetraoctyl-1,3-dioxaoxydithion (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 (isomers) 1,1,3,3-tetraoctyl-1,3-dipentoxydistannoxane (each isomer), 1.1.3.3-tetraoctyl-1,3-dihexyloxyditin Oxystane (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-dimethoxyoxydistannoxane (each isomer), 1, 1,3,3-tetraoctyl-1,3-dimethoxyoxystannane (each isomer), etc. 1,1,3,3-tetraalkyl-1,3-dialkoxy- Distannoxane, 1,1,3,3-tetradecyl-131505.doc -32- 200948760 1'3-Diethoxydecyloxanediolybdenum (all isomers), 113 four 'Diyl 仏 dipropenyloxyoxylated (four) structure), U3;, A:, 3 · dibutyl oxyditin (each isomer, tetracene · 1,3 · pentaneoxy Di-n-oxoxane物))1,1,3,3-四甲一一/_!__ * (in each case, soil _, one (dodecyloxy) distannoxane: sputum), 1'1, 3,3-tetrabutyl_1>3_diethyloxydi tin isomer), 1,133-tetrabutyl, 1,1,3, dipropene, oxydix, gas, f -Limang), 1,1,3,3-tetrabutyl_13·dibutyl g_oxo (each isomer' rolling base-stannoxaline (isomeric oxime), 1, 1,3,3-tetrabutyl_ι 3_ - & sulphate) s), pentane succinyl octoxide (each isomeric MW-tetrabutyl {3 - bis(dodecyloxy) chlorination (isomeric 1,1'3,3-tetraoctyl qj·diethoxynonantaxane) (isomeric U'3'3-four Octyl dipropenyloxydistannoxane (isomeric 1,1,3,3-tetraoctyl-indole 3) dibutyloxane distannoxane (isomeric 1,1,3, 3-tetraoctyldipentyloxydistannoxane (isomeric * 1,1,3,3-tetraoctylindole, 3-di(dodecyloxy)distanthanane (variety) Structure), etc. 1,1,3,3-tetraalkyl-indole, 3-dimethoxyoxydistannox, m3 tetramethyl-13-dichloro Oxyalkane, i-mountain 3,3_tetradecyldioxadistannoxane, 1,1,3,3-tetrabutyl-1,3·di-diisostannane (isomers), tetrabutyl {3-dibromodistannoxane (each isomer), ^^^tetraoctyl-1,3-dichlorodistannoxane (each isomer), u, 3,3_tetraoctyl U,3,3-tetraalkyl-1,3-dihaloxystannane such as bismuth, 3_dimoxetane (each isomer). Among these, 1,1,3,3-tetradecyl-1,3-didecyloxydixanthene, 1,1,3,3-tetradecyl-1,3- is more preferred. Diethoxytin oxide, 1,1,3,3-tetradecyl-1,3-dipropoxydistannoxane (isomers), 1,1,3,3-tetramethyl Base - 131505.doc -33- 200948760

】, 3-dibutoxydistannoxane (each isomer), u, 3,3 • tetramethylpentaloxydistannoxane (isomeric), soil, - - tin oxide (each isomer), U, 3 ~ Yinji _!, 3-dihexyloxyalkane (each isomer), 1,1,3,3-tetraf-based soil, _-heptyloxyditin Oxygen isomer), i,l,3,3-tetraroyl-l3 _'3-octyloxydistannoxane (each), 1,1,3,3-tetraf-based"••2 Di-decyloxydistannoxane (isomeric.-U.s.-di-di-dioxydi-x-oxygen (each isomer), base-U·diethoxy]; Isomer)

1, ί, 3, 3_ four 1,1,3,3-four 1,1,3,3-four 1,1,3,3-four 1,1,3,3-four 1,1,3, 3-tetra 1,1,3,3-tetra 1,1,3,3-tetra 1,1,3,3' tetra 1,1,3,3-tetraoxane (each isomer), tin Oxystane (each isomer), stannous oxide (each isomer), stannous oxide (each isomer), stannoxane (each isomer), stannoxane (each isomer), xin Oxydistanoxane (each isomer), nonyloxystannal (each isomer), 1133 πα立# 癸 二 octoxide (isomer), i, · ί ,·3-tetraoctyl} U,3,3-tetraoctyl-diethyl=distannium oxime (each isomer), ! 1 3 ^ Pellets-monostannoxane (isomers), M,3'3-tetraoctyl], 3_II113·, ^propoxydistannoxane (each isomer), hydrazine, 1,3,3·tetraoctyl-1,3-dibutyl&amp ; * 1 1 .. oxydistannoxane (each isomer), 1'1,3,3-tetraoctyldodeto-dioxaoxydistannoxane (each isomer), 1 mountain) , 3-tetraxinmei, 1-hexyloxydistannoxane (each isomer), - Sixinyi 1 〇_,,,, _,·二Heptyloxystannane (each isomer), 1,1,3'3-tetraoctyl q 3 -octyl distannoxane (each isomer), thio-U-dipropoxy-1 ,3-dibutoxy-1,3.dipentyloxy-1,3-yl-l,3-yl- 1 ,3-yl-1,3-yl-1,3-hexyloxyglycol Oxylate 131505.doc •34· 200948760 1,1,3'3-tetraoctyl_i,3_didecyloxystannane (isomers), 1,1,3,3-tetraxin 1,1,3,3-tetraalkyldialkoxy-distannoxane, such as 丨, 3_dimethoxy distannoxane (each isomer), wherein, further preferably 1, 1,3,3-tetrabutyl-i,3-dibutoxydistannoxane (each isomer), 1,1,3,3-tetrabutyl], 3-dipentyloxyditin Oxane (each isomer), I,1,3,3-tetrabutyl-1,3-dihexyloxystannane (each isomer), 1,1,3,3-tetrabutyl Base 丨, 3 bis heptyloxydistannoxane (each isomer), 1,1,3,3_tetrabutyl 丨, 3_dioctyloxydistannoxane (each isomer) ), 〇丨'1,3'3·tetraoctyl-1,3-dibutoxydistannoxane (each isomer), 1,1,3,3-tetraoctyl-丨,3_ Dipentane 1, octaneoxane (each isomer), 1,1,3,3-tetraoctyl], 3·dihexyloxydistannoxane (each isomer), I,1,3,3- Tetraoctyl-1,3·diheptyloxydistannoxane (each isomer), 1,1,3'3-tetraoctyl-indole, 3-dioctyloxydistannoxane Structure). The tetraalkyldialkoxydistannoxane represented by the above formula (15) behaves as a monomer structure' but may also be a multimeric structure or an associate. ^ It is known that usually organotin compounds are prone to form association structures, for example, dialkyltin dialkoxides form a dimer structure, or tetraalkyldialkoxydistannoxanes form associations of 2 molecules or 3 The trapezoidal structure of the molecule exists, and even if the state of association changes, it is common for the manufacturer to express the compound as a monomer structure. Further, the above-mentioned dialkyltin compound may be used singly or in combination of two or more kinds. As a method for producing the dialkyltin compound, the disclosed production method can be preferably used (WO 2005/1 1 1049, etc.). This step is a step of producing a calcining compound from a dialkyl oxide 131505.doc -35- 200948760 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. , heptanol (each isomer), (each isomer), decyl alcohol (each isomer), decyl alcohol (each isomer), etc. 'The number of carbon atoms constituting the alcohol is selected from 1~ An integer of 12 alcohols. The dialkyltin oxide used in the oxidation-forming step of the Xingxi Xiyuan oxide is a dialkyltin oxide represented by the following formula (16). ® [Chem. 9] / R9 \ (wherein R9 and R1G independently represent a linear or branched carbon number of 1 to 烧). As R9 and Ri. Examples thereof include methyl group, ethyl group, propyl group (each isomer), butyl group (each isomer), pentyl group (each isomer), hexyl group (each isomer), and heptyl group ( Each isomer), octyl (each isomer), thiol (each isomer), thiol (each isomer), undecyl (each isomer), dodecyl (each The isomer is an alkyl group or the like having an aliphatic hydrocarbon group having a carbon number of 1 to 12. More preferably, it is a linear or branched saturated alkyl group having a carbon number of 1 to 8, and more preferably n-butyl or n-octyl. Dehydrating the alcohol with dialkyltin oxide, removing the formed water to the outside of the system, and obtaining tetraalkyldialkoxydistannoxane and/or dialkyl 131505.doc -36· 200948760 tin II Alkoxide. 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 produced water to the outside of the system, the reaction temperature also depends on the reaction pressure, preferably 100 ° C to 180 ° C. The reaction rate is increased, and the reaction temperature is preferably high temperature. On the other hand, it also causes an adverse reaction such as decomposition at a high temperature, which sometimes causes a decrease in yield. Therefore, the reaction temperature is preferably 100 ° c to 160 ° C. The range "Reaction pressure is the pressure at which the generated water can be removed to the outside of the system, and also depends on the reaction temperature, and is carried out at 2 〇 to 1 χ 106 Pa. The reaction time of the dehydration reaction is not particularly limited, and is usually 0.001 to 50 hours', preferably 0.01 to 10 hours, more preferably 01 to 2 hours. The reaction is terminated if the desired alkyltin oxide composition is obtained. 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 119Sn-NMR. In order to produce the mixture of the present embodiment in the step, it was confirmed that the following composition was obtained, that is, the tetraalkyldialkoxy group contained in the alkyl tin alkoxide composition obtained by the above reaction was obtained. The molar ratio of distannoxane to dialkyltin dialkoxide oxime, expressed as the molar % of the two, is 〇: ~go: 20 range, more preferably 1〇: 9〇~7 〇: A composition in the range of 3 。. The alcohol used can be used directly in a coexistent state, and the alcohol can be distilled off depending on the situation. Since there is an advantage that the reactor can be reduced in other steps, it is preferable to The method of removing the alcohol is preferably by using the well-known method of removing the steam, and the steaming museum used in the steaming hall can use the well-known steaming equipment as a better steaming device. The time is removed, so that the film evaporation apparatus can be preferably used. The form of the reactor for the dehydration reaction is not particularly limited, and a well-known tank-shaped, column 131505.doc -37-200948760-shaped reactor can be used. The compound can be discharged from the reactor in a gaseous form by distillation and the high boiling reaction mixture comprising the alkyltin alkoxide or alkyltin alkoxide mixture produced can be discharged from the lower portion of the reactor in liquid form. As such a reactor, for example, a reactor including a stirring tank 'multistage 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 body inside can be used. , a method of a forced circulation reactor, a falling film evaporator, a falling drop evaporator, a fine flow phase reactor, a bubble column, and a method of combining the same, etc. In the case where the equilibrium is effectively biased toward the side of the formation system, it is preferred to use a column reactor, and it is preferred to rapidly transfer the formed water to a gas-liquid contact area having a large contact area. A continuous process using a multi-tubular reactor, a multi-stage distillation column, and a packed column packed with a filler, but the dialkyltin oxide used in this step is usually solid, so the best is Firstly, it is carried out in a trough reactor, and then the method of increasing the content of dialkyltin dioxane in the column reactor. If no adverse effect is caused, the material of the reactor and the line can be any known material. Among them, SUS304, SUS316, SUS316L, etc. are relatively inexpensive, so they can be used well. If necessary, a measuring instrument such as a flow meter or a thermometer, a well-known processing device such as a reboiler, a pump, and a condenser can be added; Well-known methods such as a heater, and a well-known method such as natural cooling, cooling water, and brine can be used for cooling. Step (1) is a reaction in which a dialkyl tin compound produced by the above method is reacted with gaseous carbon dioxide. The step of carbonate. This step is better than 131505.doc • 38. 200948760. It is better to use the disclosed method of producing carbonate (WO 03/055840, WO 04/014840, etc.). The alkyltin compound supplied to the present step may be supplied from the alkyltin oxide synthesis step at the time of startup; sometimes from the dialkyltin compound production step of the following step (4) at the time of continuous production, via the step (5) and supply.

In the step (1), the above dialkyltin alkoxide and gaseous carbon dioxide are first absorbed to carry out a chemical reaction to obtain a mixture of a carbon dioxide bond containing a dialkyltin alkoxide. When the chemical reaction is carried out, the dialkyltin oxide oxide is brought into a liquid state to carry out a reaction. When the dialkylstannane oxide is a solid, in order to make the dialkylstannane oxide liquid, a method of bringing it into a liquid by heating can be preferably used. Further, it may be made into a liquid form by using a solvent or the like. The reaction pressure also depends on the temperature of the reaction, and is preferably in the range of normal pressure to 1 MPa, and further preferably in the range of atmospheric pressure to 〇 6 Mpa. The reaction temperature also depends on the pressure of the reaction, but is preferably in the range of _4 (rc 80 C. If the fluidity during transportation is considered, it is preferably -80 art, and the best range is normal temperature (for example, 2). :. (:)~8〇. (: The reaction can be carried out in the range of several seconds to 100 hours, and in consideration of productivity, etc., it is preferably from several minutes to 10 hours. The reactor can use a well-known groove type reaction. , a column type reactor, X, a plurality of reactors can be used in combination. Since the reaction is a reaction between carbon dioxide gas (gas) and an alkyl tin alkoxide composition (liquid), in order to carry out the reaction efficiently, It is good to expand the liquid interface to enlarge the contact area between the gas and the liquid. Thus, the method of expanding the gas-liquid interface and using the reaction can utilize well-known knowledge, for example, if the tank type reactor is used, it is better to increase the mixing. Speed, or the side that causes bubbles in the liquid 131505.doc -39- 200948760 Method 'If a tower type reactor is used, it is preferable to use a packed column or a method of using a layered tower. As such a tower type reactor For example, for example Use a slab tower method using a tray such as a bubble tray, a perforated tray, a valve tray, a countercurrent tray, or the like, or filled with a Raschig ring, a Lexin ring, a Paul ring (PaU ring), an arc saddle filler ( Berl saddle), Intalox saddle, Dixon Packing, McMahon Packing, Heli pack, Sulzer Packing, corrugated packing (Mellapak), etc., such as a packed tower method of various fillers. If the adverse effect is not caused, the material of the reactor and the line may be any known material, and SUS304, SUS316, SUS316L, etc. are relatively inexpensive, so that it can be preferably used. If necessary, a measuring instrument such as a flow meter or a thermometer, a well-known processing device such as a reboiler, a pump, and a condenser may be added; heating may be performed by a well-known method such as steaming or heating, and cooling may also use natural cooling and cooling water. Well-known methods such as brine. The reaction is usually an exothermic reaction, so it can be cooled, or it can be cooled by using the exotherm of the reactor. The carbonation reaction can be carried out by heating. The cooling and heating of the reactor can be carried out by a known method such as a method using a water jacket or a method using an internal coil. The carbon dioxide gas and the alkyl tin alkoxide composition supplied to the reactor can be used. They may be supplied to the reactor separately or may be previously mixed before being supplied to the reactor. The mixture may be supplied from a plurality of parts of the reactor. The completion of the reaction can be determined, for example, by mSn_NMR*. Next, the following method is used. The carbon dioxide bond of the dialkylstannane oxide was obtained to obtain a reaction liquid containing a carbonate. 131505.doc -40- 200948760 Range of ~200 ° C 'In order to increase the reaction rate, the reaction condition was 11 Torr. (3 On the other hand, it also causes a decrease in yield when it is caused by a high temperature. Therefore, it is preferable that the reaction temperature is a high temperature, decomposition or the like, and there is a case of 12 (TC to 180. (: range of ' The reaction time is in the range of 〇"h~1 hr". The reaction pressure is 1.5 MPa~20 MPa, preferably 2 〇 MPa~1 〇 MPa, the reaction can be completed after the desired carbonate is formed in the reactor. The progress of the reaction in the apparatus can be confirmed by the following method or the like:

The reaction solution was sampled, and the produced carbonate was analyzed by a method such as lH_NMR or gas chromatography. For example, a carbon dioxide bond of a dialkyl tin oxide oxide and/or a dialkyl tin alkoxide contained in a carbon dioxide bond of a dialkyl tin alkoxide and/or a dialkyl tin alkoxide. The number of moles of the knot is 10% or more, and 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 or SUS316, SUS3 16L, etc. are relatively inexpensive, so that it can be preferably used. If necessary, a measuring instrument such as a flow meter or a thermometer can be attached, and a well-known processing device such as a Buddha, a pump, or a condenser can be added. The heating can be performed by a well-known method such as steam or a heater. '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 carbonic acid ester obtained in the above step (1), and obtaining a residual gastric juice. The separation method can be suitably carried out using a well-known method or I 131505.doc • 41 - 200948760. 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 steaming method is a method in which the reaction liquid is supplied to a distiller. The carbonic acid 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 carbonated vinegar, which is in the range of normal temperature (for example, 20 Ό) to 200 ° C. 'The tin compound may be modified in the residual liquid at high temperature, or bismuth carbonate. Since it is reduced by the reverse reaction, it is preferably in the range of normal temperature (for example, 20 C) to 150C. The pressure also depends on the type of carbonate or the temperature at which the reaction is carried out. 'It is usually carried out under normal pressure to reduced pressure. If productivity is considered, then it is preferably in the range of 1 〇〇pa to 80 KPa, and the best is i〇〇Pa~50 KPa range. The reaction time can be carried out in the range of from 1 hour to 1 hour. If the reaction is carried out at a high temperature for a long period of time, the tin compound contained in the reaction solution is modified or the carbonate is reduced by the reverse reaction, so Good is a range of 0.01 hours to 0. 5 hours, and the best is a range of 1 hour to 〇 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 type thin film evaporator and a thin film distiller are preferable, and a thin film evaporator and a thin film distiller having a distillation column are preferable. If the adverse effects are not adversely affected, the material of the distiller and the line can be any known material. Among them, SUS304, SUS316, SUS316L and the like 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 used. 131505.doc -42- 200948760 Using well-known methods such as steam and heater, cooling can also be used. Well-known methods such as natural cooling, cooling water, and brine. The step (3) is a step of reacting the carbonated vinegar separated in the step (7) with the aromatic transaluminum compound A to obtain a diaryl carbonate, and recovering the alcohol as a by-product. Here, the aromatic radical compound corresponds to a compound of the compound Ri〇H, and the compound R1〇H is a group R1〇 constituting the diaryl carbonate represented by the above formula (1) (R1 represents the above definition) The fragrant base, 〇 indicates that the gas is added early, and the original one is added to the hydrogen atom. Specifically, it is exemplified as an example of the aromatic (tetra)-based compound which is preferably used, and examples thereof include: benzophenone, methylbenzene (each isomer), [base benzene (each isomer), propyl benzoquinone (monoisomers), butyl benzene (each isomer), pentane & benzophenone (each isomer), hexyl phenol (each isomer) and other monosubstituted phenolic dimethyl phenol (variety Structure), diethylphenol (each isomer), dipropyl benzene (each isomer), methyl ethyl phenol (each isomer), methyl propyl phenol (each isomer) , mercaptobutylphenol (each isomer), methyl amyl phenol (isomeric ruthenium): ethyl propyl phenol (each isomer), ethyl butyl benzene (each isomer) Equivalent-substituted benzene, di-based benzene (individual isomers), triethylbenzene (individual isomers), dimethylethylphenol (each isomer), dimethylpropylphenol ( Each of the isomers), a trisubstituted phenol such as dimethylbutylphenol (each isomer), a 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 VIII to obtain diaryla carbonate. A method for obtaining an alkyl aryl carbonate or a diaryl carbonate from a carbonated vinegar and an aromatic sulfonic acid-based compound has been proposed so far as to have a plurality of methods 131505.doc-43-200948760, which may be better in this embodiment. These technologies are used. The reaction of the step (3) comprises an ester exchange 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 trans group compound, and the difference in boiling point is preferably At 2 ° C, if the ease of separation is considered, it is preferably 10 ° C. As an example of the carbonic acid calcination used in the step (3), for example, dimethyl carbonate 'diethyl carbonate, dipropyl carbonate (each isomer), dibutyl carbonate (each isomer), Dipentyl carbonate (each isomer), dihexyl carbonate (different oxime), diheptyl carbonate (each isomer), dioctyl carbonate (each isomer), dinonyl carbonate ( Each isomer), dinonyl carbonate (each isomer), dicyclopentanyl carbonate 'dicyclohexyl carbonate, dicycloheptyl carbonate (each isomer), monobenzyl carbonate, diphenyl carbonate Ester (each isomer), di(phenylpropyl) carbonate (each isomer), di(phenylbutyl) carbonate (each isomer), di(chlorobenzyl) carbonate (each Isomer), bis(methoxybenzyl)carbonate (each isomer bis(methoxyindenyl)polycarbonate, bis(methoxyethyl)carbonate (each isomer), carbonic acid Two (gas ethyl) brewing (each isomer), di(ethyl ether) vinegar (each isomer), methyl ethyl carbonate, methyl propyl carbonate (each isomer), carbonic acid 131505. Doc -44- 200948760 methyl butyl vinegar (each isomer), ethyl propylene carbonate (each isomer), ethyl butyl carbonate (each isomer), ethylene carbonate, propylene carbonate, etc. The carbonate may be one kind or a mixture. Among the above-mentioned dialkyl carbonates, it is preferably used in the embodiment that the standard boiling point of the alcohol constituting the carbonate is higher than the standard boiling point of water, and the carbon number is An alkyl alcohol having 4 to 12 alkyl groups, an alkenyl alcohol having a linear or branched alkenyl group having a carbon number of 4 to u, a cycloalkyl alcohol, or an aralkyl alcohol. The reaction carried out is advantageously carried out, and the alcohol formed by the reaction of the step (3) is removed, and further preferably an alcohol having a standard boiling point lower than the standard boiling point of the aromatic hydroxy compound used in the step (3). It 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. The amount of the aromatic mercapto compound used in the step (3) is separated from that in the step (2). The amount of dialkyl carbonate used in the step (3), in stoichiometric ratio It can be used in the range of Oi times to 1〇〇〇〇. The Q reaction in the step (3) is mainly an equilibrium reaction, so the amount of the aromatic hydroxy compound is more favorable. Large, and the separation of the subsequent products also requires a larger distillation column or the like, and therefore it is preferably in the range of 1 to 1000 times, more preferably 1 to 1 inch, relative to the dialkyl carbonate. The compound to be supplied to the step (3) is mainly a dialkyl carbonate or an aromatic hydroxy compound. The catalyst is supplied as needed, and impurities which do not particularly adversely affect the reaction may be mixed in. The raw materials may be contained as a product. The alcohol, the alkyl aryl Ss, and the diaryl carbonate, etc., the reaction is a reversible reaction. Therefore, when the agricultural product of 131505.doc -45·200948760 is produced, the reaction rate of the raw material sometimes decreases. Therefore, it is bad. 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 molar ratio is 供给. 〇 1 to 1000 times the range of the supply of the aromatic hydroxy compound. The reaction time of the vinegar exchange reaction in the step (3) also varies depending on the reaction conditions or the type or internal structure of the reactor, and is usually 〇〇〇1 to 5 hrs, 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 mercapto compound, and is usually 5 Torr to 350 ° C, preferably 100 ° C. It is carried out within the range of ~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 one of pressure reduction, normal pressure, and pressurization, and is usually carried out in the range of 1 〇 Pa to 2 〇 Mpa. In the present embodiment, it is not necessary to use a solvent, and in order to facilitate the reaction operation, an appropriate inert solvent such as an ether, an aliphatic hydrocarbon, an aromatic hydrocarbon, a condensed aliphatic hydrocarbon, or an aromatic aromatic may be used. A hydrocarbon or the like is used as a reaction solvent. Further, an inert gas such as nitrogen gas, gas gas or argon gas which is inert to the reaction may be allowed to coexist in the reaction system, and in order to accelerate the formation of the low-fossil by-product, it may be from the lower part of the continuous multi-stage distillation column. The above inert gas or a low melting point organic compound which is inert to the reaction is introduced as 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 carbonic acid-aryl ester 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, since 131505.doc • 46-200948760 When a diaryl carbonate is produced, 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, 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 total weight of the carbonate and the aromatic hydroxy compound as a raw material to be supplied. Further, in the case of using a solid catalyst, it is preferred to use 0.01 to 75% by volume of the catalyst amount with respect to the empty column volume of the reactor. As a proposal relating to a catalyst for accelerating the reaction rate, a large number of metal-containing catalysts are known. In the present embodiment, a well-known vinegar exchange reaction catalyst can also be used. 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 oxide oxide or an organotin oxide, a metal or a soil test, a metal salt and an alkoxide, a lead compound, copper, Metal complexes such as iron, erbium, etc., titanates, mixtures of Lewis acids and proton acids, compounds of 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. Here, the heterogeneous reaction means a reaction of producing a dialkyl carbonate and a diaryl carbonate from two molecules of an alkyl aryl carbonate. The carbonic acid aryl group S is further reacted with the aromatic sulfhydryl compound, and also causes the reaction to become a diaryl carbonate, which is caused by the unevenness of 131505.doc •47- 200948760 Π:: When the acid-depleting base is obtained, the diaryl vinegar carbonate is obtained, and the reaction is an equilibrium reaction. In the exchange reaction of m #方酉曰, the alkyl alcohol is discharged - - in the 'unevenness step', while discharging the carbonic acid (four) while taking 1, taking: 4 is advantageous. Therefore, the preferred reaction conditions are different in each stage. ';,,,' When the reaction is carried out, it is necessary to carry out the reaction in two stages. When the batch is carried out and the mixture is used, it can also be carried out in the same reactor for 0 Ο 逐. The catalyst for promoting the heterogeneous reaction coexists with the above vinegar exchange 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 are proposed, and the polymer tin compound 'is passed through m (= Q) 〇H (wherein χ is selected from, for example, R is selected from a monohydrocarbyl group) A compound of the formula, a mixture of a Lewis acid and a protonic acid, a catalyst of the wrong catalyst 'titanium or bismuth (IV), a tin compound, a compound such as Sc, M〇, Μη, Bi, Te, or the like. The unevenness step is a step of obtaining a non-homogeneous carbonic acid aromatic vinegar obtained in the vinegar exchange step, thereby obtaining 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 respectively carried out, there is also a case where a diaryl carbonate is obtained simultaneously with an alkyl aryl carbonate, and in this case, an uneven reaction can be directly carried out. The heterogeneous reaction is as shown above, which is a step of obtaining an alkyl aryl carbonate by transesterification of a dialkyl carbonate with an aromatic hydroxy compound, 131505.doc -48-200948760, in order to facilitate the equilibrium reaction, one side It is advantageous to carry out the reaction while discharging the side. The heterogeneous reaction is also limited by the balance w < Therefore, in order to carry out the reaction, the reaction is carried out by discharging the bis(tetra) and the dicarbonate produced by the heterogeneous reaction to the outside of the line. The method is more advantageous. In the present embodiment, it is preferable that the alkoxy group and the aryl group are respectively selected so that the boiling point of the carbonated vinegar is lower than that of the diaryl vinegar, and the carbonic acid is discharged to the outside of the system. _ while performing * homogenization reaction. 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 polymeric tin compound, having the formula RX(=〇)〇H (wherein 'X is selected from Sn&Ti, R is selected from 1 a compound represented by a valence hydrocarbon group, a mixture of a Lewis acid and a protonic acid, a lead catalyst, a compound of a cis or a wrong compound, a tin compound, a compound of Sc, MO, Mn, Bi, 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), basic hexane vinegar (each isomer), heptyl benzene carbonate (isomeric 131505.doc -49· 200948760 , octyl cresyl carbonate (each isomer), decyl carbonate (ethyl phenyl) ester (each isomer), decyl phenyl (butyl phenyl) ester (each isomer), carbonic acid Methyl benzene vinegar (each isomer), ethyl cresyl carbonate (each isomer), propyl methyl acrylate (each isomer), butyl phenyl phenyl carbonate (each isomer), Dyl propyl carbonate (each isomer), methyl decyl phenyl carbonate (each isomer), methyl (trimethylphenyl) carbonate (each isomer), methyl carbonate (chlorine) Phenyl) ester (each isomer), decyl carbonate (nitrophenyl) ester (each isomer), decyl carbonate (decyloxy) ester (each isomer), cesium carbonate N-pyridyl)ester (each isomer), ethyl cumyl carbonate (each isomer), guanidinium carbonate (benzimidyl) ester (each isomer), ethyl carbonate Xylene ester (each isomer), benzyl cresyl carbonate (each isomer), and the like. These alkyl aryl carbonates may be one type or a mixture of two or more types. 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 aromatic hydroxyl group of the alkyl aryl ester has a boiling point selected, for example, from an alkyl alcohol having a linear or branched alkyl group having 4 to 12 carbon atoms, and having a linear or branched carbon. The alkenyl alcohol, cycloalkyl alcohol, and aralkyl alcohol having 4 to 12 alkenyl groups are considered to be advantageous in that the heterogeneous reaction is carried out to remove the dialkyl carbonate formed by the heterogeneous reaction. It is preferably 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 an alcohol selected from the group consisting of pentanol (each isomer), hexanol (each isomer), and heptanol (each isomer), aryl 131505.doc -50- 200948760 aromatic base compound It is selected from the group consisting of benzene and abipan. The compound supplied to the unevenness step is mainly a aryl carbonate, and a catalyst is supplied as needed, and impurities which do not particularly adversely affect the reaction can be mixed. The amount of the catalyst used in the present embodiment depends on the type of the catalyst to be used, the type of the reactor, the type or amount of the carbonated aromatic vinegar, or the reaction temperature.

The reaction conditions such as the reaction pressure and the like are different, and are expressed as a ratio of the weight of the aryl carbonate as a raw material to be supplied, and are usually used in an amount of from 1 to 5 % 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 in 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 of the components is too high, the reaction rate of the raw material may decrease, which is not preferable. . The reaction time of the heterogeneous reaction varies depending on the reaction conditions or the type of the reactor or the internal structure. Usually, it is (four) hours, preferably g〇i~i〇 hour. More preferably, G.G5~5 hours〇 The reaction temperature varies depending on the type of the carbonated aromatic vinegar to be used, and is usually carried out at a temperature ranging from 5 Torr to 35 Torr, more preferably I'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 a reduced pressure, a normal or a magnetic property, and is usually carried out in the range of Pa to 20 MPa. In the step of deuteration, it is not necessary to use a solvent. In order to make the reaction operation easy, etc., an inert solvent such as an ether, an aliphatic hydrocarbon, or an aromatic hydrocarbon is used. Class, toothed aliphatic hydrocarbons, dentate aromatics 131505.doc 200948760 Aroma = smoke, etc. as a reaction, and can coexist as an inert gas such as nitrogen, helium or argon which is inert to the reaction. In the reaction system, in order to accelerate the distillation of the low-boiling by-product formed, the inert gas or the low-melting organic compound inert to the reaction may be introduced in a gas form from the lower portion of the continuous multi-stage distillation column. After the end of the heterogeneous reaction, the catalyst, the alkyl carbonate, the aromatic hydroxy compound, and the alcohol are separated by a well-known method to obtain a diaryl carbonate.

The form of the reactor used in the Sg 0 〇81 exchange step and the unevenness step is not particularly limited, and a stirring tank method, a multi-stage stirring tank method, a multi-stage distillation column, and the like may be employed. Various methods are well known. These reactors can be used in either batch or continuous mode. In view of effectively balancing the equilibrium 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 steaming tower refers to a multi-stage steaming tower in which the number of theoretical stages of steaming is two or more, and any one can be continuously distilled if Q can be used. 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 Raschig ring, a Lexin ring, a Pall ring, or the like is used. Arc saddle packing, moment saddle ring packing, Dixon packing, net saddle packing, spiral packing, wire mesh corrugated packing, orifice corrugated packing, etc., which are usually used as multi-stage steaming tower users, Any one can be used. Further, a laminate/filler mixing tower in which the laminate portion and the filler-filled portion are combined may be preferably used. When a continuous process is carried out using a multi-stage distillation column, the starting materials and the reaction materials are continuously supplied to a continuous 131505.doc -52-200948760 multi-weight steaming tower in the presence of a metal-containing catalyst in the distillation column. Conducting a transesterification reaction and/or a heterogeneous reaction between the two substances in a liquid phase or a gas-liquid phase, and simultaneously containing the prepared alkyl aryl carbonate and/or diaryl carbonate The lower portion of the steaming tower is discharged as a liquid, and on the other hand, the low-boiling reaction mixture containing the by-product formed is continuously discharged in a gaseous state by distillation from the upper portion of the distillation column, thereby producing a diaryl carbonate. The above shows the production 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-oxo-1⁄4 bond and water, and removing the water from the reaction system; 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). ❹ Step (4) is a step of reacting the residual liquid obtained in the step (2) with an alcohol to regenerate the dialkyltin compound. As the alcohol used in this step, decyl alcohol, ethanol, propanol (each isomer), butanol (each isomer), pentanol (each isomer), hexanol (isomeric) 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 The alcohol of the integer number of 12 is more preferably the same alcohol as that used in the alkyltin alkoxide synthesis step described above. 131505.doc -53- 200948760 It is preferred that the conditions of the dehydration reaction are also carried out under the same conditions as the above-mentioned alkyltin alkoxide synthesis step. 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 u9Sn_NMR. In order to produce the mixture of the present embodiment in the step (", it is confirmed that the following composition is obtained, that is, the tetraalkyldialkoxy group contained in the alkyl tin alkoxide composition obtained by the above reaction. The molar ratio of distannoxane to dialkyltin dialkoxide, expressed as % of the combination of the two, is 0: 丨〇〇 ~ 80: 20, more preferably 1 〇: 90 The composition of the range of ~70:30. The alcohol used may be used directly in the coexisting state, and may be used by distilling off the alcohol according to the situation. Since it has the advantage of reducing the reactor of other steps, it is preferred that The alcohol is removed as much as possible. The removal method is preferably carried out by the use of distillation which is well known, 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 usually not used, so the reactor is less restrictive. The form of the reactor for the water reaction is not particularly limited, and a well-known tank-like or column-shaped reactor can be used. The low-water/fuss-point reaction mixture is discharged from the reactor in a gas form by distillation, and is produced by a gas system. The high-boiling reaction mixture of the base-burning oxide or the base-burning oxide mixture is discharged from the lower portion of the reactor as a liquid. As such a reactor, for example, a stirring tank, a multi-stage stirring tank, a distillation column, Multi-stage distillation column, multi-tubular reactor, continuous multi-stage distillation column, filling 131505.doc -54- 200948760 charging tower, thin crucible evaporator, reactor with internal and optional support, forced circulation reaction , the falling film evaporator, the falling enthalpy, the same as the reactor fine-phase reactor, the bubble, the way of the reactor, and the methods of combining them, etc. In terms of the side of the formation system, it is preferable to use a columnar reactor. Preferably, the formed X is rapidly transferred to the gas phase, and the gas-liquid contact area is large. Particularly preferably, a multi-tube is used. Reactor, multi-stage steaming (four), continuous method filled with filler filling tower. If * caused by Μ, the material of reaction n and the line can be any known material, of which SUS3〇44Sus3i6, SUS316L, etc. are relatively cheap, so It can be used well. It can be equipped with measuring instruments such as flow meters and thermometers, well-known processing devices such as reboilers, pumps, and condensers. Heating can be done by well-known methods such as steam and heaters. A well-known method such as cooling water, brine, etc. The dialkyl tin compound produced in the above step (4) is reused as the dialkyl tin compound used in the step (丨) by the step (5) (reuse step). Step (5) is the step of using the organotin compound having the tin-oxygen-carbon bond obtained in the step (4) as the organotin compound having the tin-oxygen-carbon bond in the step (1). 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. 131505.doc -55- 17) 200948760 [Chemical] R2 is as h2: (wherein R2 is selected from aliphatic groups containing carbon atoms selected from carbon and oxygen, and having a carbon number of 6 to 20 One of the groups consisting of aromatic groups has an valence equal to η, and η is an integer of 2 to 10. ❹ In the above formula (17), it is preferred that the above polyamine is more preferably a diamine compound having η of 2. R2 of the above formula (17) is more preferably a burnt beauty having a carbon number of (d), and a carbon number of 5 to a ring-shaped filament. As an example of such R2, it is preferable to make =: methylene group, two subunits a straight-chain hydrocarbon group such as a methyl group, a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group or an octamethyl group; a cyclopentane, a cyclohexane, a cycloglycine, a cyclooctane, a bis (ring) An unsubstituted alicyclic nicotinyl such as a hydrocarbon; decylcyclopentane, ethylcyclopentane, nonylcyclohexane (each isomer, ethylcyclohexanone (each isomer), propyl Cyclohexane (each isomer), butylcyclohexane (each isomer), pentylcyclohexan (each isomer), hexylcyclohexane (each isomer), etc. a dialkyl group substituted cyclohexane H' such as dimethylcyclohexane (each isomer), diethylcyclohexane (each isomer), dibutylcyclohexane (each isomer) 5,5_trimethylcyclohexane, M,5-triethylcyclohexane, 1,5,5-tripropylcyclohexane (each isomer), M,5-tributylcyclohexane Then, each isomer) is substituted with a trialkyl group to replace the cyclohexane; a monoalkyl substituted benzene such as a stupid, ethylbenzene or propylbenzene; Dimethylbenzene, hydrazine, monoethylidene, dipropylbenzene, etc., dialkyl-substituted benzene; diphenylalkane, benzene, etc., Fangfanyou, Netchu, I Fangjin hydrocarbon, etc. Among them, it is better to use six 131505.doc • 56· 200948760 methylene, phenyl, diphenylmethane, toluene, cyclohexane, xylene, methylcyclohexane, isophorone and dicyclohexyl曱基. Examples of such a polyamine compound include hexamethylenediamine, 4,4'-methylenebis(cyclohexylamine) (each isomer), and cyclohexanediamine (each isomer). , 3-aminomethyl-3,5,5-trimethylcyclohexylamine (each isomer), such as adiamine, phenylenediamine (each isomer), toluenediamine (isomeric) An aromatic diamine such as 4,4,_-decylene diphenylamine. Among them, hexamethylenediamine 4'4-methylenebis(cyclohexylamine) (each isomer), cyclohexene diamine (each isomer), and 3-aminocarbonyl group are preferably used. -3,5,5-tridecylcyclohexylamine (each isomer), such as an aliphatic diamine, wherein hexamethylenediamine, 4,4,-indenyl bis(cyclohexylamine) is better used. ), 3-aminomethyl-3,5,5-tridecylcyclohexylamine. <Reaction of diaryl carbonate with an 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 ruthenium 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. Examples of the aromatic hydroxy compound used for the reaction of the diaryl carbonate with the amine compound include benzophenone, methyl benzophenone (each isomer), and ethyl benzophenone 131505.doc -57- 200948760 (various Structure), propyl-phenol (each isomer), butyl-p-phenol (each isomer), pentyl-phenyl age (each isomer), hexyl-benzene (each isomer), Heptyl benzophenone (each isomer), octyl-phenol (each isomer), mercapto-phenone (each isomer), mercapto-phenol (each isomer), dodecyl - monosubstituted phenols such as phenol (each isomer), phenyl-phenol (each isomer), phenoxyphenol (each isomer), cumyl-phenol (each isomer), Mercapto-phene (each isomer), diethyl-phenol (each isomer), dipropyl-phenol (each isomer) monobutyl _ _ (isomeric), di-pentane -Benzene (each isomer), ® Dihexyl-phenol (each isomer), Diheptyl-phenol (each isomer), Dioctyl-phenol (each isomer), Dimercapto _phenol (each isomer), dimercapto-stupid Each isomer), _mono(dodecanyl)-benzene (each isomer), diphenyl-mild (each isomer), diphenoxyphenol (each isomer), Diisopropylphenyl- phenol (each isomer), decyl-ethyl-phenol (each isomer), methyl propyl-polyphenol (each isomer), methyl butyl _ Phenol (each isomer), methyl-pentyl-polyphenol (each isomer), methyl-hexyl-phenol (each isomer), methyl-heptyl-stupylphenol (each isomer) ), methyl-octyl-phenol (each isomer), methyl-mercapto-ylphenol (each isomer), methyl-mercapto-phenol (each isomer), methyl-tine Alkyl-p-phenol (each isomer), methyl-phenyl-phenol (each isomer), nonylphenoxyphenol (each isomer), methyl-cumyl-phenol (each Isomers), 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-benzene -Phenol (each isomer 13l505.doc -58 - 200948760), ethyl-phenoxyphenol (each isomer), ethyl-isopropylphenyl-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-hydrazino-phenol (each isomer), propyl-mercapto-phenol (each isomer), propyl-dodecane - phenol (each isomer), propyl-phenyl-phenol (each isomer), propyl-phenoxybenzene (each isomer), propyl-isopropylphenyl-phenol (each Isomers), butyl-pentyl-phenol (each isomer), butyl-hexyl-phenol (each isomer), butyl-heptyl-heptyl-phenol (each isomer), butyl- Octyl-phenol (each isomer), butyl-mercapto-phenone (each isomer), butyl-nonylbenzene (each Structure), butyl-dodecyl-phenol (each isomer), butylphenyl-phenol (each isomer), butyl-phenoxyphenol (each isomer), butyl- Phenylphenol·phenol (each isomer), amyl-hexyl-phenol (each isomer), amyl-heptylphenol (each isomer), amyl-octyl-phenol (isomeric , pentyl-fluorenyl-phenol (each isomer), pentyl-fluorenyl-phenol (each isomer), amyl-dodecyl-nonylphenol (each isomer), pentyl Phenyl-phenol (each isomer), pentylphenoxyphenol (each isomer), pentyl-isopropylphenyl-phenol (each isomer), hexyl-heptyl-phenol (each Isomers), hexyl-octyl-phenol (each isomer), hexyl-mercapto-phenol (each isomer), hexyl-fluorenyl-phenol (each isomer, hexyl-dodecyl- Phenol (each isomer), hexylphenylphenol (each isomer), hexyl-phenoxyphenol (each isomer), hexyl-cumenyl-phenol (each isomer), heptyl- Octyl-phenol (each isomer), heptyl-mercapto-phenol (each isomer) , heptyl-decyl-phenol (each isomer), heptyldodecyl-phenol (each isomer), heptyl-phenyl-p-phenol (each isomer), heptylphenoxyl 131505 .doc •59- 200948760 phenol (each isomer), heptyl-cumyl-phenol (each isomer), octyl-fluorenyl-phenol (each isomer), octyl-fluorenyl _Phenol (each isomer), octylundecyl-p-phenol (each isomer), octyl-phenyl-phenol (each isomer), octyl-phenoxyphenol (isomeric , octyl-cumyl-phenol (each isomer), mercapto-fluorenyl-phenol (each isomer), mercapto-dodecyl-phenol (each isomer), hydrazine -Phenyl-phenol (each isomer), mercapto-phenoxyphenol (each isomer), mercapto-cumenyl-phenol (each isomer), dodecyl-phenyl -Diphenols such as phenol (each isomer), dodecyl-phenoxyphenol (each isomer), dodecyl-cumylphenol-phenol (each isomer), Methyl-phenol (each isomer), triethyl-phenol (each isomer), tripropyl-benzene Phenol (each isomer), tributyl-phenol (each isomer), tripentyl-phenol (each isomer), trihexyl-phenol (each isomer), triheptyl-phenol (each Isomers), trioctyl phenol (each isomer), tridecyl-phenol (each isomer), tridecyl-phenol (each isomer), tris(dodecylphenol) Isomers), triphenyl-phenol (each isomer), triphenyloxyphenol (isomeric), triisopropylphenyl-phenol (each isomer), dimethyl-ethyl - phenol (each isomer), dimercapto-propyl-benzoin (each isomer), dimethyl-butyl-benzene (each isomer), dimethyl-pentyl-phenol ( Each isomer), dimethylhexyl-phenol (each isomer), dimethyl-heptyl-phenol (each isomer), dimethyl-octyl-phenol (each isomer), Dimercapto-indenyl-phenol (each isomer), dimercapto-indenyl-benzoate (each isomer), dimercapto-dodecyl-p-stoke (each isomer), two Methyl-phenyl-phenol (each isomer), dimethyl-phenoxy group (each isomer), two Methyl-isopropylphenyl-phenol (each isomer), diethyl-methyl-phenol (each isomer), diethyl-propyl-phenol (each isomer), 131505.doc - 60- 200948760 Monoethyl-butyl-phenol (each isomer), diethyl·pentylphenol (each isomer), diethyl-hexyl-phenol (each isomer), diethyl_ Heptylphenol (each isomer), diethyl-octyl-phenol (each isomer), diethyl thiol phenol (each isomer), diethyl-mercapto-phenol (each Isomers), diethyl-dodecyl-phenol (each isomer), diethyl-phenyl-phenol (each isomer), diethyl-phenoxyphenol (each isomer) ), diethyl-cumylphenol (each isomer), dipropyl-fluorenyl-benzoic acid (each isomer), dipropyl-ethyl-phenylene (each isomer), Dipropyl-butyl-phenol (each isomer), dipropyl-pentyl-polyphenol (each isomer), dipropyl-hexyl-phenol (each isomer), dipropyl- Heptyl-phenol (each isomer), dipropyl-octyl-phenol (each isomer), dipropyl-fluorenyl- Phenol (each isomer), dipropyl-indenyl-phenol (each isomer), dipropyl-dodecyl-phenol (each isomer), dipropyl-styl-phenol (each Isomers), dipropyl-phenoxyphenol (each isomer), dipropyl-cumylphenol-phenol (each isomer), dibutyl-methyl-phenol (each isomer) ), monobutyl-ethyl-benzene (each isomer), dibutyl-propyl-benzene (each isomer), dibutyl-pentyl-phenol (each isomer) , dibutyl-hexyl-p-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-cumylphenol-phenol (each isomer), dipentyl-indenyl-phenol (each Isomer), dipentyl-ethyl-phenol (each isomer), dipentyl-propyl-phenol (each isomer), two -butyl-phenol (each isomer), dipentyl-hexyl-phenol (each isomer), dipentyl-heptyl-phenol (each isomer), 131505.doc • 6b 200948760 II Pentyl-octyl-phenol (each isomer), dipentyl-mercapto-phenol (each isomer), dipentyl-indolyl-phenol (each isomer), dipentyl-tweldium Alkyl-phenol (each isomer), dipentyl-phenyl-phenol (each isomer), dipentyl-phenoxyphenol (each isomer), dipentyl-isopropylidene Phenol (each isomer), dihexyl-methyl-phenol (each isomer), dihexyl-ethyl-phenol (each isomer), monohexyl-propyl·phenol (each isomer) Dihexyl-butylphenol (each isomer), dihexyl-pentyl-phenol (each isomer), dihexyl-heptyl-phenol (each isomer), dihexyl-octyl-phenol (each Isomers), dihexyl-fluorenyl-phenol (each isomer), dihexyl-fluorenyl-phenol (each isomer), dihexyl-dodecyl-phenol (each isomer), two Hexyl-phenyl-phenol (each isomer), dihexyl-phenoxy Phenol (each isomer), dihexyl-cumylphenol (each isomer), diheptyl-methyl-phenol (each isomer), diheptylethyl-phenol (isoisomer) , diheptyl-propyl-phenol (each isomer), diheptyl-butyl-phenol (each isomer), diheptyl-pentyl-phenol (each isomer), diheptan -hexyl-phenol (each isomer), diheptyl-octyl-phenol (isomeric), diheptyl-fluorenyl-phenol (each isomer), diheptyl-fluorenyl- Phenol (each isomer), diheptyl-dodecyl-phenol (each isomer), diheptyl-phenyl-phenol (each isomer), diheptyl-phenoxyphenol (each Isomers), diheptyl-isopropylphenyl·phenol (each isomer), dioctyl-fluorenyl-phenol (each isomer), dioctyl-ethyl-phenol (each isomer) ), dioctyl-propylphenol (each isomer), dioctyl-butyl-phenol (each isomer), dioctyl-pentyl-phenol (each isomer), dioctyl- Hexyl-phenol (each isomer), dioctyl-heptyl-phenol (each isomer), dioctyl·壬Base-phenol (each isomer), dioctyl-fluorenyl-phenol (each isomer), dioctyl-dodecyl-phenol (isomeric 131505.doc-62-200948760), two Octyl-phenyl-phenol (each isomer), dioctylphenoxyphenol (each isomer), dioctyl-cumenyl-phenol (each isomer), dimercapto -Phenol (each isomer), Dimercapto-ethyl-phenol (each isomer), Dimercapto-propyl-phenol (each isomer), Dimercapto-butylphenol (variety) Structure), dimercapto-pentyl-phenol (each isomer), dimercapto-hexylphenol (each isomer), dimercapto-heptyl-phenol (each isomer), diterpenes Base-octyl-p-phenol (each isomer), dimercapto-fluorenyl-phenol (each isomer), didecyl-deca-alkyl-phenol (isomer), dimercapto Phenyl·phenol (each isomer), —mercapto-phenoxyphenol (each isomer), dimercapto-cumylphenyl-phenol (each isomer), dimercapto-indenyl group_ Streptophenol (each isomer), dimercaptoethyl phenol (each isomer), dimercapto-propyl-benzene (each isomer), didecyl-butyl-phenol (each isomer), dimercapto-pentyl-phenol (each isomer), dimercapto-hexyl-phenol (each isomer) , dimercapto-heptylphenol (each isomer), dimercapto-octyl phenol (each isomer), dimercapto-fluorenyl-phenol (each isomer), dimercapto-ten Dialkyl·phenol (each isomer), dimercapto-phenyl-cupolic phenol (each isomer), dimercapto-phenoxyphenol (each isomer), dimercapto-isopropyl Phenylphenol (each isomer), di(dodecyldecyl-phenol (each isomer), one (undecyanyl)-ethyl-benzene (each isomer), two (ten) Dialkyl) propyl-benz (each isomer), di(dodecyl)-butyl-phenol (each isomer), one (undecyanyl)-pentyl-benzene ( Each isomer), bis(dodecyl)-hexyl-benzene (each isomer), di(dodecyl)-heptyl-phenol (each isomer), di(dodecyl) )-octyl phenol (each isomer), di(dodecyl)-decyl-phenol (each isomer), two ( Dodecyl)-mercapto-phenol (each isomer), di(dodecyl)-dodecyl-phenol (each isomer), di(dodecane 131505.doc -63- 200948760 Phenyl-phenyl-benzine (each isomer), di(dodecyl)-phenoxyphenol (each isomer), di(dodecyl)-isopropylphenyl-phenol (each Isomers), diphenyl-methyl-phenol (each isomer), diphenyl-ethyl-phenol (each isomer), monophenyl-propyl-phenol (each isomer), Diphenyl-butyl-phenol (each isomer), diphenyl-pentyl-phenol (each isomer), diphenyl-hexyl-phenol (each isomer), diphenyl-heptyl - phenol (each isomer), diphenyloctylphenol (each isomer), diphenyl-mercapto-phenol (each isomer), diphenyl-fluorenyl-phenol (each isomer) ), diphenyl-dodecyl-phenol (each isomer), diphenyl-phenoxyphenol (each isomer), diphenyl-cumylphenyl-phenol (each isomer) , diphenoxymethyl-phenol (each isomer), diphenoxyethyl benzophenone (each isomer) , diphenoxypropyl-phenol (each isomer), diphenoxybutyl-phenol (each isomer), diphenoxypentyl-benzoan (each isomer), diphenyloxide Hexyl-phenol (each isomer), diphenoxyheptyl-phenol (each isomer), one oxyoctyl-benzene (iso-isomer), diphenoxynonyl-benzene Expectant (each isomer), diphenoxynonyl-phenol (each isomer), diphenoxydodecyl-phenol (each isomer), diphenoxyphenyl·phenol (each Isomers), diphenoxyisopropyl phenyl-phenol (each isomer), diisopropylphenyl-methyl phenol (each isomer), dicumyl-ethyl phenol (isomeric), diisopropylphenyl-propyl-phenol (each isomer), diisopropylphenyl-butyl-benzoin (each isomer), monoisopropylphenyl-fluorenyl - benzene (each isomer), diisopropylphenyl hexyl _ Benzine (each isomer), · isopropyl phenyl - heptyl - benzene (each isomer), dicumyl Benzyl-octyl-benzene (each isomer) 'diisopropylphenyl-fluorenyl-the present (each isomer), dicumyl - decyl - age benzene (including isomers), a cumyl - twelve burn-yl - benzene numerous (including isomers), dicumyl - phenyl 131505.doc • 64 - 200948760 Ο

Phenol (each isomer), diisopropylphenyl-phenoxyphenol (each isomer), methyl-ethyl-propyl-p-phenol (each isomer), mercapto-ethyl -Phenol (each isomer), methyl-ethyl-pentyl-phenol (each isomer) 'Methyl-ethyl-hexyl-phenol (each isomer), mercapto-ethyl·g -Phenol (each isomer), methyl-ethyl-octyl-phenol (each isomer), methyl-ethyl-nonylphenol (each isomer), methyl-ethyl-oxime -Phenol (each isomer), methyl-ethyl-dodecyl-phenol (each isomer), mercapto-ethyl-phenyl-phenol (each isomer), mercapto-B -Phenoxyphenol (each isomer), mercapto-ethyl cumyl-phenol (each isomer), mercapto-propyl-butyl-phenol (each isomer), methyl -propyl-pentyl-phenol (each isomer), methyl-propylhexylphenol (each isomer), methyl propyl-heptyl-phenol (each isomer), mercapto-propyl -octyl-phenol (each isomer), methyl-propyl-fluorenyl-phenol (each isomer), methyl-propyl-decyl-phenol (each Structure), mercapto-propyl-dodecyl-phenol (each isomer), mercapto-propyl-phenyl-phenol (each isomer), methyl-propyl-phenoxyphenol (each isomer), methylpropyl cumylphenol (each isomer), methyl-butyl-pentyl phenol (each isomer), methyl butyl-hexyl-phenol ( Each isomer), methyl-butyl-heptyl-phenol (each isomer), mercapto-butyl-octyl-phenol (each isomer)' methylbutylsulfonyl-phenol (isomeric , fluorenyl-butyl-hydrazino-phenol (each isomer), methyl-butyl-dodecyl-phenol (each isomer), methyl-butyl-phenyl-phenol ( Each isomer), mercapto-butyl-phenoxyphenol (each isomer), mercapto-butyl-cumenyl-phenol (each isomer), mercapto-pentyl-hexyl_ Phenol (each isomer), mercapto-pentylheptyl-phenol (each isomer), methyl-pentyloctyl_benzene (each isomer), mercapto-pentyl-fluorenyl - phenol (each isomer), methyl · 131505.doc -65- 200948760 pentyl thiol-phenol (each isomer), methyl - -dododecylphenol (each isomer), mercapto-pentyl-phenyl-benzene (iso-isomer), methyl-pentyl-phenoxyphenol (each isomer), A -Pentyl-cumyl-phenol (each isomer), methyl-hexyl-heptyl-phenol (each isomer), methylhexyloctyl-phenol (each isomer), A -hexyl-fluorenyl-phenol (each isomer), methyl-hexyl-indenyl-phenol (each isomer), methyl-hexyl-dodecyl-phenol (each isomer), A Hexyl-hexyl-phenyl-benz (each isomer), methyl-hexylphenoxyphenol (each isomer), methyl-hexyl-isopropylphenyl-p-phenol (isomeric) , ethyl·propyl·butyl-p-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-fluorenyl-phenol (isoisomer) , ethyl-propyl-fluorenyl-phenol (each isomer), ethyl-propyl-dodecyl-phenol (each isomer) Ethyl-propyl-phenyl- phenol (each isomer), ethyl propyl phenoxy phenol (each isomer), ethyl-propyl-isopropyl phenyl-phenol (variety) Structure), ethyl _ 0 butyl-phenol (each isomer), ethyl butyl pentyl phenol (each isomer), ethyl-butyl-hexyl-phenol (each isomer) ), ethyl-butylheptyl-phenol (each isomer), ethyl-butyl-octyl-phenol (each isomer), ethylbutyl-mercapto-benzene (isoisomer) , ethyl-butyl-mercapto-phenol (each isomer), ethyl-butyl-dodecyl-phenol (each isomer), ethyl-butyl-phenyl-p-phenol (each isomer), ethyl-butyl-phenoxyphenol (each isomer), ethyl-butyl-isopropylphenyl-phenol (each isomer), ethyl-pentyl-hexyl -Phenol (each isomer), ethyl-pentyl-heptyl-phenol (each isomer), ethyl-pentyl-octyl-phenol (each isomer), ethyl-pentyl-oxime Base-phenol (isomeric 131505.doc -66- 200948760

, ethyl-pentyl-indolyl-phenol (each isomer), ethylpentyl-dodecyl-benzene age (each isomer), ethyl-pentyl-phenyl-benzene (each isomer), ethyl·pentyl-phenoxyphenol (each isomer), ethyl-pentyl-cumyl-phenol (each isomer), ethyl-hexyl-g -Phenol (each isomer), ethylhexyl-octyl-phenol (each isomer), ethyl-hexyl-decyl-phenol (each isomer), ethyl-hexyl-fluorenyl- Phenol (each isomer), ethyl-hexyl-dodecyl-phenol (each isomer), ethyl-hexyl-phenylphenol (each isomer), ethyl-hexylphenoxy Phenol (each isomer), ethyl-hexyl-isopropylphenyl·phenol (each isomer), ethyl-heptyl-octyl-phenol (each isomer), ethyl-heptyl-fluorene -Phenol (each isomer), ethyl-heptyl-fluorenyl phenol (each isomer), ethyl-heptyl-dodecyl-phenol (each isomer), ethyl-g Phenyl-phenol (each isomer), ethyl-heptyl-phenoxyphenol (each isomer), ethyl-heptyl-cumene - phenol (each isomer), ethyl-octylphenol (each isomer), ethyl octyl decyl phenol (each isomer), ethyl-octyl hydrazino-phenol ( Each isomer), ethyl-octyl-dodecylphenol (each isomer), ethyl-octyl-phenyl-phenol (each isomer), ethyl-octylphenoxy Phenol (each isomer), ethyl-octyl-isopropylphenyl-phenol (each isomer), ethyl-mercapto-indolyl-phenol (each isomer), ethyl-mercapto group_ Dodecyl-phenol (each isomer), ethyl-mercapto-phenyl-phenol (each isomer), ethyl-mercapto-the presentoxyne (each isomer), ethyl- Mercapto-isopropylphenyl-benzene (each isomer), ethyl-mercapto-dodecyl-phenol (each isomer), ethylmercapto-phenyl-phenol (each isomer) ), ethyl-mercapto-phenoxyphenol (each isomer), ethyl-mercapto-isopropylphenyl-phenol (each isomer), ethyl-dodecyl-phenyl-phenol (each isomer), ethyl-dodecyl-phenoxyphenol (each 131505.doc •67-200948760 isomer), ethyl-tweldium -Phenylphenyl-phenol (each isomer), ethyl-phenyl-phenoxyphenol (each isomer), ethyl-phenyl-isopropylphenyl-benzene age (each isomer) ''propyl-butyl-phenol (each isomer), propyl-butyl-pentyl----(iso-isomer), propyl-butyl-hexyl-benzene powder (each isomer) ), propyl-butyl-heptyl-benzene (each isomer), propyl-butyl-octyl-phenol (each isomer), propyl·t-butyl-fluorenyl-benzene 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-isopropylphenyl-phenol (each isomer), propyl-pentyl -Benzene (each isomer), propyl-pentyl-hexyl-stupid (each isomer), propyl-pentyl-heptyl-phenol (each isomer), propyl-pentyl Benzyl-octyl-phenol (each isomer), propyl-pentyl-indolyl-phenol (each isomer), propyl-pentyl-mercapto-phenol (each isomer), propyl- E - dodecyl-phenol (each isomer), propyl-pentyl-phenyl-phenol (each isomer), propyl-pentyl-phenoxyphenol (each isomer), propyl -pentyl-cumyl-phenol (isomeric oxime), propyl-hexyl-benzene (each isomer), propyl-hexyl-heptyl-benzene (each isomer), C Hexyl-octyl-octyl-phenol (each isomer), propyl-hexyl-fluorenyl-isolated (each isomer), propyl-hexyl-fluorenyl-benzone (each isomer), C -hexyl-dodecyl-phenol (each isomer), propyl-hexyl-phenyl-phenol (each isomer), propyl-hexyl-phenoxyphenol (each isomer), C -hexyl-isopropylidene-phenol (each isomer), propylheptyl-octyl-benzine (each isomer), propyl-heptyl-fluorenyl-benzene (isoisomer) , propyl-heptyl-fluorenyl-phenol (each isomer), propylheptyl-dodecyl-phenol (each isomer), propyl-heptyl-phenyl-benzene (each isomer), propyl-heptyl- phenyloxy 131505.doc -68 · 200948760 phenol (each isomer), propyl-heptyl cumyl- Phenol (each isomer), propyl-octyl-decyl-phenol (each isomer), propyloctylfluorenyl-phenol (each isomer), propyl-octyl-dodecyl - phenol (each isomer), propyl-octyl-phenyl-phenol (each isomer), propyl-octylphenoxyphenol (each isomer), propyl-octyl-isopropyl Phenyl-phenol (each isomer), propyl-mercapto-indolyl-phenol (each isomer), propyl-indenyl-dodecyl-phenol (each isomer), propyl- Mercapto-phenyl-phenol (each isomer), propyl nonylphenoxyphenol (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-indenyl-cumenyl-phenol (each isomer), propyl-dodecyl-phenyl-phenol (each isomer), propyl-dodecyl-phenoxy Phenol (each isomer), propyl-dodecyl-cumylphenyl-phenol (each isomer), nonylphenol (each isomer), -Phenol (each isomer), propyl-phenol (each isomer), butyl-phenol (each isomer), pentyl-phenol (each isomer), hexyl phenol Isomers), heptyl-phenol (each isomer), octyl-phenol (each isomer), mercapto-phenol (each isomer), mercapto-phenol (each isomer), ten Dialkyl-phenol (each isomer), phenyl-phenol (each isomer), phenoxyphenol (each isomer), cumyl-phenol (each isomer), propyl _ Phenylphenoxyphenol (each isomer), propyl-phenyl-cumenyl-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 131505.doc -69· 200948760 base-fluorenyl - Benzene (each isomer), propyl-butyl-t-yard benzene (each isomer), C Base-butyl-phenyl-phenol (each isomer), propyl-butyl-phenoxybenzene (each isomer), propyl-butyl-cumyl-phenol (variety) Structure), propyl pentyl phenol (each isomer), propyl-pentyl-hexyl phenol (each isomer), propyl-pentyl-heptyl-phenol (polyisomer) ), propyl-pentyl-octyl-benzene (each isomer), propyl-pentyl-mercapto-phenylene (each isomer), propyl-pentyl-mercapto-phenol (each isomer), propyl-pentyl-dodecyl-phenol (each isomer), propyl-pentyl-phenyl-phenol (each isomer), propyl-pentyl-pentyl- The present oxybenz (each isomer), propyl-pentyl-cumyl-phenol (each isomer), propyl-hexyl-heptyl phenol (each isomer), propyl _ Hexyl-octyl-phenol (each isomer), propyl-hexyl-fluorenyl phenol (each isomer), propyl-hexyl-fluorenyl-benzoic acid (isomeric), propyl·hexyl _12-alkyl-phenol (each isomer), propyl·hexyl-phenyl-phenol (each isomer), propyl-hexyl-phenoxyphenol (each isomer) , propyl-hexyl cumylphenol (each isomer), propyl-heptyl-octyl phenol (each isomer), propyl-heptyl-fluorenyl-phenol (isomeric , propyl-heptyl-fluorenyl-phenol (each isomer), propyl-heptyl-dodecyl-phenol (each isomer), propylheptyl-styl-phenol ( Each isomer), propyl-heptylphenoxyphene (each isomer), propyl-heptyl··cumyl-phenol (each isomer), propyl-octyl group _ Mercapto-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-fluorenyl-fluorenyl-phenol (each isomer), propyl-mercapto-dodecyl-phenol (each isomer), propyl nonylbenzene 131505.doc -70- 200948760 base- Phenol (each isomer), propyl-mercapto-phenoxyphenol (each isomer), propyl decyl-isopropylphenyl-phenol (each Structure), propyl-fluorenyl-dodecyl-phenol (each isomer), propyl-mercapto-phenyl-phenol (each isomer), propyl-mercapto-phenoxyphenol (each isomer), propyl-mercapto-cumyl phenyl-phenol (each isomer), propyl-dodecyl-phenyl-phenol (each isomer), propyl-tweldium Alkyl-phenoxyphenol (each isomer), propyl-dodecyl-cumyl-phenol (each isomer), propyl-phenylphenoxyphenol (each isomer) ), propyl-phenyl-cumyl phenyl-phenol (each isomer), butylpentyl-hexyldecyl-phenol (each isomer), butyl-pentyl-heptyl-phenol (each Isomers), butyl-pentyl-octyl-phenol (each isomer), butyl-pentyl-fluorenyl-phenol (each isomer), butyl-pentyl-decyl-phenol ( Each isomer), butyl-pentyldodecyl-phenol (each isomer), butyl-pentyl-phenyl-phenol (each isomer), butyl-pentyl-phenoxy Phenol (each isomer), butyl-pentyl-cumyl-phenol (each isomer), butyl-hexyl-heptyl-phenol (each isomer) , butyl-hexyl-octyl-phenol (each isomer), butyl-hexyl-fluorenyl phenol ◎ (each isomer), butyl-hexyl-decyl-phenol (each isomer) Butylhexyl-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-fluorenyl-phenol (each isomer) , butyl-heptyl-fluorenyl-phenol (each isomer), butyl-heptyl-dodecylphenol (each isomer), butyl-heptyl-phenyl-phenol (isomeric , butyl-heptyl-phenoxyphenol (each isomer), butyl-heptyl-isopropylphenyl-phenol (each isomer), butyl-octyl-fluorenyl-stupid (each isomer), butyl-octyl-mercapto-phenylene (isomeric 131505.doc •71 · 200948760), butyl-octyl-dodecyl-phenol (each isomer) , butyl-octyl-phenyl·phenol (each isomer), butyl-octyl-phenoxyphenol (each isomer), butyl- -Phenylphenyl-phenol (each isomer), butyl-nonylnonylphenol (each isomer), butyl-mercapto-dodecyl-phenol (each isomer), - mercapto-phenyl-phenol (each isomer), butyl-mercapto-phenoxyphenol (each isomer), butyl thiol cumene-phenol (each isomer) ), butyl-mercapto-dodecyl-phenol (each isomer), butyl-fluorenyl-phenyl-phenol (each isomer), butyl-mercapto-phenoxyphenol (each Isomers), butyl-fluorenyl-cumenyl-phenol (each isomer), butyl-dodecyl-phenol (each isomer), butyl-dodecyl-phenyl - benzene age (each isomer), butyl doxyl-phenoxyphenol (each isomer), butyl-dodecyl-cumylphenol-phenol (each isomer), Benzyl phenyl benzene (each isomer), butyl phenyl-phenoxy phenol (each isomer), butyl phenyl cumene phenol (each isomer), pent -hexyl-heptyl-phenol (each isomer), amyl-hexyl-octyl-phenol (each isomer), pentyl-hexyl-fluorenyl- Phenol (each isomer), amyl 〇 〇 hexyl-fluorenyl-phenol (each isomer), pentyl-hexyl-dodecyl phenol (each isomer), pentyl-hexyl-phenyl- Phenol (each isomer), amylhexylphenoxyphenol (each isomer), amyl-hexyl-cumylphenol (each isomer), pentyl-heptyl-octyl-phenol ( Each isomer), amyl-heptyl-fluorenyl-phenol (each isomer), pentyl-heptyl-fluorenyl-phenol (each isomer), pentyl-heptyl-dodecyl -phenol (each isomer), pentyl-heptyl-phenyl-phenol (each isomer), pentyl-heptyl-phenoxyphenol (each isomer), pentyl-heptyl group Propyl phenyl-phenol (each isomer), amyl-octyl-fluorenyl-phenol (each isomer), amyl-octyl-fluorenyl-phenol (each isomer), pentyl-octyl Base-dodecane 131505.doc -72- 200948760 base-phenol (each isomer), amyl-octyl-styl-phenol (each isomer), amyl-octyl-phenoxyphenol ( Each isomer), amyl-octyl-isopropylidene-p-phenol (each isomer), pentyl-fluorenyl-fluorenyl-phenol (each isomer), fluorenyl-fluorenyl-dodecanyl-phenol (each isomer), amyl-fluorenyl-phenyl-phenol (each isomer), pentyl-fluorenyl-benzene Oxyphenol (each isomer), amyl-fluorenyl-cumenyl-phenol (each isomer), amyl-fluorenyl-dodecyl-phenol (each isomer), pentyl - mercapto-phenyl-phenol (each isomer), mercapto-mercapto-phenylnonylphenol (each isomer), pentyl-mercapto-isopropylphenyl-phenylene (isomeric oxime) , pentyl-decyl-dodecyl-phenol (each isomer), amyl-decyl-phenyl-phenol (each isomer) 'pentyl-mercapto-phenoxy phenol (each isomer), pentyl·decyl-isopropyl-phenyl-benzene (each isomer), pentyl-dodecyl-phenyl-phenol (each isomer), pentyl- Dodecyl-phenoxyphenol (each isomer), amyl-dodecyl-isopropylphenyl-phenol (each isomer), pentylphenyl-phenoxyphenol (isomeric , pentyl-phenyl-cumylphenol (each isomer), hexyl-heptyl-octyl-phenol (each isomer), hexyl-heptyl-oxime - phenol (each isomer), hexyl-heptyl-fluorenyl phenol (each isomer), hexyl-heptyl-dodecyl-phenol (each isomer), hexyl-heptyl-benzene -Phenol (each isomer), hexyl-heptyl-phenoxyphenol (each isomer), hexylheptyl-isopropylphenyl-phenol (each isomer), hexyl-octyl-壬Phenol (each isomer), hexyl-octyl-fluorenyl-phenol (each isomer), hexyloctyldodecyl-phenol (each isomer), hexyl-octyl-phenyl-phenol (each isomer), hexyl-octyl-phenoxyphenol (each isomer), hexyl-octyl-cumenyl-phenol (each isomer), hexyl-mercapto-nonylphenol ( Each isomer), hexyl-decyl-dodecyl-phenol (each isomer), hexyl-fluorenyl-phenyl-phenol (each 13I505.doc-73-200948760 isomer), hexyl-oxime -Phenoxyhexyl-fluorenyl-dodecyl-phenol (each isomer), hexyl-fluorenyl-phenyl-phenol (each isomer), hexyl-nonylphenoxyphenol (variety) Structure), hexyl-fluorenyl-cumylphenyl-phenol (isomeric) - dodecyl-phenyl-phenol (each isomer), hexyl-dodecyl-phenoxyphenol (each isomer), hexyl-dodecyl-cumylphenyl-phenol (each Isomers), hexyl-phenyl-phenoxyphenol (each isomer), hexyl-phenyl-isopropyl-p-styl-stupid (each isomer), heptyl-octyl-decylbenzene (variety) Structure), heptyl-octyl-fluorenyl-phenol (each isomer), heptyl-octyl-dodecyl-alkyl-phenol (each isomer), heptyl-octyl-phenyl- Phenol (each isomer), heptyl-octyl-phenoxyphenol (each isomer), heptyl-octyl-cumylphenyl-phenol (each isomer), heptyl-fluorenyl- Mercapto-phenol (each isomer), heptyl-decyl-dodecyl-phenol (each isomer), heptyl-fluorenyl-phenylphenol (isomeric), heptyl-hydrazine Phenyloxyphenol (each isomer), heptyl-fluorenyl-cumenyl-phenol (each isomer), heptyl-fluorenyl-dodecyl-phenol (each isomer) , heptyl-fluorenyl-phenyl-phenol (each isomer), heptyl-nonylbenzene Q-oxyphenol (each isomer), heptyl- -Phenylphenyl-phenol (each isomer), heptyl-dodecyl-phenyl-phenol (each isomer), heptyldodecyl-p-oxyphenol (each isomer) ), heptyl-dodecyl-cumylphenol-phenol (each isomer), heptyl-phenyl-anthoxyphenol (each isomer), heptyl-phenyl-isopropylphenyl - phenol (each isomer), octyl-fluorenyl-fluorenyl-phenol (each isomer), octyl-decyl-dodecyl-phenol (each isomer), octyl-oxime Phenyl-phenyl-phenol (each isomer), octyl-fluorenyl-p-oxyphenol (each isomer), octyl-fluorenyl-cumyl phenyl-phenol (each isomer), octyl Base-fluorenyl-dodecylphenol (each isomer), octyl-mercapto-phenyl-phenol (isomeric 131505.doc •74·200948760), octyl-decyl-phenoxy Phenol (each isomer), octyl-fluorenyl-cumyl phenol (each isomer), octyl-dodecyl-phenyl-phenol (each isomer), octyl- Dodecyl-phenoxyphenol (each isomer), octyl-dodecyl-cumyl-phenol (each isomer), octyl- Dialkyl-phenyl-phenol (each isomer), octyl-dodecyl-phenoxyphenol (each isomer), octyl-dodecyl-cumenyl-phenol (each Isomers), octyl-phenyl-phenoxyphenol (each isomer), octyl-phenyl-isopropylphenyl-phenol (each isomer), decyl-decyl-dodecane -Phenol (each isomer), mercapto-mercapto-phenylhydrazine-phenol (each isomer), mercapto-nonyl-phenoxyphenol (each isomer), mercapto-fluorenyl - cumyl-phenol (each isomer), mercapto-dodecyl-phenyl-phenol (each isomer), mercapto-dodecyl-phenoxyphenol (each isomer) ), mercapto-dodecyl-cumyl-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-cumyl-phenol (each isomer), mercapto-phenyl-phenoxyphenol (each isomer), hydrazine

Q-phenyl-isopropylphenyl-phenol (each isomer), dodecyl-phenyl-phenoxyphenol (each isomer), dodecyl-phenyl-isopropylphenyl - Trisubstituted phenols such as phenol (each isomer) and phenyl-phenoxyisopropylphenyl-phenol (each isomer). Among these aromatic hydroxy compounds, it is more preferred to use a compound corresponding to the compound RhH, wherein the group WCKR1 constituting the diaryl carbonate is an aromatic group as defined above, and Ο represents an oxygen atom. There are hydrogen atoms. 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 by 131505.doc -75 - 200948760. The amine compound is preferably supplied in a liquid state to a reactor for producing aryl sulfonate. In general, the amine compound exemplified above is mostly solid at normal temperature (for example, 20 C), and in this case, the amine compound may be heated to above the melting point and supplied as a liquid, but at an excessively high temperature. When the amine compound is supplied to the lower side, a side reaction such as a thermal modification reaction may be generated by heating, so that the mixture of the short amine compound and the above aromatic aromatic mercaptocarbonate is preferably used as a mixture with water or a lower temperature. It is supplied in a liquid state. The reaction conditions for the reaction of the diaryl carbonate and the amine compound vary depending on the sigma of the reaction, and the diaryl carbonate is in a stoichiometric ratio with respect to the amine group of the amine compound. In the range of 〇〇〇 times, in order to increase the reaction rate, the reaction is completed early, and it is preferred that the carbonic acid diaryl vinegar has an excess amount with respect to the amine group of the amine compound, and it is preferable to consider the size of the reactor. The range of 1.1 to 50 times, and thus the range of 15 to 1 times. As for the amount of the aromatic Q-group hydroxy compound, the amount of the aromatic-based compound is preferably 1.2 to 50 times in the range of 丨~丨(9) times, relative to the amine group of the amine compound. Furthermore, it is 15~1 times better. The reaction temperature is usually in the range of 〇 °C to 15 〇t. In order to increase the reaction rate, it is preferred that the temperature is high, and on the other hand, it may cause an adverse reaction at room temperature. Therefore, the range of i〇<>c 〇〇 C is preferred. In order to fix the reaction temperature, a well-known cooling device and a heating device can be provided in the above reactor. Further, the reaction is repeated 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 x 6 Pa. There is no particular limitation on the reaction time of 131505.doc -76· 200948760 (the residence time in the case of the continuous method), and it is usually a care of ~5〇 small day, preferably 0.01 to 20 hours, more preferably 〇 (4) Hours: Further, a reaction liquid may be used, for example, by liquid chromatography to confirm the formation of the desired amount of the aryl carbamate, and the reaction is terminated. In the present embodiment, the reaction of the diaryl carbonate with the amine compound is preferred, and the catalyst is not used. In the thermal decomposition reaction of the following reaction mixture and the amino carboxylic acid vinegar contained in the reaction mixture, if the aryl carboxylic acid is heated in the presence of the metal f component from the catalyst, the urethane is sometimes produced. Aromatization heat modification reaction, etc. It is also possible to use a catalyst in the reaction of the diaryl aryl carbonate with the amine compound, and carry out the reaction mixture or the thermal decomposition reaction after the step of removing the catalyst, but the step is increased, which is disadvantageous. Second, in order to complete the reaction in the time, reduce the reaction temperature, etc., it is not possible to deny the use of the catalyst. In general, since the aromatic amine compound has lower reactivity than the aliphatic amine, when an aromatic amine compound is used as the amine compound, the use of a catalyst may be effective. In the case of using a catalyst, for example, an organometallic compound or an inorganic metal compound such as tin, erbium, copper, or chin, or a metal alkoxide of a soil test such as a bell, a nano, a retort, a hydrazine, or a hydrazine may be used. An organic catalyst such as a salt, an ethanol salt 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, The separation of the isocyanate or the aromatic hydroxy compound formed by the reaction of the thermal group 131505.doc-77·200948760 of the following urethane is troublesome. 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 phthalate> With 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). [化11]

(wherein R2 is a group defined above, and represents a group derived from an amine compound, and R1 is a group defined above, and represents a group derived from a diaryl carbonate, and η is an integer of 2 to 10, which is the same as the number of amine groups of the amine compound. number). Examples of the urethane represented by the above formula (18) include hydrazine, fluorenyl-hexanediyl-bis-carbamic acid diphenyl ester, and fluorenyl-hexanediyl-bis-aminocarbamic acid. (nonylphenyl) ester (each isomer), hexamethylene bis-aminocarbamic acid mono(ethylphenyl) vinegar (each isomer), iV, iV"'-hexanediyl-bis- Di(propylphenyl) carbamate (each isomer), see #, _ hexanediyl-bis-amino phthalic acid di(butyl 131505.doc -78- 200948760 phenyl) vinegar (variety Structure), fool #,_hexanediyl-bis-aminocarbamic acid bis(pentylphenyl)s (each isomer), diphenyl-4,4,-indenyl-dicyclohexylamine Based on acid vinegar, bis(indenyl)-4,4,-ylidene-dicyclohexylcarbamate, bis(ethylphenyl)-4,4'-arylene-bicyclic Hexyl carbazate, bis(propylphenyl)-4,4'-methylene-dicyclohexylcarbamate (each isomer), di(butylphenyl)-4,4 '-Methylene-dicyclohexylamino phthalate (each isomer), bis(pentylphenyl)-4,4'-arylene-dicyclohexylamino decanoate (isomeric Object , bis(hexylphenyl)-4,4,-methylene-dicyclohexylcarbamate (isomeric oxime), bis(heptylphenyl)-4,4,-anthracene- Dicyclohexylcarbamate (each isomer guang (octylphenyl)-4,4,-methylene-dicyclohexylcarbamate (each isomer), 3-(benzene Oxycarbonylaminomethyl-methyl)_3,5,5·trimethylcyclohexylaminocarboxylic acid phenyl vinegar, 3·(nonylphenoxycarbonylamino-methyl)_3,5,5-trimethyl Cyclohexylaminocarbamic acid (methylphenoxy) ester (each isomer), 3-(ethylphenoxylamino-indenyl)-3,5,5-trimethylcyclohexylamino Formic acid (ethylphenyl) cool (each isomer), 3-(propylphenoxycarbonylamino-indenyl)-3,5,5-trisqmethylcyclohexylamine decanoic acid (propyl Phenyl)S (each isomer), 3-(butylphenoxymethylamino-methyl)-3,5,5-trimethylcyclohexylaminocarboxylic acid (butylphenyl) cool (each isomer), 3·(pentylphenoxycarbonylamino-methyl)-3,5,5-trimethylcyclohexylaminodecanoic acid (pentylphenyl) ester (each isomer) ), 3_(hexylphenoxyamino)-A -3,5,5-trimethylcyclohexylaminocarboxylic acid (hexylphenyl) (each isomer), 3-(heptylphenoxycarbonylamino-indenyl)_3,5,5_three Nonylcyclohexylaminocarbamic acid (heptylphenyl) ester (each isomer), 3-(octylphenoxyamino-methyl)-3,5,5·trimethylcyclohexylamino Formic acid (octylphenyl) (each isomer), toluene-diamino phthalic acid diphenyl ester (each isomer), A 131505.doc -79- 200948760

❹ Benzene-diaminocarbamic acid bis(nonylphenyl) vinegar (each isomer), methyl*diamine, bis(ethylphenyl)acetate formic acid (each isomer), toluene·diaminocarbamic acid - (C: phenyl) vinegar (each isomer), toluene-diaminocarbamic acid di(butylphenyl) vinegar (each isomer), toluene-diaminocarbamic acid bis(pentyl stupyl W ( Each isomer>, toluene-diaminocarbamic acid di(hexylphenyl) brewed (each isomer), toluenediminoformic acid di(glyphosic isomer), toluene-diaminocarbamic acid (Xin: phenyl) brewed (each isomer), α^·(4,4,_methylenediphenyl)·diphenylcarbamate, 'TO, methylene·diphenyl Rhodium (methylphenyl) S, W'-(4,4'-methylene-diphenyl)-diaminopyruic acid di(ethylphenyl), methylene- Diphenyl)-di(propylphenyl) bis-dicarboxylate, iV, iV-(4,4-methylene-diphenyl)-diamino decanoic acid di(butylphenyl) ester, Imidyl-diphenyldiaminocarbamate di(pentylphenyl) ester, ΛΜ'-(4,4.-methylene-diphenyl)-diaminocarbamic acid di(hexylphenyl)S , W-(4,4·-indenylene-diphenyl)-diaminocarbamic acid di(heptylphenyl)S, 7VK4,4'-indenylene-diphenyl)-diaminocarboxylic acid An aryl carbamate such as bis(octylphenyl)ester (each isomer). <Transportation of the urethane-based 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 carry out the amine group. In the reactor for thermal decomposition reaction of aryl formate (hereinafter referred to as a 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. 131505.doc -80- 200948760 The urethanes (4) are easy to form hydrogen bonds between molecules by constituting the amino carboxylic acid urethane bond of the amino carboxylic acid, and therefore have a relatively high melting point. When such an amino aryl phthalate is transported, for example, a shaped processor which pulverizes or processes the solid urethane to a granular form 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. Aromatic vinegar vinegar* 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 amino aryl decanoate in a liquid form to the thermal decomposition reactor, a method of supplying the reaction mixture obtained by the reaction of a diaryl carbonate and an amine compound can be preferably employed. It is also possible to use a method in which the aryl urethane is heated to a temperature higher than the melting point to allow the aryl carbamate to be liquid and transported, but if it is also considered to prevent the solidification in the crucible, the amino citrate must be used. The ester is heated to a temperature above the melting point (e.g., 200 ° C). In the case where the aryl carbamate is maintained at such a high temperature, the thermal decomposition reaction of the aryl carbamate arylate is often produced at a non-ideal point to produce an isocyanate or to produce a thermally modified reaction of the aryl carbamate as described above. The reaction mixture obtained by the reaction of the diaryl carbonate with the amine compound is liquid at normal temperature (20 ° C), or is solid at room temperature, and may often be lower than the amine carboxylic acid. The temperature at the melting point of the ester becomes a homogeneous liquid', so that the thermal modification reaction of the aryl carbamate aryl ester can be suppressed. 131505.doc • 81 · 200948760 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 inhibition is suppressed. The thermal modification reaction of the aryl urethane or the like results in a decrease in the aryl sulfonium carbamate. The reason for achieving such an effect is not clear, but the inventors of the present invention presumed that 'in the reaction for forming a urea bond represented by the above formula (2), 'the aromatic hydroxy compound contained in the reaction mixture, and the uric acid The ester amino phthalate bond (_nhcoo_) b forms a hydrogen bond, whereby a urethane bond is in a state in which it is 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 in the temperature range of it~i 8〇〇c, more preferably 30°C to 17 (TC, and further preferably 5 (TC~15) in the temperature range of TC. The aryl aryl phthalate 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 vaporization separation operation or the like, and thus has a The advantage of the hydrazine step is simplified. Further, as a method of separating 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 simplify the steps. <Thermal decomposition reaction of aryl carbamate> Next, an isogastric acid ester is produced by thermal decomposition reaction of an amino aryl phthalate. The thermal decomposition reaction of this embodiment is a reaction of an isocyanate and an aromatic hydroxy compound from an amino aryl phthalate. 131505.doc -82 · 200948760 The reaction temperature is usually a bribe ~ 30 (the range of rc, in order to increase the reaction rate '匕 is better high temperature, on the other hand, sometimes at high temperatures due to the amino carboxylic acid aromatic vinegar and / or as a generation The isocyanic acid vinegar causes the side reaction as described above, so it is preferably in the range of 15 passages to 25 generations. It is (iv) the reaction temperature °; the above-mentioned reactor is provided with a well-known cooling device, and the heating reaction pressure is according to the The type of the compound to be used or the reaction temperature is different, and it may be any one of dust reduction, normal pressure, and dusting, and is usually not limited in the case of the reaction time of the Shishi ία6 (four) D (the residence time in the case of the continuous method). It is usually 0.001 to 100 hours, preferably 0.005 to 50 hours, more preferably 1 to 1 hour. In the present embodiment, it is preferred that no catalyst is used. The catalyst can be used to promote thermal decomposition. Although the reaction is carried out, it is often easy to produce a side reaction caused by the above-mentioned amino formic acid aryl g and/or isocyanate as a product, and thus it is disadvantageous. When the amino carboxylic acid aromatic vinegar is kept at a high temperature for a long period of time, it sometimes occurs as described above. The side reaction, in addition, the sulphuric acid sulphuric acid formed by the thermal decomposition reaction sometimes causes a side reaction as described above. Therefore, the amino carboxylic acid aromatic broth and the isocyanate vinegar are kept at a high temperature for a longer period of time. Preferably, it is as short as possible, and the thermal decomposition reaction is preferably carried out in a continuous process. The so-called continuous process means that a mixture containing the aryl aryl carbamate is continuously supplied to the reactor for thermal decomposition reaction. a method of continuously discharging the produced isocyanate and aromatic hydroxy compound from the thermal decomposition reactor. In the continuous method, a low-boiling component formed by thermal decomposition reaction of an amino aryl phthalate is preferably used as The gas phase component is recovered from the upper part of the thermal decomposition reactor, and the remaining portion is recovered as a liquid phase component from the bottom of the thermal decomposition reactor. All compounds present in the thermal decomposition reactor of J31505.doc -83- 200948760 can also be used. It is recovered as a gas phase component, but by the presence of a liquid phase component in the thermal decomposition reactor, a polycondensation by a side reaction caused by an aryl aryl phthalate and/or an isocyanate can be obtained. The dissolution of the compound compound has the effect of preventing the polymer compound from adhering to and accumulating in the thermal decomposition reactor. The thermal decomposition reaction of the amino aryl phthalate is used to form an isocyanate and an aromatic hydroxy compound, and the compounds are neutralized. One of the compounds is recovered as a gas phase component, and which compound is recovered as a gas phase component depends on the thermal decomposition reaction conditions. Here, the term used in the present embodiment is the heat of the aryl aryl phthalate. The low-boiling component formed by the decomposition reaction corresponds to an aromatic hydroxy compound and/or isocyanate Sa formed by thermal decomposition reaction of the urethane, and particularly refers to a condition for carrying out the thermal decomposition reaction. A compound which can be present as a gas. For example, 'isocyanate formed by a thermal decomposition reaction and an aromatic meso-based compound can be recovered as a gas phase component, and the diaryl vinegar and/or amino phthalate are contained. The method of recovering the liquid phase component. In this method, the isocyanate and the aromatic mercapto compound can be separately recovered by a thermal decomposition reactor. The recovered gas phase component containing an isocyanate is preferably supplied in a gas phase to a steaming unit for purifying and separating the isogas. The recovered gas phase component containing the dissociated acid S may be supplied to the distillation apparatus by a condenser or the like, and then supplied to the distillation apparatus. However, the apparatus is often complicated or the energy used is increased. . On the other hand, a liquid phase component containing a diaryl carbonate and/or an aryl phthalate is recovered from the bottom of the thermal decomposition reactor, and when the liquid component contains a diaryl carbonate, a preferred 131505.doc -84- 200948760 疋' The diaryl carbonate was separated and recovered from the liquid phase component, and the diaryl vinegar was reused. 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, the system 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 maintained at 5 (TC 18 (TC ' is more preferably 7 {rc to 17 〇). <t, and further preferably 100°C to i5〇°c. Further, for example, the isocyanate, the aromatic hydroxy compound and the diaryl carbonate formed by the thermal decomposition reaction can be recovered as a gas phase component, and the liquid phase component containing the aryl aryl phthalate can be thermally decomposed. The bottom of the reactor is recovered by a method. In this method, the recovered Q-containing gas component containing isocyanate is preferably supplied in a vapor phase to a vaporizer apparatus for purifying and separating the isocyanate. Further, a part or all of the liquid phase component containing the aromatic aryl aryl vinegar is supplied to the upper portion of the thermal decomposition reactor, and the amine sulfonium ester 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 maintained at 疋50C to 180. (:, more preferably 7〇〇c~17〇〇c, and further preferably C~15 0°C and transported. # Further', for example, an isocyanate formed by thermal decomposition reaction and a Fangxiang group can be used. In the base compound, the aromatic trans group-based compound is recovered as a gas phase component 131505.doc-85-200948760. A method of recovering a mixture containing the isocyanate as a liquid phase component from the bottom of the thermal decomposition reactor. The liquid phase component is supplied to the distillation apparatus to recover the isocyanate. When the liquid phase component contains a diaryl carbonate, it is preferred to separate and recycle the diaryl carbonate. In the case where the component contains an aryl carbamate, it is preferred to supply a part or all of the mixture containing the aryl aryl citrate to the upper part of the thermal decomposition reactor to make the amino arsenic vinegar The thermal decomposition reaction is carried out 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 maintained at 疋50C to 180C', more preferably 70°C to 170°. °C, into Preferably, it is transported at a temperature of from 1 ° C to 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 polymerous by-product formed by the side reaction caused by the aryl aryl phthalate and/or the isocyanate is dissolved by the presence of the liquid phase component in the thermal decomposition reactor, and Q is used as the liquid phase component autothermal decomposition reactor. Discharging, thereby 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 thereto. The upper part of the reactor is thermally decomposed, and the amino formic acid is again subjected to a thermal decomposition reaction. When this step is repeated, a polymer-form by-product may be accumulated in the liquid phase component. In this case, the liquid phase component may be obtained. Part or all of it is removed from the reaction system to reduce the accumulation of polymer-like by-products, or may be maintained at a certain concentration. The gas phase component and/or liquid phase component obtained by the above thermal decomposition reaction is 131505. Doc -86- 200948760 The aromatic trans-based compounds and/or diaryl carbonates can be separated and reused separately. Specifically, the aromatic trans-based compounds can be reused as carbonic acid, and the reaction of aromatic and amine compounds The reaction solvent, and/or the aromatic hydroxy compound A of the step (3) for producing a diaryl carbonate, the diaryl carbonate can be reused as a raw material for producing an aryl urethane. The form of the thermal decomposition reactor is not In particular, in order to efficiently recover the gas phase component, it is preferred to use a well-known distillation apparatus. For example, a steaming tower, a multi-stage steaming tower, a multi-tubular reactor, a continuous multi-stage distillation tower can be used. a method of filling a column, a thin film evaporator, a reactor having a support inside, a forced circulation reactor, a falling film evaporator, and a falling drop evaporator, and a method of combining the same, etc. Various methods. 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, and a better drying chamber. The resulting low-boiling component is rapidly transferred to a structure in which the gas-liquid contact area of the gas phase is large. The material of the thermal decomposition reactor and the line may be any known material, such as SUS3〇4 or SUS316, SUS316L, if the arylamine carboxylic acid ester or the aromatic hydroxy compound or isocyanate as a product is adversely affected. It is cheaper, so it can be used well. <Cleaning of Thermal Decomposition Reactor> In the present embodiment, the reaction liquid containing an aryl urethane obtained by reacting a diaryl carbonate with an amine compound contains, for example, the above formula (5), formula (6), A polymer-formed side reaction product represented by the formula (7). The side reaction 131505. Doc-87 - 200948760 Most of the two products are easily dissolved in the aromatic mercapto group compound, and therefore are dissolved in the reaction liquid in which the amino acid is used. However, in the thermal decomposition reactor, if most of the aromatic trans group-based 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 urethane carboxylic acid, for example, a polybinder product derived from a side reaction represented by the above formula (8), formula (9), formula (10), or the like, and a by-product of the thermal decomposition reaction are produced. It is also often attached to the ❹=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 that the compound attached to the thermal decomposition reactor was found to be 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 35-decomposition reactor, the wall surface of the thermal decomposition reactor is washed with acid, and the high-boiling substances are dissolved and heated therefrom. The decomposition reactor is removed, thereby keeping the inside of the thermal decomposition reactor (especially the wall) clean. By using the 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 production efficiency of the isocyanate is higher than that of the cleaning acid. In the case of dissolving the polymer-form by-product, it is not particularly limited, and any of an organic acid and an inorganic acid can be used, and an organic acid is preferably used. The organic acid may, for example, be a carboxylic acid, a sulfonic acid, a sulfinic acid, a benzophenone, a female alcohol, a sulfur (tetra), a quinone imine, a fat, or an aromatic extender amine 13I505. Doc-88- 200948760 class, etc., it is preferred to use carboxylic acid, phenol. Examples of such a compound include formic acid, acetic acid, propionic acid, n-butyric acid, isobutyric acid, valeric acid, isovaleric acid, 2-methylbutyric acid, pivalic acid, caproic acid, isohexanoic acid, and decylethyl. Butyric acid, 2,2-dimethylbutyric acid, heptanoic acid (each isomer), octanoic acid (each isomer), citric acid (each isomer), citric acid (each isomer), eleven Acid (each isomer), dodecanoic acid (each isomer), tetradecanoic acid (each isomer), palmitic acid (each isomer), acrylic acid, crotonic acid, isobutyl acid, ethylene Saturated or unsaturated aliphatic monocarboxylic acid compounds such as acetic acid, methacrylic acid, leucovoric acid, glyceryl acid, allyl acetic acid, undecylenic acid (each isomer), oxalic acid, malonic acid, Succinic acid, glutaric acid, adipic acid, pimelic acid (each isomer), suberic acid (each isomer), sebacic acid (each isomer), azelaic acid (each isomer) ), maleic acid, fumaric acid, methyl maleic acid, decyl fumaric acid, glutaconic acid (isomers), itaconic acid, allyl propane Saturated or unsaturated sulphate Saturated or unsaturated aliphatic tricarboxylic acid compounds such as carboxylic acid, propane tricarboxylic acid, propylene propylene tricarboxylic acid, 2'3-methylbutane tricarboxylic acid, benzoic acid, methyl benzoate (various Fragrance, ethyl benzoate (each isomer), propyl benzoate (each isomer), dinonyl benzoate (each isomer), trimethyl benzoic acid (isomeric), etc. An aromatic dicarboxylic acid compound such as phthalic acid, phthalic acid, isophthalic acid, terephthalic acid or methyl isophthalic acid (each isomer), hydrazine, 2,3-benzenetricarboxylic acid , aromatic tris(tetra) compounds such as 1'2'4-benzenetricarboxylic acid and trimellitic acid, benzophenone, methyl-benzoin (each isomer), ethyl-benzoin (each isomer), propyl - Benzene (each isomer), butyl-benzene (each isomer), pentyl-benzene (each isomer), hexyl-benzene age (each isomer), heptyl-benzene (All isomers 131505. Doc •89· 200948760 Octyl-phenol (each isomer), mercapto-phenol (each isomer), mercapto-phenol (each isomer), dodecyl-phenol (each isomer) Monosubstituted phenols such as phenyl-phenol (each isomer), phenoxyphenol (each isomer), cumyl-phenol (each isomer), dimethyl-phenol (isomeric , 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)' Cumyl-phenol (each isomer), methyl-ethyl-phenol (each isomer), methyl-propyl-phenol (each isomer), methyl-butyl-phenol (each Isomer), mercapto-pentyl-phenol (each isomer) , methyl-hexyl-phenol (each isomer), mercapto-heptyl-phenol (each isomer), mercapto-octyl-phenol (each isomer), mercapto-fluorenyl-phenol ( Each isomer), methyl-mercapto-phenol (each isomer), mercapto-dodecylphenol (each isomer), methyl-phenyl-benzene (each isomer), Methyl-phenoxybenzene (each isomer), methyl-isopropylphenyl-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-fluorenyl-phenol (each isomer), ethyl-mercapto-phenol (each isomer), ethyl-dodecyl group Benzine (each isomer), ethyl-phenyl-phenol (each isomer), ethylphenoxyphenol (each isomer), ethyl-cumylphenol-phenol (each isomer) ), propyl-butyl-phenol (each isomer), propyl-pentyl-phenol (each isomer), propyl·131505 . Doc -90- 200948760 Hexyl-phenol (each isomer), propyl-heptyl-phenol (each isomer), propyl-octyl·phenol (each isomer), propyl-mercapto group_ Phenol (each isomer), propyl-mercapto-phenol (each isomer), propyl-dodecyl-phenol (each isomer), propyl-phenyl-p-phenol (isoisomer) , propyl-phenoxyphenol (each isomer), propyl-isopropylphenyl·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 (isomeric) , 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), pentyl-heptyl-phenol (variety) Structure), amyl _ octyl phenol (each isomer), pentyl-fluorenyl phenol (iso areomers) ), pentyl hydrazino-phenol (each isomer), pentyl-dodecyl phenol (each isomer), pentyl phenyl-phenol (each isomer), pentyl-phenoxy Phenol (each isomer), pentyl-cumyl-phenol (each isomer), hexyl-heptyl phenol (each Q 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), hexylphenoxyphenol (each isomer), hexyl-cumylphenol-phenol (each isomer), heptyl-octyl-phenol (each isomer), heptyl group Mercapto-phenol (each isomer), heptyl-decyl-phenol (each isomer), heptyl-dodecyl-phenol (each isomer, heptyl-phenyl-phenol (each isomer) ), heptyl-phenoxyphenol (each isomer), heptyl-isopropylphenyl-phenol (each isomer), octyl-fluorenyl-phenol (each isomer), octyl·癸Base-phenol (each isomer), octyl-dodecyl-stupid 13I505. Doc -91 · 200948760 Phenol (each isomer), octyl-phenyl-phenol (each isomer), octylphenoxyphenol (each isomer), octyl-isopropylphenyl-phenol ( Each isomer) 'mercapto- fluorenyl phenol (each isomer), fluorenyl-dodecyl-polyphenol (each isomer), fluorenyl-stupyl-stupylphenol (each isomer) ), fluorenyl-phenoxy abundance (each isomer), mercapto-cumyl-benzoquinone (isomers), twelfth phenyl phenyl benzene (all isomers), Dodecyl-phenoxyphenol (each isomer), dodecyl-isopropyl-based-division--(iso-isomers) and other disubstituted benzenes, trimethyl-benzene (various Structure), triethyl-phenol (each isomer), tripropyl-benzene (each isomer), dibutyl-benzene (each isomer), tripentyl-benzene (each Isomers), trihexyl-phenol (each isomer), triheptyl-phenol (each isomer), trioctyl-phenol (each isomer), tridecyl-phenol (each isomer) ), tridecyl-phenol (each isomer), tris(dodecyl)-phenol (each isomer), three Base-bens (each isomer), triphenyloxybenzene (each isomer), triisopropylphenyl·phenol (each isomer), dimethyl-ethylphenol (isoisomer) , dimercapto-propyl-phenol (each isomer), dimethyl-butyl-phenol (each isomer), dimethyl-pentyl-phenol (each isomer), diterpene -hexyl-phenol (each isomer), dimethyl-heptyl-phenol (each isomer), dimercapto-octyl-phenol (each isomer), dimercapto-indenyl-phenol (each isomer), dimethyl-hydrazino-p-phenol (each isomer), didecyl-dodecyl-phenol (each isomer), dimercapto-phenyl-phenol ( Each isomer), dimercapto-phenoxyphenol (each isomer), dimethyl-isopropylphenyl-phenol (each isomer), diethyl-fluorenyl group Structure), diethyl-propyl-benzene (each isomer), diethyl-butyl-phenol (each isomer), diethyl-pentyl-phenol (each isomer), Diethyl-hexyl-phenol (each isomer), diethyl-heptyl-phenol (each isomer), 131505. Doc •92- 200948760—ethyl-octyl-phenol (each isomer), diethyl-mercapto-phenol (each isomer), diethyl-mercapto-phenol (each isomer), Diethyl-dodecyl-phenol (each isomer), diethyl-phenyl-phenol (each isomer), diethylphenoxyphenol (isomeric), diethyl - cumyl phenyl 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-benzoquinone (each isomer), dipropyl-octyl-phenol (each isomer), dipropyl decyl phenol (each isomer), dipropyl-fluorenyl phenol (each isomer) , dipropyl-dodecyl-phenol (each isomer), dipropyl-phenyl-phenol (each isomer), dipropyl-phenoxyphenol (each isomer), dipropyl -Phenylphenyl·phenol (each isomer), dibutyl-mercapto-phenol (each isomer), dibutyl -ethyl-phenol (each isomer), dibutyl-propyl-phenol (each isomer), dibutyl-pentyl-phenol (each isomer), dibutyl-hexyl-phenol (each isomer), monobutyl-heptyl-phenol (each isomer), dibutyl-octyl-phenol (each isomer), dibutyl-mercapto-phenol (each isomer) ), dibutyl-nonylphenol (each isomer), dibutyl-dodecyl-phenol (each isomer), dibutyl styryl-phenol (each isomer), dibutyl -phenoxyphenol (each isomer), dibutyl cumene-phenol (each isomer), dipentyl-methyl-phenol (each isomer), dipentyl-ethyl - phenol (each isomer), dipentyl-propyl-phenol (each isomer), dipentyl-butyl-phenol (each isomer), dipentyl-hexylphenol (isoisomer) , dipentyl-heptyl-phenol (each isomer), dipentyloctyl-phenol (each isomer), dipentyl-mercapto-p-phenol (isomeric), dipentane Base thiol-phenol (each isomer), dipentyl-dodecyl-phenol (isomeric 131505. Doc-93- 200948760), dipentyl-phenyl-phenol (each isomer), dipentyl-phenoxyphenol (each isomer), dipentyl-iso. Propyl phenyl-phenol (each isomer), dihexyl-methyl-phenol (each isomer), dihexyl-ethyl-phenol (each isomer), dihexyl-propyl-phenol (different Structure), dihexyl-butyl-phenol (each isomer), dihexyl-pentyl-phenol (each isomer), dihexyl-heptyl-phenol (each isomer), dihexyl-octyl -Phenol (each isomer), dihexyl-fluorenyl-benzoic acid (each isomer), dihexyl-fluorenyl-benzoic acid (each isomer), dihexyldecyl-dialkyl-phenol ( Each isomer), dihexyl-phenyl-phenol (each isomer), monohexyl-p-oxybenzone (each isomer), dihexyl-cumenyl 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), heptyl-indenyl-phenol (isomeric), diheptane _nonylphenol (each isomer), monoheptyl-dodecyl-benzoic acid (each isomer), diheptyl-phenyl-cupolic phenol (each isomer), diheptyl group Phenoxyphenol (each isomer), diheptyl-isopropylphenyl-phenol (each isomer), dioctyl-fluorenyl-phenol (each isomer), dioctyl-ethyl- Phenol (each isomer), dioctyl-propyl-phenol (each isomer), dioctyl-butyl-phenol (each isomer) 'dioctyl-pentyl-phenol (isoisomer) , dioctyl-hexyl-phenol (each isomer), dioctyl-heptyl-phenol (each isomer), dioctyl-fluorenyl-phenol (each isomer), dioctyl - mercaptophenol (each isomer), dioctyl-dodecylphenol (each isomer), octyl-phenyl-phenol (each isomer), dioctyl-phenyloxy Phenol (each isomer), dioctyl-isopropylphenyl-phenol (each isomer), dimercapto-methyl-benzene 131505. Doc -94- 200948760 (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), monodecyl-heptyl-phenol (each isomer) ), dimercapto-octyl-phenol (each isomer), dimercapto-fluorenyl-benzoic acid (isomeric), dimercapto-t-cylylene-benzene (each isomer) , dimercapto-phenyl-benzene (each isomer), dimercapto-p-oxyphenol (each isomer), dimercapto-cumyl-phenol (each isomer), two Mercapto-methyl-phenol (each isomer), dimercapto-ethyl-phenol (isomeric product), dimercapto-propyl-phenol (isomeric), dimercapto-butyl -Phenol (each isomer), Dimercapto-pentyl-phenol (each isomer), Dimercapto-hexylbenzene (each isomer), Dimercapto-heptyl-Benzene (each Isomers), dimercaptooctyl-present (each isomer), dimercapto-mercapto-phenyl age (each isomer), Mercapto-eleven-alkyl-isolated (iso-isomers) 'dimercapto-phenyl-phenanthrene (each isomer), dimercapto-phenoxybenzene (each isomer), Dimercapto- isopropylidene phenol (each isomer), di(dodecyl)-fluorenyl-phenol (each isomer), di-Q (dodecyl)-ethyl-phenol (each isomer), di(dodecylpropylphenol (each isomer), di(dodecyl)-butyl-phenol (each isomer), di(dodecyl)- Pentyl-phenol (each isomer), bis(dodecyl)-hexyl-phenol (each isomer), di(dodecyl)-heptyl-p-phenol (each isomer), two (dodecyl)-octyl-phenol (each isomer), di(dodecyl)decylphenol (each isomer), di(dodecyl)-fluorenyl-phenol (each Isomer), di(dodecyl)-dodecyl-phenol (each isomer), di(dodecyl)-phenyl-phenol (each isomer), di(dodecane) Phenoxyphenol (each isomer), di(dodecyl)-isopropylphenyl-phenyl (isomer), diphenyl 131505. Doc -95- 200948760 base-p-phenol (each isomer), diphenyl-ethylphenol (each isomer), di-p-propyl-phenol (each isomer), di-phenyl group -Phenol (each isomer), diphenyl-pentyl-phenol (each isomer), diphenyl-hexyl-phenol (each isomer), diphenyl-heptyl-phenol (different Structure), diphenyl-octyl-phenol (each isomer), diphenyl-mercapto-p-phenol (each isomer), diphenyl-mercapto-p-phenol (isomeric) , diphenyl-dodecyl-phenol (each isomer), diphenyl-phenoxyphenol (each isomer), diphenyl-cumylphenyl-phenol (each isomer), Diphenoxymethyl-phenol (each isomer), diphenoxyethyl-phenol (each isomer), diphenoxypropyl-phenol (each isomer), diphenoxybutyrate Base-p-phenol (each isomer), diphenoxypentyl-phenol (each isomer), diphenoxyhexyl-phenol (each isomer), diphenoxyheptyl-phenol (each Isomers), diphenoxyoctyl-phenol (each isomer), diphenoxynonyl-phenol (each Structure), diphenoxynonyl-phenol (each isomer), diphenoxydodecyl-phenol (each isomer), diphenoxyphenyl-phenol (each isomer) , diphenoxyisopropylphenyl·•phenol (each isomer), diisopropylphenyl-methyl-benzene Q phenol (each isomer), dicumyl-ethyl-phenol (each Isomers), diisopropylphenyl-propyl-polyphenol (each isomer), dicumyl-butyl-phenol (each isomer), diisopropylphenyl-pentyl-phenol (each isomer), dicumyl-hexyl-phenol (each isomer), diisopropylphenylheptylphenol (each isomer) diisopropylphenyl-octyl-phenol (different Structure), diisopropylphenylindolyl-phenol (each isomer), diisopropylphenyl-fluorenyl-phenol (each isomer), dicumyl-dodecyl-phenol ( Each isomer), dicumylphenyl-phenol (each isomer), diisopropylphenyl-phenoxyphenol (each isomer), methylethyl-propyl-phenol (each Isomer), methyl-ethyl-butyl-phenol (each isomer), 131505. Doc -96- 200948760 Methyl-ethyl-pentyl-phenol (each isomer), methyl-ethylhexyl-phenol (each isomer), methyl-ethylheptyl-phenol (variety) Structure), methyl-ethyl-octyl-phenol (each isomer), mercapto-ethyl-fluorenyl-phenol (each isomer), methyl-ethyl-decyl-phenol (each Isomers), methyl-ethyldodecanyl-phenol (each isomer), methyl-ethyl-phenyl-phenol (each isomer), mercapto-ethylphenoxyphenol (each isomer), methyl-ethyl-cumyl-phenol (each isomer), mercapto-propyl-mercapto-propyl-butyl-phenol (each isomer), A -propyl-pentyl-phenol (each isomer), methyl-propyl-hexyl_© phenol (each isomer), methyl-propyl-heptyl-phenol (each isomer), Methyl-propyl-octylphenol (each isomer), methyl-propyl-mercapto-phenol (each isomer), methyl-propyl-indolyl-phenol (each isomer) , methyl-propyl-dodecyl-polyphenol (each isomer), mercapto-propyl-phenylphenol (each isomer), methyl-propyl-benzene Phenol (each isomer), methyl-propyl-cumyl-benzophenone (each isomer), methyl butyl-pentyl-benzene age (each isomer), methyl- Butyl-hexyl-phenol (each isomer), mercapto-butyl-heptyl-phenol (isomeric & thiol), mercapto-butyl-octyl-phenol (each isomer), A — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — Methyl-butyl-phenyl-phenol (each isomer), methyl butyl phenoxy phenol (each isomer), methyl butyl _ cumyl phenol (isoisomer) , methyl-pentyl-hexyl-phenol (each isomer), mercapto-pentyl-heptyl-phenol (each isomer), mercapto-pentyl-octyl-phenol (isomeric) , fluorenyl-pentyl-fluorenyl-phenol (each isomer), fluorenyl _ pentyl-fluorenyl-stupid (each isomer), fluorenyl _ «pentyl _ 12 base Benzine (each isomer), mercapto-pentyl phenyl-phenol (each isomer), methyl-pentyl-stupid 131505. Doc •97· 200948760 oxyphenol (each isomer), methyl-pentyl cumene-phenol (each isomer), methyl-hexyl-heptyl-phenol (each isomer), Methyl·hexyl-octyl_phenol (each isomer), methyl-hexyl-mercapto-phenol (each isomer), methyl-hexyl-fluorenyl-phenol (each isomer), methyl -hexyl-dodecyl-phenol (each isomer), methyl-hexyl-phenyl-phenol (each isomer), methylhexyl-phenoxyphenol (each isomer), methyl group_ Hexyl cumylphenol (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-decyl-phenol (each isomer), ethylpropyl decyl-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 Q (each isomer), ethyl-butyl-octyl-phenol (each isomer) , ethyl butyl-mercapto-phenol (each isomer), ethyl-butyl decyl phenol (each isomer), ethyl-butyl-dodecyl phenol (isoisomer) , ethyl-butyl phenyl-phenol (each isomer), ethyl-butyl-phenoxyphenol (each isomer), ethyl butyl-isopropylphenyl phenol ( Each isomer) 'ethyl-pentyl-hexylphenol (each isomer), ethyl·pentyl-heptyl-benzene (each isomer), ethyl-pentyl-octyl-phenol ( Each isomer), ethyl·pentyl-nonylphenol (each foreign matter), ethyl-pentyl-mercapto-phenol (each isomer), ethylpentyl decyl-benzene (each Isomer), ethyl-fluorenyl, stupyl-phenol (each isomer), $ Qin 131505. Doc 200948760 yl-pentyl-phenoxyphenol (each isomer), ethyl-pentyl-cumylphenol (each isomer), ethyl-hexyl-heptyl-phenol (each isomer) ), ethyl-hexyl-octyl-phenol (each isomer), ethyl-hexyl-fluorenyl-phenol (each isomer), ethyl-hexyl-decyl-phenol (each isomer), Ethyl-hexyl-dodecyl-phenol (each isomer), ethyl-hexyl-phenyl-phenol (each isomer), ethylhexyl-phenoxyphenol (each isomer), Ethyl-hexyl-cumylphenyl-phenol (each isomer), ethyl-heptyl-octyl-phenol (each isomer), ethyl-heptyl-decyl-phenol (each isomer) ), ethyl-heptyl-fluorenyl-p-phenol (each isomer), ethylheptyl-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-fluorenyl-phenol (each isomer), ethyl-octyl-mercapto-phenyl age (variety) , ethyl-octyl-dodecylphenol (each isomer), ethyl-octyl-phenyl-phenol (each isomer), ethyl-octyl-phenoxyphenol (each Isomers), ethyl-octyl-isopropylphenyl-phenol (each isomer), Q ethyl-mercapto-indolyl-phenol (each isomer), ethyl-mercapto- 12 Alkyl-benzoin (each isomer), ethyl-mercapto-phenyl-phenol (each isomer), ethylmercapto-phenoxyphenol (each isomer), ethyl-mercapto group - cumyl phenol (each isomer), ethyl-mercapto-dodecyl-phenol (each isomer), ethyl-mercapto-phenyl-phenol (each isomer), Ethyl-indenyl-phenoxyphenol (each isomer), ethyl-mercapto-isopropylphenyl·phenol (each isomer), ethyl-dodecyl-phenyl-phenol (each Isomer), ethyl-dodecyl-phenoxybenz (each isomer), ethyl-dodecyl-isopropylidene phenol (each isomer), ethyl-benzene -Phenoxybenzene (each isomer), ethyl-phenyl-cumylbenzene 131505. Doc -99· 200948760 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 phenoxy phenol (each isomer), propyl-butyl-isopropyl phenyl-phenol (each isomer) ), propyl-pentyl-phenol (each isomer), propyl-pentyl-hexyl-phenol (isomeric product), propyl-pentyl-heptyl-phenol (each isomer), Propyl-pentyl-octyl _ present age (each isomer), propyl-pentyl-fluorenyl-benzoic acid (each isomer), propyl-pentyl-fluorenyl-benzene (variety) Structure), propyl-pentyl-dodecyl-benzene (iso-isomer), propyl-pentyl-phenyl-phenol (each isomer), propylpentyl Essentially (each isomer), propyl·pentyl-cumyl-benzene (each isomer), propyl-hexyl-benzone (each isomer), propyl·hexyl-heptyl _ phenol (each isomer), propyl-hexyl-octyl-phenol (each isomer), propyl-hexyl fluorenyl-fluorenyl-phenol (each isomer), propyl-hexyl-fluorene Phenol (each isomer), propyl·hexyl-dodecyl-phenol (each isomer), propyl·hexyl-styl-phenol (each isomer), propyl-hexyl-benzene Oxyphenol (each isomer), propyl-hexyl-cumyl-phenol (each isomer), propyl-heptyl octylphenol (each isomer), propyl-heptyl-hydrazine -Phenol (each isomer), propyl-heptyl-decyl-phenol (each isomer), propyl-heptyl-dodecyl-phenol (each isomer)' propyl-g -Phenyl-phenol (each isomer), propylheptyl phenoxy phenol (each isomer), propyl-heptyl-isopropylphenyl-phenol (each isomer), propyl- Octyl-fluorenyl-phenol (each isomer), propyl-octyl fluorenyl _ 131505. Doc •100- 200948760 Benzene (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 (isomeric , propyl-mercapto-dodecyl phenol (each isomer), propyl-mercapto-phenyl-phenol (each isomer), propyl-mercapto-phenoxyphenol ( Each isomer), propyl-hydrazino-cumyl-phenol (each isomer), propyl-indenyl-dodecylphenol (each isomer), propyl-mercapto group_ 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), mercapto-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 (variety) Structure), mercapto-phenol (each isomer), mercapto-phenol (each isomer), decadecyl-phenol (each isomer), phenyl-phenol (each isomer) , phenoxyphenol (each isomer), cumyl-phenol (each isomer), propyl-phenyl-phenoxyphenol (each isomer), propyl-phenyl-isopropyl Phenyl-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-p-phenol (each isomer), propylbutyl-decyl-phenol (each isomer), propyl-butyl-dodecyl-phenol (each isomer) , propyl-butyl-phenyl-phenol (each isomer), propylbutyl oxyphylline 131505. Doc -101- 200948760 phenol (each isomer), propyl-butyl-isopropylphenyl-phenol (each isomer), propyl-pentyl-benzene (each isomer), propyl -pentyl-hexyl-phenol (each isomer), propyl-pentyl-heptyl-phenol (each isomer), propyl-pentyl-octyl-phenol (each isomer), propyl -pentyl-fluorenyl-phenol (each isomer), propyl-pentyl-mercapto-benzene (each isomer), propyl-pentyl-dodecyl-phenol (each isomer) ), propyl-pentyl-phenyl-phenol (each isomer), propyl-pentyl-phenoxyphenol (each isomer), propyl-pentyl-cumylphenol (variety) Structure), propyl-hexyl-heptyl-phenol (each isomer), propyl-hexyl benzyl-octyl-phenol (each isomer) 'propyl-hexyl decyl phenol (variety) Structure), propyl-hexyl-decyl-phenol (each isomer), propyl·hexyl-dodecyl-phenol (each isomer), propyl-hexyl-phenyl-phenol (variety) Structure), propyl-hexyl-presentoxyl (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-heptylbenzene Q-phenylphenol (each isomer), propyl-heptylphenoxyphenol ( Each isomer), propyl-heptyl-cumyl-phenol (each isomer), propyl-octyldecyl-phenol (each isomer), propyl-octyl-decyl-phenol ( Each isomer), propyl-octyl-dodecyl-phenol (each isomer), propyl-octyl-phenyl-phenol (each isomer), propyl-octyl-phenoxy Phenol (each isomer), propyl-octyl-isopropylphenyl-phenol (each isomer), propyl-mercapto-mercapto-phenol (each isomer), propyl-fluorenyl - dodecyl-phenol (each isomer), propyl decyl-phenyl-phenol (each isomer), propyl-mercapto-phenoxyphenol (each isomer), propyl- Mercapto-cumenyl-phenol (each isomer), propyl-fluorenyl _ 131505. Doc •102- 200948760 base-phenol (each isomer), propyl-mercapto-phenyl-phenol (each isomer), propyl·nonyl-phenoxyphenol (each isomer), Propyl-fluorenyl-cumylphenyl-benzoate (each isomer), propyl-dodecyl-phenyl-phenol (each isomer), propyl-dodecyl-phenoxy Phenol (each isomer), cumene-phenol (each isomer) 'propyl-phenyl-phenoxyphenol (each isomer), propyl-phenyl-cumylphenol-phenol (each isomer), butyl-pentyl-hexyl-phenol (each isomer), butyl-pentyl-heptyl-phenol (each isomer), butyl-pentyl-octyl-phenol (each isomer), butyl-pentyl-fluorenyl-phenol (each isomer), butyl _ pentyl-mercapto-phenol (each isomer), butyl-pentyl-tweldium Alkyl-phenol (each isomer), butyl-pentyl-phenyl-phenol (each isomer), butyl-pentyl-phenoxyphenol (each isomer), butyl-pentyl _Phenylphenyl-phenol (each isomer), butyl-hexylheptyl-phenol (each isomer), butyl-hexyl-octyl_benzene Phenol (each isomer), butyl-hexyl-fluorenyl-phenol (each isomer), butyl-hexyl-fluorenyl-phenol (each isomer), butyl-hexyl-dodecyl group Phenol (each isomer), butyl-hexyl-phenyl-phenol (each isomer), butylhexyl-benzene oxyphenol (each isomer), butyl-hexyl cumene _ Phenol (each isomer), butyl-heptyl-octyl phenol (each isomer), butyl-heptyl-fluorenyl phenol (each isomer), butyl-heptyl-fluorenyl - phenol (each isomer), butyl-heptyl-dodecyl-phenol (each isomer), butyl-heptyl-phenyl-phenol (each isomer), butyl heptyl -phenoxyphenol (each isomer), butyl.heptyl-cumene-phenol (each isomer), butyl-octyl-nonylphenol (each isomer), butyl- Octyl-fluorenyl-phenol (each isomer), butyl-octyldodecyl-phenol (each isomer), butyl-octyl-phenyl-phenol (each isomer), Base-octylphenoxyphenol (each isomer), butyl-octyl cumyl-benzene 131505. Doc -103- 200948760 Age (each isomer), butyl-mercapto-fluorenyl phenol (each isomer), butyl-mercapto-dodecyl-phenol (each isomer), butyl Base-fluorenyl phenyl-phenol (each isomer), butyl-mercapto-phenoxybenz (each isomer), butyl fluorenyl cumene-phenol (isoisomer) , butyl decyl-dodecyl phenol (each isomer), butyl-fluorenyl phenyl phenol (each isomer) 'butyl 癸 _ _ phenoxy phenol ( Each isomer), butyl-mercapto-cumyl-phenol (each isomer), butyl-dodecyl-phenol (each isomer), butyl-dodecyl group -Phenols (each isomer), butyl-dodecyl-phenoxyphenol (each foreign matter), butyl-deuterine-p-isopropylphenyl-benzene (each isomer), Butyl-phenyl·.phenol (each isomer), butyl-phenyl-phenoxyphenol (each isomer), butyl-phenyl-isopropylphenyl-phenol (each isomer) , pentyl-hexylheptylphenol (each isomer), amyl-hexyl-octyl-phenol (each isomer), pentyl-hexyl-fluorenyl- Phenol (each isomer), amyl-hexyl-fluorenyl-phenol (each isomer), amyl-hexyl-dodecyl-phenol (each isomer), amyl-hexylphenyl-phenol (each isomer), amyl-hexyl-phenoxyphenol (each isomer), ◎ pentylhexyl-isopropylidene Benzene (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), pentyl-heptyl-phenyl-phenol (each isomer), pentyl-heptyl-phenoxyphenol (each isomer), pentyl group Heptyl-cumylphenyl-phenol (each isomer), amyl-octyl-fluorenyl-phenol (each isomer), pentyl-octyl-fluorenyl-phenol (each isomer), Amyl-octyl-dodecyl-phenol (each isomer), amyl-octyl-styl-phenol (each isomer), amyl-octyl-phenoxyphenol (isomeric) , pentyl octyl-isopropylphenyl-phenol (each isomer), pentyl _ 131505. Doc 200948760 fluorenyl-fluorenyl-benzoquinone (each isomer), pentyl-mercapto- 12-alkyl group Benzene (each (four)), pentyl-fluorenyl-phenyl-benzene (variety) Structure), fluorenyl-fluorenyl phenoxybenzene (each isomer), & yl thiol cumene benzophenone (isomeric), pentyl-fluorenyl-ten Dialkyl·phenol (each isomer), amyl-mercapto-phenyl-phenol (each isomer), pentyl-fluorenylphenoxyphenol (each isomer), pentyl-hydrazine -Phenylphenyl-phenol (each isomer), amyl-mercapto-dodecyl-phenol (each isomer), pentyl-fluorenyl-phenyl-phenol (each isomer) , pentyl-fluorenyl-phenoxyphenol (each isomer), pentyl-fluorenyl-cumenyl-phenol (each isomer), pentyl-dodecyl-phenyl-phenol ( Each isomer), pentyl-dodecylphenoxyphenol (each isomer), amyl-dodecyl-isopropylphenyl-phenol (each isomer), pentyl-styl -phenoxyphenol (each isomer), pentyl-phenyl-isopropylphenyl·phenol (each isomer), hexyl-heptyl-octyl·phenol (each Isomers), hexyl-heptyl-fluorenyl-phenol (each isomer), hexyl-heptyl-fluorenyl-phenol (each isomer), hexyl-heptyl-dodecylphenol (variety) Structure), hexyl-heptyl-phenyl-phenol (each isomer), hexyl-heptyl-yl-phenoxyphenol (each isomer), hexyl-heptyl-isopropylphenyl-phenol (each Isomers), hexyl-octyl-fluorenyl phenol (each isomer), hexyl-octyl-fluorenyl-phenol (each isomer), hexyl-octyl-dodecyl-phenol (each Isomers), hexyl-octyl-phenyl-phenol (each isomer), hexyl-octyl-phenoxyphenol (each isomer), hexyl-octyl-cumylphenyl-phenol (each Isomers), hexyl-fluorenyl-fluorenyl-phenol (each isomer), hexyl fluorenyl-dodecyl-phenol (each isomer), hexyl-mercapto-phenyl-phenol ( Each isomer), hexyl fluorenyl-phenoxyhexyl-fluorenyl-dodecyl-phenol (each isomer), hexyldecyl-phenyl-phenol (each isomer), hexyl-oxime Ketophenoxyphenol (isomeric 131505. Doc-105- 200948760), hexyl-mercapto-isopropylphenyl-benzene (each isomer), hexyldodecyl-phenyl-phenol (each isomer), hexyl-dodecyl -Phenoxyphenol (each isomer), hexyl-dodecyl-isopropylphenyl-phenol (each isomer) 'hexyl-phenyl-phenoxyphenol (each isomer), hexyl _ Phenyl-cumylphenol (each isomer), heptyl-octyl-decyl-phenol (each isomer), heptyloctyl-decyl-phenol (each isomer), g - octyl-dodecylphenol (each isomer), heptyl-octyl-phenyl-phenol (each isomer), heptyl-octyl-phenoxyphenol (each isomer) , heptyl-octyl-isopropylphenyl-phenol (each isomer), heptyl-fluorenyl-decyl-phenol (each isomer), heptyl-fluorenyl-dodecyl-phenol (each isomer), heptyl-fluorenyl-phenyl-phenol (each isomer), heptyl-fluorenyl-phenoxyphenol (each isomer), heptyl-fluorenyl-cumene —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-dodecane -Phenyl-phenol (each isomer), heptyl-dodecyl-phenoxyphenol Q (each isomer), heptyl-dodecyl-isopropylphenyl-phenol (variety) Structure), heptyl-phenyl-phenoxyphenol (each isomer), heptyl-phenyl-cumylphenyl-benzene (iso-isomer), octyl-fluorenyl-fluorenyl- Phenol (each isomer), octyl-decyl-dodecyl-phenol (each isomer), octyl-fluorenyl-phenyl-phenol (each isomer), octyl-fluorenyl- Phenoxyphenol (each isomer), octyl-fluorenyl-cumenyl-phenol (each isomer), octyl-fluorenyl-dodecyl-phenol (each isomer), xin - mercapto-phenyl-phenol (each isomer), octyl-fluorenyl-phenoxyphenol (each isomer), octyl-fluorenyl-cumyl-phenol (each isomer) ), octyl-dodecyl-phenyl-phenol (each isomer), octyl-dodecane 131505. Doc-106- 200948760 Benzyl-phenoxyphenol (each isomer), octyl-dodecyl-isopropylphenyl-phenol (each isomer), octyl-dodecyl-phenyl- Phenol (each isomer), octyl-dodecyl-phenoxy phenol (each isomer), octyl-dodecyl-isopropylphenyl-phenol (each isomer), xin -Phenyl-phenoxyphenol (each isomer), octyl-phenyl-isopropylphenyl-phenol (each isomer), fluorenyl-fluorenyl-dodecyl-phenol (variety) Structure), mercapto-mercapto-phenyl-phenol (each isomer), mercapto-fluorenyl-phenoxyphenol (each isomer), mercapto-fluorenyl-cumenyl-phenol (each isomer), mercapto-dodecyl-phenyl-phenol (each isomer), mercapto-dodecyl-phenoxyphenol (each isomer), mercapto-ten Dialkyl-isopropylphenyl-phenol (each isomer), mercapto-phenyl-phenoxyphenol (each isomer), mercapto-phenyl-cumylphenol-phenol (isomeric , mercapto-dodecyl-phenyl-phenol (each isomer), mercapto-dodecyl-phenoxyphenol (each isomer), -dodecyl-cumylphenol-phenol (each isomer), mercapto-phenyl-phenoxyphenol (each isomer), mercapto-phenyl-isopropylphenyl-phenol ( Each isomer), dodecyl-phenyl-phenoxyphenol (each isomer), dodecyl-phenyl-isopropylphenyl-phenol (each isomer), phenyl-benzene Oxypyridinyl phenyl-phenol (each isomer) and the like. Among these organic acids, in view of the influence of the cleaning solvent remaining after the cleaning operation of the thermal decomposition reactor, an aromatic hydroxy compound, more preferably a reaction with a diaryl carbonate and an amine compound, is preferred. The aromatic hydroxy compound used is the same compound. Further, when an aromatic mercapto compound is used as the acid for cleaning, the standard boiling point of the aromatic hydroxy compound is preferably from the viewpoint of the cleaning effect, and is equivalent to the above-mentioned aryl aryl phthalate. a compound which is thermally decomposed to form an isocyanate, or a heat of the aryl aryl ester 131505. Doc -107- 200948760 The standard boiling point of the aromatic hydroxy compound formed by the decomposition reaction has a difference in boiling point above 丨〇〇c. 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 into the bottom of the thermal decomposition reactor to make S Various methods such as a method in which the washing solvent is boiled upward in the thermal decomposition reactor to clean the inside. The 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 in an operation time of from 1 hour to 20,000 hours, preferably. It is the operation time every 1 day ~ 1 year, and then the operation time is every month ~ the work year

The decomposition reactor has a line for introducing a cleaning solvent. Also, to clean the thermal decomposition; 5 廄 盔 盔 θ .., ___^.

A compound which does not react with cyanic acid vinegar, for example, 'for example, the literature (journal

The reaction mixture obtained by carrying out the reaction is transported to the reaction of the compound with phenyl isocyanate. The complex can be added to the thermal decomposition reactor when the isocyanate is reacted with the diaryl carbonate and the amine. 13I505.doc -108- 200948760 The mixture is supplied to the thermal decomposition reactor, and may be supplied separately from the line for supplying the reaction mixture, and the line for supplying the aromatic hydroxy compound is 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, and 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. <Analytical method> 1) NMR analytical method device. 曰本, FT-NMR system manufactured by Sakamoto Electronics Co., Ltd. (1) Preparation of Η and 3C-NMR analysis samples 〇 Weighing amount 〇.3 § Sample solution Add about 0.7 g of chlorinated chloroform to the solution (manufactured by the US company Α1ί^, "Dog and 〇.〇5 g as the internal standard substance of tetramethyltin (Sakamoto, manufactured by Wako Pure Chemical Industries, Ltd., and light grade) ) Uniform mixing 'The obtained solution is analyzed as a sample by NMR. (2) Quantitative analysis method: Quantitative analysis of the calibration sample solution prepared by performing the analysis of the quasi-substance. 2) Liquid chromatography method Lc,at system manufactured by Japan, Nakamoto, and Sakamoto Shimao Corporation 131505.doc 200948760 Pipe column: Silica_6〇 pipe column manufactured by Tosoh Corporation, Japan 2 connected in series with solvent: hexane/tetrahydrofuran=80/20 (volume Mixture solvent flow rate: 2 mL/min Tube temperature: 35t: Detector: RI (refractive index meter) (1) Liquid chromatography method to sample a sample weighing about 0.1 g, adding about 1 g to it Tetrahydrofuran (Japan, Wako Pure Chemical Industries Co., Ltd. Making, dehydration) and approximately 〇.〇2 g of bisphenol A as the internal standard substance (Japan, Wako Pure Chemical Industries, Ltd., a), uniformly mixed, and the resulting solution was used as a sample of the liquid chromatography analysis. (2) Quantitative analysis The quantitative analysis of the analytical sample solution is carried out based on the calibration curve prepared by analyzing each standard substance. 3) Gas Chromatography Analysis Method Device: GC-2010 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: After 5 minutes at 50 ° C, 1 Torr. (: / minute temperature rises the temperature to 200. (:

After holding at 200 ° C for 5 minutes, 1 〇. (: / / temperature rise rate to 300 ° C detector: FID (1) gas chromatography analysis sample said 1 about 0.05 g sample 'to add 1 g of polypropylene network (Japan, and light I31505.doc • 110 - 200948760 manufactured by Pure Chemical Industries, Ltd., dehydrated) and about 0.02 g of benzene as an internal standard substance (manufactured by Wako Pure Chemical Industries, Ltd., dehydrated), uniformly mixed, and the obtained solution was sampled by gas chromatography. (2) Quantitative analysis method Quantitative analysis of analytical sample solution is carried out based on a calibration curve prepared by analyzing each standard substance. 4) Inductively coupled plasma mass spectrometry device: manufactured by Seiko Instruments Inc., Japan, SPQ -8000 (1) Inductively coupled plasma mass analysis samples were ashed with dilute sulfuric acid. After the 15 g sample was ashed, it was dissolved in dilute nitric acid. (2) Quantitative analysis The quantitative analysis of the analytical sample solution is carried out based on a calibration curve prepared by performing analysis on each reference substance. [Reference Example 1] Production of diphenyl carbonate • Step (1-1): Production of dialkyltin catalyst To an eggplant type flask having a volume of 3000 mL, 692 g (2.78 mol) of di-n-butyl oxide was added. Tin and 2 〇〇〇g (27 mol) 1-butanol (manufactured by Wako Pure Chemical Industries, Ltd., Japan). A flask in which the mixture was added in the form of a white slurry was attached to an evaporator. The evaporator was connected to an oil bath with a temperature regulator and a vacuum pump. The vent valve outlet of the evaporator is connected to a line that flows nitrogen at atmospheric pressure. Close the evaporator vent valve, 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 t, and the flask was immersed in the oil bath to start the rotation of the evaporator. After the vent valve of the evaporator is opened, the mixture is rotated under normal pressure for about 30 minutes and heated, and then the mixture is boiled to start steaming of the low-fog component. After maintaining this state for 8 hours, the vent valve was closed and the inside of the system was slowly decompressed, and the residual low boiling component was steamed in a state where the pressure in the system 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 aeration chamber 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 of (1)~, towel, and 13C-NMR, it was confirmed that the product 1,1,3,3-tetra-n-butyl fluorene (n-butyl) was obtained in a yield of 99% based on di-n-butyltin oxide. Oxy)-distannoxane. The same operation was repeated 12 times to obtain a total of 1148 〇 g of 1,1,3,3-tetra-n-butyl-1,3·di(n-butoxy)-distannoxane. • Step (1-2): Production of dibutyl carbonate In the continuous production apparatus shown in Fig. 1, a carbonate was produced. From line 4, at 4201 g/hr, the steps were made), "tetra-n-butyl hydrazine, % bis(n-butoxy)-distannoxane, and by line 2, to 24,717 g/ Hr, the purified 丨-butanol in the Q distillation column 101 is supplied to a column reactor 1 having an inner diameter of 151 mm and an effective length of 5040 mm filled with a filler mellapak 750Y (manufactured by Sulzer Chemtech Ltd., Switzerland). 〇 2 in. The reactor was conditioned by a heater and reboiler 112 to bring the liquid temperature to 16 〇 C and adjusted with a pressure regulating valve to bring the pressure to about 15 〇 kpa _ G. The residence time in the reactor was about 1 minute. From the upper part of the reactor, the aqueous 1-butanol was fed via line 6 at 24,715 g/hr, and the 1-butanol was conveyed via line 1 at 824 g/hr to a filled filling material, Metai Gauze (Switzerland, manufactured by Sulzer Chemtech Ltd.). And equipped with a reboiler lu and a cold 131505.doc -112- 200948760 coagulator 121 in the steaming tower 1〇1, steaming purification. In the upper part of the steaming tower IQ], the hall containing the high-concentration water is condensed by the condenser 12ι and then recovered by the line 3. Purified 1-butanol is delivered via line 2 below the steaming tower (8). From the lower part of the column reactor 1〇2, an alkyl stane alkoxide containing di-n-butyltin-di-n-butoxide oxide 3,3_tetra-n-butyl-n-butoxy)-distannoxane was obtained. The medium composition is supplied to the thin film evaporation apparatus 1G3 via the line 5 (K〇bele, eeG s(), manufactured by iuti., Japan). In the thin film evaporation apparatus 1〇3, debutanol is returned to the column reactor 1〇2 via the condenser 123, the line 8 and the line 4. The alkyl tin alkoxide catalyst composition is transported from the lower portion of the thin film evaporation device 103 via line 7, and dibutyltin dibutoxide and 匕^^-tetra-n-butylbis(n-butoxy)-distannoxane The flow rate of the active ingredient was adjusted to about 4812 cents and supplied to the autoclave 104. Carbon dioxide was supplied to the autoclave at 973 g/hr via line 9, and the high pressure dad internal pressure was maintained at 4 MPa_G. The temperature in the autoclave was set to 12 (TC, and the residence time was adjusted to about 4 hours, and the reaction of Q carbon dioxide with the alkyl tin alkoxide catalyst composition was carried out to obtain a reaction liquid containing dibutyl carbonate. And the regulating valve transports the reaction liquid to the carbon removal tank 105, removes residual carbon dioxide, and recovers the carbon dioxide by the line. Thereafter, the reaction liquid is transported via the line i 2 to be set to about 140 ° C. A flow rate of H3 3 · tetra-n-butyl _13 bis(n-butoxy)-distannoxane in a film evaporation apparatus 1〇6 (manufactured by K〇beU〇eco-solutions Co., Ltd., Japan) of about 1.4 kPa Adjusted to about 4201 g/hr for supply, to obtain the risk of including dibutyl sulphate. On the other hand, the evaporation residue was passed through line 13 and line 4, and 1,1,3,3-tetra-n-butyl hydrazine was 3_bis(n-butoxy)_ditin 131505.doc -113- 200948760 The oxane flow rate was adjusted to about 4201 g/hr, and was recycled to the column reactor 102. The dibutyl carbonate-containing fraction was passed through a condenser 126. And line 14, supplied at 830 g/hr to the filled Metal Gauze CY (Switzerland, Sulzer Chemtech Ltd) The company manufactured and equipped with a reboiler U7 and a condenser 127 in a distillation column 107, after performing distillation purification, 99 wt% of dibutyl carbonate was obtained from line 15 at 814 g/hr. Using ii9Sn, iH, 13C- NMR analysis of the alkyl tin oxide oxide catalyst composition of line 13 resulted in 1,1,3,3-tetra-n-butyl-1,3-di(n-butoxy)-distannoxane. Does not contain di-n-butyltin-di-n-butyl oxide. After the continuous operation described above for about 600 hours, the alkyltin alkoxide catalyst composition is supplied by line 16 at 16 g/hr, and on the other hand, by line 17. 1,1,3,3-tetra-n-butyl-1,3-di(n-butoxy)-distannoxane produced in the step (1-1) at 16 g/hr. • Step (1-3) ): Preparation 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 water formed by 0 was distilled off together with phenol. 2.5 g of water. Thereafter, the catalyst was prepared by distilling off the phenol from the upper part of the reactor. [Manufacture of aromatic carbonate] The apparatus shown in Fig. 2 was used. The inside was packed with Dixon packing (6 mm φ). The tower is about 5 cm in diameter The middle section of the continuous multi-stage distillation column 2〇2 of 2 m long, via the preheater 2〇1, continuously feeds the liquid carbon dioxide obtained by the step (^2) from the line 21 at about 270 g/hr' a mixture of butyl ester, phenol, and a catalyst prepared as described above (the weight ratio of dibutyl carbonate to phenol in the mixture is about 65/35, and the lead concentration is 131505.doc -114-200948760 is about 1% by weight) 'Respond. The heat necessary for the reaction and steaming is supplied by circulating the liquid in the lower portion of the column via line 23 and reboiler 204. The liquid temperature at the bottom of the continuous multi-stage distillation column 202 is 238 t: the overhead pressure is about 250 kPa, and the reflux ratio is about 2. The gas from the tower top of the continuous multi-stage distillation column 202 is discharged from the line 22, and is continuously discharged to the storage tank 2〇5 by the line 24 at about 67 g/hr via the condenser 203. From the bottom of the column, it was continuously discharged into the storage tank 2〇6 via line 23 at about 204 g/hr. The composition of the liquid discharged from line 24 is about 33-butanol of about 33 wt%/〇 and ❹ phenol of about 65 wt%. Niobium, dibutyl carbonate is about 2% by weight. The liquid composition discharged to the storage tank 206 is such that the phenol is about 丨 丨 by weight, the dibutyl acrylate is about 60% by weight, the butyl phenyl carbonate is about 26% by weight, the diphenyl carbonate is about 1.6% by weight, and the lead concentration is It is about 1 weight 〇/0. Next, use the device shown in Figure 3. The middle portion of the continuous multi-stage distillation column 302 having an inner diameter of 5 cm and a column length of 2 m filled with a Dixon packing (6 mm φ), via a preheater 3 ,, from the line 31 ◎ at about 203 g/hr 'Liquid discharged into the sump 206 as a continuous feed in liquid form. The heat necessary for the reaction and steaming is supplied by circulating the lower portion of the liquid through the line 33 and the reboiler 304. The bottom of the column of the continuous multi-stage steaming tower 302 has a liquid im-degree of 240 C 'top pressure of about 27 kPa and a reflux ratio of about 2. The gas distilled from the top of the continuous multi-stage distillation column 302 is condensed in the condenser 303 via line 32 and continuously discharged into the sump 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 layers/inch. Ppm, the composition of the liquid discharged from line 34 is such that the butanol is about 5 〇〇 131505. doc - 115 · 200948760 phenol is about 13% by weight, dibutyl carbonate is about 85% by weight, and butyl phenyl carbonate is about It is 2% by weight. The liquid discharged to the storage tank 3〇6 has a composition of about 0.3% by weight of dibutyl carbonate, about 32% by weight of butyl phenyl carbonate, about 61% by weight of diphenyl carbonate, and a lead concentration of about 7% by weight. /0. [Reuse of Alcohol] The use of the alcohol as shown in Fig. 4 was carried out. The continuous multi-stage distillation column 4〇2 filled with Dixon packing (6 mm φ) and having an inner diameter of about 5 cm and a column length of 2 m is about 7 melons from the bottom of the tower, and the line 41 is passed through the preheater. 4〇1, the liquid continuously discharged to the storage tank 205 in the above step was continuously fed at about 2〇1 g/hr, and distillation separation was carried out. The heat necessary for the distillation separation is obtained by circulating the liquid in the lower portion of the column through the line 43 and the reboiler 4〇4, and the liquid temperature at the bottom of the column of the σ continuous multi-stage distillation column 402 is 145 乞 'the top pressure is about 13 kPa. 'The reflux ratio is about 〇3. The gas distilled from the continuous multi-stage distillation column 402 was condensed in the condenser 4〇3 via line 42, and discharged to the storage tank 4〇5 by line 44 at about 68 g/hr. From the bottom of the tower, it is continuously discharged to the storage tank 4〇6 at a center of about 133 via the line 43'. The composition of the liquid discharged from line 44 is about 99% by weight of 丨-butanol, and 100 pp of phenol 7 is discharged to the storage tank 4〇6. The composition of the liquid is about 2% by weight of monobutyl carbonate. Phenol was about 98 wt%/〇. [Purification of diaryl carbonate] Purification of diaryl carbonate was carried out using the apparatus shown in Figures 5 and 6. The filling was carried out with a Dixon filler (about 6 mm inner diameter). It is a continuous section of 5 cm, a column length of 2, and a middle section of the distillation column 502, which is continuously fed to the tank 3 〇6 by a line 51 via a preheater at about 195 g/hr. Distillation 131505.doc.116 · 200948760

Condensation in unit 503 is continuously discharged by line 54. The device 5 04 is placed under the column; the bottom liquid temperature reflux ratio is about 1. The self-certification is condensed via line 52. 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 such that dibutyl carbonate is about weight. /. , butyl styrene carbonate is about 34% by weight, and diphenyl vinegar is about "% by weight". Continuously multi-stage with an inner diameter of about 5 cm and a length of 2 m filled with Dixon packing (6 mm φ). In the middle of the distillation column 602, the liquid discharged from the line 54 is continuously fed by the line 61 via the preheater 601' at about 181 g/hr. The heat necessary for the distillation separation is passed through the line 63 and the reboiler 6〇4. The liquid in the lower portion of the column is circulated and supplied. The liquid temperature at the bottom of the continuous multi-stage distillation column 6 〇 2 is 232 C 'the top pressure is about 15 kPa, and the reflux ratio is about 2. The top of the continuous multi-stage distillation column 602 is distilled off. The gas is condensed in line condensed in condenser 603 by line 64. It is discharged from line to column 606 via line 63 at about 119 g/hr. The composition of the liquid discharged from line 64 is about dibutyl carbonate. It is 6% by weight, butyl phenyl carbonate is about 99% by weight, and diphenyl carbonate is about 〇. 4% by weight. The composition of the liquid discharged to the storage tank 606 is 0.1% by weight of butyl phenyl carbonate. Diphenyl carbonate is about 99.9% by weight. The diphenyl carbonate is contained as a metal component. 22 ppm of iron. [Example 1] 131505.doc -117· 200948760 • Step (1-1): 制造, ΛΤ-hexyldi-di-amino phthalic acid diphenyl ester was used as shown in Fig. 7 In the state in which the line 74 is closed, 135 〇g (6.3 mol) of diphenyl carbonate of Reference Example 1 is supplied from the storage tank 701 via the line 71 to a SUS system with an internal volume of 5 L and a support plate. In the reaction vessel 704, 987 g (10 〇·5 mol) of phenol (manufactured by Aldrich Co., Ltd.) was 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 At 50 ° C, 244 g (2.1 mol) of hexamethylenediamine (manufactured by Aldrich Co., USA) was supplied from the storage tank 703 to the reactor 704 at about 200 g/hr via line 73'. The solution after the reaction was analyzed, and as a result, dihexyl-bis-amino phthalic acid diphenyl ester was formed in a yield of 99.5%. The reaction liquid was transferred to the storage tank 7〇5 via line 74. • Step (1-2): The isocyanate is produced by thermal decomposition of ruthenium, hexamethylene-bis-carbamic acid diphenyl ester, as shown in Figure 8. The reaction was carried out. A thin film distillation apparatus 801 (manufactured by Kobelco Eco-solutions Co., Ltd.) having a heat transfer area of 0.1 m2 was heated to 220 ° C to have an internal pressure of about 13 kPa. The mixture recovered in storage tank 705 was heated to 15 ° C and supplied via line 81 to the upper portion of the film evaporation unit go! 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 unit 8 through the line 84 and the line 81. The gas phase components are discharged from line 82. 131505.doc -118- 200948760 To the middle of a continuous multi-stage distillation column 802 filled with Dixon packing (6 mm φ) having an inner diameter of about 5 cm and a column length of 2 m, continuous feeding is carried out by the thin film distillation apparatus 801. The gas phase component discharged from line 82 performs the distillation separation of the gas phase component. 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 8〇2 was 150. (:, the top 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 line 85. It is continuously discharged by line 87. From the continuous multi-stage distillation column 802 〇 The liquid phase component is discharged at a line 89 lower than the position of the line 82. 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 filled with a Dixon packing (6 mm φ) The liquid phase component discharged from the line 89 is continuously distilled to carry out the distillation separation of the liquid phase component. The heat necessary for the distillation separation is supplied by circulating the liquid in the lower portion of the column via the line 91 and the reboiler 807. Continuous multi-stage distillation The liquid temperature at the bottom of the column of column 805 is i50 〇c, and the pressure at the top of the column is about 1.5 kPa. The gas from the top of the continuous multi-stage distillation column 805 is condensed in the condenser 806 via line 90, via line 92. It is continuously discharged to the storage tank 809. The discharge amount in the steady state is about 1 〇 4 g / hr. In a steady state, the liquid phase component is discharged from the line 94 to the storage tank 810 at about 140 g / hr. The liquid phase component contains about 97. Weight % diphenyl carbonate. discharged by line 92 The liquid system contains a solution of about 99.8% by weight of hexamethylene diisocyanate. The yield relative to the hexamethylenediamine is 95.3%. • Step (1-3): Reuse of the diaryl carbonate is shown in the figure. The apparatus shown in 9, 10 'Recycling the diaryl carbonate 0 131505.doc • 119- 200948760 The liquid discharged from the line 94 in the step (1-2) is passed from the line 95 via the preheater 901 ' 195 g/hr was continuously fed to the middle section of a continuous multi-stage distillation column 9〇2 filled with Dixon packing (6 mm Φ) with an inner diameter of about 5 cm and a column length of 2 m. Steaming the heat necessary for separation The liquid 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 9〇2 is 210. (:, the top pressure 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 storage tank 906 at about 14 g/hr via the enthalpy line 97. Continuous multi-stage distillation column with a diameter of about 5 cm and a length of 2 m filled with Dixon packing (6 mm φ) In the middle section of the second stage, the liquid discharged from the line 99 is continuously fed by the line phantom through the preheater 1001 at about 181 g/hr. The heat necessary for the separation of the steam is passed through the line A3 and the reboiler 丨〇〇4. The liquid in the lower part of the tower is circulated and supplied. The liquid temperature at the bottom of the continuous multi-stage distillation tower 丨002 is 232C 'the top pressure is about 15 kPa' and the reflux ratio is about 2. The self-connected ◎ continues the multi-stage steam tower 1002 tower top pavilion The gas discharged was condensed in the condenser 1003 via the line A2, and the Q was continuously discharged from the bottom line via the line A3, and discharged to the storage tank 1〇〇6 at about 119 g/hr. The liquid discharged to the storage tank 1〇〇6 contained about 99.9% by weight of diphenyl vinegar. • Step (1-4): Recycling of phenol The phenol was reused using the apparatus shown in Fig. 11. The liquid discharged from the line 87 in the step (1 - 2) is continuously fed from the line B through the preheater 1101 at about 200 g/hr to the inner diameter filled with the Dixon packing (6 mm φ). The middle section of a continuous multi-stage steaming tower with a length of 5 cm and a length of 2 m. 131 350.doc • 120· 200948760. The heat necessary for the steaming chamber 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 11〇2 is 230°c. 'The top pressure 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 passed through the line B2 to the condenser 11 Condensation in crucible 3 is continuously discharged from line A4 to storage tank 1 105. The liquid discharged to the storage tank 11〇5 contained about 99.9% by weight of benzene. The continuous operation was carried out for 10 days. 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 vaporization apparatus 801. [Example 2] Step (2-1): Production of phenyl 3-(phenoxycarbonylamino-methyl)-3,5,5-trimethylcyclohexylaminocarboxylate was carried out as shown in Fig. 7 The device is reacted. 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 the SUS reaction vessel 704 with an internal volume of 5 l. 1311 g (14. 〇m〇l) benzene was supplied from the storage tank 702 via line 72 to the SUS reactor. The liquid temperature in the reactor 704 was adjusted to about 50 ° C, and 528 g (3.1 mol) of 3-aminomercapto-3,5,5·trimethyl group was transferred from the storage tank 703 via line 73' at about 250 g/hr. Cyclohexylamine (manufactured by Aldrich, USA) was supplied to the reactor 7〇4. The solution after the reaction was analyzed by liquid chromatography to give 3-(phenoxyamino-indenyl)-3,5,5-trimethylcyclohexylaminocarboxylic acid in a yield of 99-3%. Phenyl ester. 131505.doc -121- 200948760 The line 74 is opened and the reaction liquid is transported via line 74 to storage tank 705. • Step (2-2): The isocyanate is produced by thermal decomposition of phenyl 3-(phenoxycarbonylamino-methyl)_3,5,5-trimethylcyclohexylcarbamate, as shown in FIG. The device reacts. A thin film distillation unit 8〇1 with a heat transfer area of 〇·1 m2 (K,belco 日本, Japan)

Heated to 22 〇〇c, the internal pressure is about 13 kPa °. The mixture recovered from the sump 705 in step (2-1) is heated to 150 C, via line 81 ' About 780 g/hr was supplied to the upper portion of the thin film distillation apparatus 801. 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. To the middle of the continuous multi-stage distillation column 802 filled with Dixon packing (6 mm φ) having an inner diameter of about 5 cm and a column length of 2 m, the continuous feeding is performed by the thin film distillation apparatus 801, 'discharged by the line 82 The gas phase component, the heat necessary for the distillation of the gas phase component to be separated from the distillation knife, is supplied by removing the lower liquid (four) ring through the line 86 and the reboiler. The liquid temperature at the bottom of the continuous multi-stage steaming tower is 150 < t, and the pressure at the top of the tower is about 15 kpa. The gas from the tower top of the continuous multi-stage steaming tower 8G2 is condensed through the line in the condenser section. The material 87 is continuous (four). The liquid phase component is discharged from the line 89' where the continuous section of the steam is moved below the line 82. To the middle brother, there is a middle section of the continuous multi-stage steaming tower 8G5 with a Dickson packing (6) having an inner diameter of about 5 (10) and a tower length of 2 m, and continuously feeding the liquid phase component from the line division to carry out the liquid phase. The distillation of the ingredients is off. The heat necessary for the distillation separation is supplied by circulating the lower liquid stream 131505.doc - 122 - 200948760 via the line 9 Bs 91 and the reboiler 807. The liquid temperature at the bottom of the continuous multi-stage distillation column 805 is 15 Torr. 〇, the top pressure is about 1.3 kPa. The gas 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 sump 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 one day, 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, Acetone iron (II), a diphenyl carbonate containing 2.3% of iron as a metal atom was prepared. 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 the line 71 to a reaction vessel 704 made of 5.2 SUS with an internal volume of 5 l in a state where the line 74 was closed, and 1189 g (1189 g ( 12.7 mol) of phenol was 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 VIII) was passed from the storage tank 703 via line 73 at about 250 g/hr. The reactor of the United States 'Aldrich Company' is supplied to the reactor 704. The solution after the reaction was analyzed by liquid chromatography to give diphenyl-4,41-methylene-dicyclohexylamino phthalate in a yield of 99.1%. The line 74' is opened to transport the reaction liquid to the sump 705 via line 74. Step (3-2): Production of isocyanate by thermal decomposition of diphenyl-4,4,-methylene-dicyclohexylamino phthalate 131505.doc-123-200948760 is used as shown in FIG. The device reacts. A thin film distillation apparatus 1201 having a heat transfer area of 0.1 m2 (Japan,

Heating by Kobelco eco-solutions) to 25 (TC, the internal pressure is about 1.3 kPa. The mixture recovered from the storage tank 705 in the step (3-1) is heated to 170 ° C, via line C1, to about 650 The g/hr is supplied to the upper portion of the thin film distillation apparatus 1201. 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 vaporization apparatus 1201 via the line C4 and the line C1. The component is discharged from the line C2. The continuous section of the continuous multi-stage distillation column 1202 having an inner diameter of about 5 cm and a column length of 2 m filled with a Dixon packing (6 mm φ) is continuously fed by the film evaporation device 1201 via the line. The vapor phase component "discharged from C2" performs the vaporization separation of the gas phase component. The heat necessary for the vaporization separation is supplied by circulating the liquid in the lower portion of the column via the line C6 and the reboiler 1204. The continuous multi-stage distillation column 丨2 The liquid temperature at the bottom of the tower is 210 ° C, and the pressure at the top of the tower is atmospheric pressure. The gas taken from the top of the continuous multi-Q section steaming tower 1201 is condensed in the condenser 1203 via the line C5, and continuous by the line C7. Discharge. Discharge from line 〇8 In 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, the liquid phase component discharged from the line C8 is continuously fed. Distillation separation of the liquid phase component. The heat necessary for the distillation separation is supplied by circulating the liquid in the lower portion of the column via the line C11 and the reboiler 12 〇 7. The liquid temperature at the bottom of the continuous multi-stage distillation column 1205 is 21 〇 ° C, The pressure at the top of the column is about 2.5 kPa. The gas from the top of the continuous multi-stage distillation column 12〇5 131505.doc -124- 200948760 is condensed in the condenser ι2〇6 via line CIO, continuously through line C12. Discharge. The liquid phase component is discharged from line C14. ❹ Ο The middle section of the continuous multi-stage steaming tower 12〇8 filled with Dixon packing (6 mm φ) with an inner diameter of about 5 cm and a tower length of 2 m The liquid phase component discharged from the line C14 is fed to perform distillation separation of the liquid phase component. The heat necessary for the distillation separation is supplied by circulating the liquid in the lower portion of the column via the line C16 and the reboiler 121. The continuous multi-stage distillation column is supplied. The liquid temperature at the bottom of the 12〇8 tower is 22 (TC 'Tower The dust power is about 55 kPa. The gas distilled from the top of the continuous multi-stage steaming tower 12〇5 is condensed in the condenser 12〇9 via line C15, and the line C17 is about 113 g/ The hr is continuously discharged. The liquid discharged from C17 contains about 99.9% by weight of 4,4,·methylene-bis(cyclohexyl isocyanate). Compared to 4,4,-methylenebis(cyclohexylamine). The yield was 93 2%. The continuous operation of ι〇天 was not found in the wall area of the film-based sloping rectification apparatus 1202. Attachment 0 [Example 4] • Step (4-1): II Phenyl_4 4,-25 Field Im, methylene cyclohexylamino phthalate production except for the supply of 1650 g (7.7 to) diphenyl carbonate of Reference Example 1, 1344 g (l 1 · 0 mol) 2,6, 曱 曱 m phenol (manufactured by Aldrich, USA) instead of phenol, and 463 g (2.2 m〇1) 4 | ; 'methylene bis(cyclohexylamine), implementation and Example 3 The step (3_υ 菔德的 m ° is analyzed by liquid chromatography for the reaction/liquid mixture after the reaction, and the fruit of the fruit is produced in a yield of 99.3% to form di-p-methylene-dicyclohexylamine formic acid. . Wind-based basis. Step (4-2): Preparation of isocyanic acid 5-amino carbamic acid by thermal decomposition of diphenyl-4-4,· 'methylene' dicyclohexylaminocarboxylic acid 131505.doc - 125- 200948760 In addition to using the mixture obtained in the step (4-1) in place of the mixture obtained in the step (3 -1), the mixture is heated to a temperature other than 14 ° C, and the step (3-2) of the embodiment 3 is carried out. The same method. A mixture of benzene and 2,6-dimethylbenzene 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 found in the wall area of the thin film steaming device 1202. [Example 5] • Step (5-1): Ν, Ν·-hexanediyl·bis-amino phthalic acid diphenyl styrene was produced in addition to 1874 g (8·8 mol) of the diphenyl carbonate of Reference Example 1. The same procedure as in the step (1-1) of Example 1 was carried out, except for vinegar, 1246 (13.3 mol) phenol and 291 g (2.5 mol) hexamethylenediamine. The solution after the reaction was analyzed by liquid chromatography, and as a result, hexamethylenediamine-diphenylacetate was formed in a yield of 99.4%. • Step (5-2): Production of isocyanate by thermal decomposition of iV,-hexanediyl-bis-carbamic acid diphenyl ester, except that the mixture obtained in the step (5-1) is used instead of the step 〇_1} The obtained mixture 'heated the mixture to 190 ° C and supplied to the outside of the film evaporation device 801' was carried out in the same manner as in the step (1_2) of Example i. 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 the hexamethylenediamine was 77.5%. The continuous operation was performed for one day, and no deposit was found in the wall area of the thin film distillation apparatus 801. [Example 6] 131505.doc -126- 200948760. Step (6-1): Manufacture of dihexyl bis-bis-carbamic acid di- bromo ester except that 2 〇 56 g (9.6 mol) of the carbonic acid of Reference Example 1 was supplied The same procedure as in Example 1 was carried out, except that phenyl ester, 15 〇 4 g (16 〇 mol) phenol, and 372 g (3.2 m 〇 1) hexamethylenediamine. The solution after the reaction was analyzed by liquid chromatography, and as a result, a yield of 99·4 ° / 〇 was produced as dihexyl bis-amino phthalic acid diphenyl ester. • Step (6-2): Isocyanic acid vinegar was prepared by thermal decomposition of hexamethylene bis- carbamic acid diphenyl vinegar. The reaction was carried out using a device as shown in Fig. 8. The thin film distillation apparatus 8〇1 having a heat transfer area of 0.1 m2 is heated to 22 〇<t, and the internal pressure is about 0.13 kPae. The step (6·υ* of the mixture recovered from the storage tank 7〇5 is heated to 1 〇 (rc It is supplied to the upper portion of the film evaporation device via line 81 at about 8 〇〇g/hr. The gas phase component is discharged from the vapor deposition device 8〇1 via line 82. It is provided at the bottom of the thin film distillation device 8〇1. Line 83, almost no liquid phase component was recovered. The middle section of the continuous multi-stage steaming tower 8G2 filled with Dixon packing (6 mm φ) with an inner diameter of about 5 cm and a tower length of 2 m was continuously fed. The vapor phase component discharged from the thin film evaporation device 801 via the line 82 performs distillation separation of the gas phase component. The heat necessary for the distillation separation is supplied by circulating the liquid in the lower portion of the column via the line 86 and the reboiler 804. The bottom of the column of the distillation column 8〇2 has a liquid temperature of 150 ° C and a column top pressure of about 8 kPa. The gas distilled from the top of the continuous multi-stage distillation column 802 is condensed in the condenser via the line, and is continuously connected by the line 87. Discharged from the continuous multi-stage distillation column 8〇2 below the line 82 The liquid composition discharge line 89. 131505.doc 127- 200948760

The liquid phase component discharged from the line μ is continuously fed to a middle portion of a continuous multi-stage steamed milk filled with a Dixon filler (6ππηφ) having an inner diameter of about 5 coffee and a column length of 2 m, and the liquid phase component is discharged. The steamed material is separated. The heat required for the steaming age is supplied by circulating the liquid in the lower portion of the tower via line 91 and again. The liquid temperature at the bottom of the tower of the continuous multi-stage steaming tower 8〇5 is 15 ° C. The top pressure is about L5 kPa. The gas distilled from the top of the continuous multi-stage steaming tower 8〇5 is condensed in the condenser 8〇6 via the line 90, and continuously discharged to the storage tank 8〇9 via the line 92. The steady state discharge is about (10) coffee. The liquid system discharged from line 92 contains about 99. The solution of 9 wt% of hexamethylenediamine diisocyanate has a yield of 95 4% relative to hexamethylenediamine. When the operation was continued for ίο, it was found that the wall area of the thin film distillation apparatus 8〇1 was deposited. [Example 7]. Step (7-1): Production of diphenyl-4,4,-indenylene-dicyclohexylcarbamate except 1874 g (8. 8 mol) Reference Example 1 diphenyl carbonate, 丨 175 Q g (12. 5 mo1) phenol and 526 g (2. The same procedure as in the step (34) of Example 3 was carried out, except that 5 mol of 4,4'-methylenebis(cyclohexylamine) was used. The solution after the reaction was analyzed by liquid chromatography, and the yield was 99. 20/〇 produces diphenyl-4,4,-methylene-dicyclohexylcarbamate. . Step (7-2): Production of isocyanate by thermal decomposition of diphenyl-4,4,-fluorenylene-dicyclohexylamine phthalic acid vinegar The reaction was carried out using an apparatus as shown in Fig. 13. The mixture recovered from the storage tank 705 in the step (7-1) was heated to 15 Torr. (:, via line D1, fed at approximately 510 g/hr to fill with Dixon packing (6 mm 131505. Doc 1〇〇 200948760 Φ) The middle section of a continuous multi-stage distillation column 1301 having an inner diameter of about 5 cm and a column length of 2 m is subjected to 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. (:, the top pressure 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. From the continuous multi-stage steaming tower 13 01 At the bottom, the liquid phase component is recovered via line D3. The middle section of the continuous multi-stage steaming tower 13 04 filled with Dixon packing (6 mm Φ) and having an inner diameter of about 5 cm and a tower length of 2 m is continuously fed. The liquid phase component "discharged through the line D6" is used to separate the liquid phase components. The heat necessary for the vapor separation is supplied by circulating the lower portion of the liquid through the line D8 and the reboiler 1306. Continuous multi-stage distillation The bottom of the tower 1304 has a liquid temperature of 220 ° C. The top pressure 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 Q 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 portion of the continuous multi-stage distillation column 13〇7 filled with Dixon packing (6 mm φ) and having an inner diameter of about 5 cm and a column length of 2 m. The liquid phase component is separated by distillation. 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 〇 4 〇 kp ^ The gas distilled from the top of the continuous multi-stage distillation column 13 〇 7 is passed through the line D12 in the condenser 13 8 condensing, 131505. Doc -129- 200948760 is continuously discharged via line D13. The steady state discharge is about 75 g/hr. The liquid system discharged from line D13 contains about 99. A solution of 8 wt% of 4,4'-arylene-bis(cyclohexyl isocyanate) having a yield of 80% relative to 4,4,-fluorenylene bis(cyclohexylamine). 4%. The continuous operation was carried out for one day, and as a result, no deposit was accumulated in the inside of the continuous multi-stage steaming tower 1301. [Example 8]. Step (8·): From the manufacture of #'-hexanediyl-bis-amino phthalic acid diphenyl ester 〇 In addition to the supply of 135 〇 g (6. 3 mol) Reference Example 1 diphenyl carbonate, 2204 g (8. 4 mol) 4-dodecylphenol (manufactured by Aldrich, USA) instead of stupid phenol, and 244 g (2. The same procedure as in the step (1-1) of Example 1 was carried out, except for the mol of hexamethylenediamine. The solution after the reaction was analyzed by liquid chromatography, and the yield was 99. 0% is produced by #'-hexanediyl-bis-carbamic acid diphenyl ester. . Step (8-2): Production of isocyanate by thermal decomposition of hydrazine, hydrazine, hexamethylene bis-amino phthalic acid diphenyl ester The reaction was carried out using an apparatus as shown in Fig. 8. The heat transfer area is 0. The 1 m2 thin film distillation unit 8〇1 is heated to 22 (rc, so that the internal pressure is about 5. 2 kPa. The mixture recovered in the storage tank 705 in the step (8-1) was heated to 15 CTC, and supplied to the upper portion of the thin film distillation apparatus 801 via a line 81 at about 12 Torr. From the bottom of the thin film distillation apparatus 〇1, the liquid phase component is discharged from the line 83, and is circulated to the upper portion of the thin film evaporation apparatus 801 via the line 84 and the line 801. The gas phase components are discharged from line 82. Filled with Dixon packing (6 mm inner diameter is about 5 cm, tower length is 2 131505. The middle section of the continuous multi-stage distillation column 802 of doc-130-200948760 m is continuously fed by the thin film distillation apparatus 801 by the gas phase component discharged from the line 82 to perform vapor separation of the gas phase components. 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 tower of the continuous multi-stage distillation column 8〇2 has a liquid temperature of 150 ° C at the bottom and a pressure of about 4. 0 kPa. The gas distilled from the top of the continuous multi-stage vaporization column 802 is condensed in the condenser 803 via line 85 and continuously discharged by line 87. The liquid phase component is discharged from the line 89 of the continuous multi-stage vaporization tower 802 which is lower than the position of the line 82. The liquid phase component discharged from the line 89 is continuously fed to a middle portion of a continuous multi-stage distillation column 805 filled with a Dixon packing (6 mm 妁 having an inner diameter of about 5 cm and a column length of 2 m) to carry out the liquid phase component. The steam is separated. 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 15 〇 (), The pressure is about 0. 8 kPa. The gas distilled from the top of the continuous multi-stage distillation column 8〇5 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 the steady state, the liquid phase component is discharged to the storage tank 810 by line 94 at about 69 〇 g/hr. The liquid phase component contains about 97% by weight of anal dodecylphenol. The liquid system discharged from line 92 contains a solution of about 99% by weight of hexamethylene diisocyanate. The yield based on hexamethylenediamine was 931%. The continuous operation was carried out for one day, and no deposit was found in the wall area of the thin film distillation apparatus 8〇1. [Example 9] • Step (9-1): 3-(phenoxyaminoamino-methyl(4)^-methylmethylcyclohexane 131505. Doc -131- 200948760 Manufacture of phenyl carbazate In addition to supply 1028 g (4. 8 mol) ginseng; &) wheat diphenyl carbonate, 2643 g (8. 0 mol) 2,4-(α,α·dimercaptobenzylidene, lean xw butylglycolyl) phenol (made by Tokyo Chemical Industry Co., Ltd.) instead of benzene, and 273 machine 6_)3_aminomethyl_3 The same procedure as in the step (IV) of Example 2 was carried out except for the 5,5-trimethylcyclohexylamine. The solution after the reaction was analyzed by liquid chromatography, and the yield was 99. 0% yielded 3_(phenoxymethylaminomethyl)355 trimethylcyclohexylcarbamate. • Step (9-2): Production of isocyanate by thermal decomposition of phenyl 3-(phenoxycarbonylamino-methyl)_3,5,5-trimethylcyclohexylcarbamate except for the use step (9-2) The obtained mixture was replaced by the mixture obtained in the step, and the mixture was heated to 150 ° C and supplied at about 131 〇 g / hr, and the same procedure as in the step (8-2) of Example 8 was carried out. The gas distilled from the top of the continuous multi-stage distillation column 8〇5 is condensed in the condenser 806 via line 9, and continuously discharged to the storage tank 809 via line 92 at about 112 g/hr. » Liquid system discharged from line 92 Contains about 99. A solution of 8 wt% isophorone diisocyanate. The yield based on 3·aminomercapto-3,5,5-trimethylcyclohexylamine was 94. 5%. The continuous operation was performed for one day, and no deposit was observed in the wall area of the thin film distillation apparatus 801. [Example 10] • Step (1 (M): ??? #'-(4,4,·-indenyl-diphenyl)-diphenyl diphenyl carbamate was produced using the apparatus shown in FIG. Reaction. Doc -132- 200948760 In the state of closing line 74, by tank 701 via line 71, 1478 g (6. 9 mol) of diphenyl carbonate of Reference Example 1 and 50. 5 g (0. A mixture of 2 mol) zinc acetate 2 hydrate (manufactured by Aldrich Co., USA) was supplied to a SUS reaction vessel 704 with a median grain product of 5 L, and a storage tank 702 was used to pass 1297 g (13) via line 72. . 8 mol) of phenol is supplied to the reactor of the SUS. The temperature of the liquid in the reactor 704 is adjusted to about 50 〇c, from the sump 703 via line 73, to about 200 g / hl ^ 456 g (23 m 〇 1) 44, fluorenyl aniline (manufactured by Aldrich, USA) ) is supplied to the reactor 7〇4. ❹ The solution after the reaction was analyzed by liquid chromatography, and the yield was 98. 8% of the formation, (4,4,-fluorenylene-diphenyl)-diphenyl dicarboxylate. The line 74' is opened to transport the reaction liquid to the sump 705 via line 74. . Step (10-2): Production of isocyanate by thermal decomposition of the condition #,-(4,4|-fluorenylene-diphenyl)-diamino decanoic acid diphenyl ester is carried out using a device as shown in FIG. reaction. The heat transfer area is 0. The 1 m2 thin film distillation unit 12〇1 is heated to 23〇〇c, and the internal pressure is about 1. 3 kPa. The mixture recovered in the storage tank 705 in the step (10-1) was heated to 13 ° C and supplied to the upper portion of the film evaporation device 1201 via line C1 at about 690 g/hr. From the bottom of the film evaporation chamber, the liquid phase component is discharged from the line C3 and circulated to the upper portion of the film evaporation device 1201 via the line C4 and the line C1. The gas phase component is discharged from line C2. The middle section of the continuous multi-stage distillation column 12〇2 filled with Dixon packing (6 mm ψ) having an inner diameter of about 5 cni and a column length of 2 m is continuously fed by the thin film distillation apparatus 1201 via line C2. The gas phase component is subjected to distillation separation of the gas phase component. The heat necessary for distillation separation is via line C6 and again 131505. Doc •133- 200948760 The boiler 1204 circulates and supplies the liquid in the lower part of the tower. The liquid temperature at the bottom of the continuous multi-stage steaming tower 12〇1 is 20 (TC, the top pressure is 6 〇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. , which is continuously discharged by line C7. The liquid phase component is discharged by the line. The middle section of the continuous multi-stage distillation column 1205 having an inner diameter of about 5 cm and a column length of 2 m filled with a Dixon packing (6 mm φ) is continuously The liquid phase component discharged from the line C8 is fed to perform 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 C11 and the reboiler 1207. The continuous multi-stage distillation column 12 The liquid temperature at the bottom of the 〇5 tower is 210C 'the top pressure is about 2. 5 kPa. The gas discharged from the tower top of the continuous multi-stage steaming tower 12〇5 is condensed in the condenser 12〇6 via the line C10, and continuously discharged through the line C12. The liquid phase component is discharged by line c14. The liquid phase component discharged from the line CM Q 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. Distillation separation of liquid phase components. The heat necessary for the distillation separation is supplied by circulating the liquid in the lower portion of the column via the line C16 and the reboiler 121. The liquid temperature at the bottom of the continuous multi-stage distillation column 12〇8 is 220 C, and the pressure at the top of the column is about 〇·5 kPa. The gas distilled from the top of the continuous multi-stage distillation column 1205 is condensed in the condenser 12〇9 via line C15, via line C17 at about 99. 6 g / hr continuous discharge. The liquid discharged from C17 contains about 99. 9 wt% of 4,4,-diphenyldecane diisocyanate. The yield of 4,4'-methylenediphenylamine was 82 3Q/(^ was continuously carried out for 1 day, and no deposit was found in the wall area of the film distillation apparatus 12〇2. 131505. Doc-134-200948760 [Example π] • Step (11-1): Production of terphenyl benzene-2,4-dicarbamic acid diphenyl ester The reaction was carried out using an apparatus as shown in Fig. 7. In the state where the line 74 is closed, 'by the sump 701 via the line 7, 2 2125 g (9. 9 mol) a mixture of a reference example of diphenyl carbonate and 35"g (〇2 m〇1) zinc acetate dihydrate is supplied to a SUS reaction cell 704 with a baffle having an internal volume of 5 l From the storage tank 702, 1534 〇g (16.3 mol) of phenol was supplied to the SUS reactor via line 72. The temperature of the liquid in the reactor 704 was adjusted to about 50. (:, by tank 703 via line 73, will be 391 g at about 230 g/hr. 2 mol) 2,4-toluenediamine (manufactured by Aldrich, USA) was supplied to the reactor 704. The solution after the reaction was analyzed by liquid chromatography, and the yield was 98. 1% produces diphenyl 2,4-diaminodecanoic acid diphenyl ester. Line 74 is opened and the reaction liquid is conveyed via line 74 to storage tank 7〇5. . Step (11-2): Thermal decomposition of toluene 2,4-dicarbamic acid dicarboxylate to produce isocyanate The reaction was carried out using a apparatus as shown in Fig. 8. The heat transfer area is 0. The 1 m2 thin film distillation apparatus 8〇1 is heated to 22 (rc, so that the internal pressure is about 13 kPa. The step (π — :)* is recovered from the mixture recovered by the storage tank 7〇5 to 130. (:, via line 81 It is supplied to the upper portion of the thin film distillation apparatus 801 at about 820 g/hr. From the bottom of the thin film distillation apparatus 8〇1, the liquid phase component is discharged from the line 83, and is circulated to the thin film evaporation apparatus 801 via the line 84 and the line 81. Upper portion. The gas phase component is discharged from line 82. The inner diameter of the filled Dixon packing (6 mm φ) is about 5 cm and the length of the tower is 2 131505. In the middle section of the continuous multi-stage distillation column 8〇2 of doc-135-200948760 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 8〇2 is 15 (TC, the column top pressure is about 15 kpa. The gas distilled from the top of the continuous multi-stage distillation column 802 is condensed in the condenser 8〇3 via line 85. Exhausted continuously by line 87. The liquid phase component is discharged from line 89 of the continuous multi-stage distillation column 8〇2 below line 82. The inner diameter of the 〇-filled Dixon packing (6 mm Φ) is about 5 Em, a middle section of a continuous multi-stage distillation column 8〇5 having a column length of 2 m, continuously feeding the liquid phase component discharged from the line 89, and performing distillation separation of the liquid phase component. The heat necessary for distillation separation is passed through The line 91 and the reboiler 807 circulate and supply the liquid in the lower part of the column. The liquid temperature at the bottom of the tower of the continuous multi-stage steaming tower 805 is 15 〇C ^^ and the top pressure is about 1. 3 kPa. The gas from the tower of the continuous multi-stage steaming tower was condensed in the condenser 806 via the line 9 and continuously discharged to the storage tank 809 at about 93 g/hr via the line Q path 92. The liquid system discharged from line 92 contains about 99. 7 wt% of a solution 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 found in the wall area of the thin film distillation apparatus 8〇1. [Example 12]. Step (12-1): Preparation of #,-(4,4,-methylene-diphenyl)-diphenyl dicarboxylate In addition to using 2055 g (9. 5 mol) Reference Example 1 diphenyl carbonate with M 9 131505. Doc -136- 200948760 g(0. 3 mol) a mixture of zinc acetate 2 hydrate, 1293 g (13. 8 mol) phenol and 496 g (2. The same procedure as in the step (10-1) of Example ι was carried out except that 5 mol of 4,4'-methylenediphenylamine was used. The solution after the reaction was analyzed by liquid chromatography, and the yield was 98. 6% was produced from #,-(4,4,-ytylene-diphenyl)-diphenyldicarboxylate. • Step (12-2): Using isothermal acid vinegar by iV, iV'-(4,4·-indenylene-diphenyl)-diamino phthalic acid monophenyl vinegar to produce isogastric acid vinegar -1) The obtained mixture was substituted for the mixture obtained in the step (7-1), and the mixture was heated to 1 30 ° C. The thermal decomposition reaction was carried out via line d 1, with 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 22 (TC, the column top pressure is about 15 kPa. The gas distilled from the top of the continuous multi-stage distillation column 1301 is condensed in the condenser 133 via line D2, The line 〇4 is continuously discharged. The liquid phase component is recovered from the bottom of the continuous multi-stage distillation column 1301 via the line d3. The inner diameter is filled with Dickson packing (6 mm φ) and the inner diameter is about 5 cm, and the length of the tower is 2 m. In the middle section of the continuous multi-stage distillation column 13〇4, the liquid phase component discharged continuously through the line 〇6 is subjected to distillation separation of the liquid phase component. The heat necessary for the distillation separation is passed through the line D8 and the reboiler 1306. The liquid in the lower part of the column is circulated and supplied. The liquid temperature at the bottom of the continuous multi-stage distillation column 1304 is 22 〇 ° 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 13〇4 is continuously discharged through the line D9 via the line D7 and condensed in the condenser 13〇5. From the bottom of the continuous multi-stage distillation column 13〇4, the liquid phase will be 131505. Doc •137- 200948760 The ingredients are recovered via line D8 and line d 11. 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 13〇7 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 contains about 99. A solution of 8 wt% of 4,4,-diphenylnonane diisocyanate. The yield relative to 4,4·-fluorenylene diphenylamine is 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): Production of dioxin-dihexyl-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. In the eggplant type flask, a three-way cock is installed, and a spiral filler No. is filled.  A distillation column of 3, a fractionation column of a reflux condenser connected to the distillate receiver, and a thermometer are subjected to vacuum-nitrogen replacement in the system to distill the purified diphenyl carbonate. The purified product was subjected to 1H-NMR measurement, and the result contained about 99. 9 wt% diphenyl carbonate. Also' contains 0. 002 ppm is the iron of the metal atom. In addition to the supply 1414 g (6. 6 mol) of diphenyl carbonate, 1 〇 34 g (11. 0 mol) phenol and 256 g (2. In addition to 2 mol) hexamethylenediamine, it was carried out with Example 1 131505. The same method as step (1-1) of doc -138· 200948760. The solution after the reaction was analyzed by liquid chromatography, and the yield was 99. 0% generated #,#,·hexanediyl-bis-aminocarboxylic acid dip vinegar. • Step _3·2): Production of isocyanate by thermal decomposition of #,-hexanediaminocarbamic acid diphenyl vinegar, except that the mixture obtained in the step (13-1) is used instead of the mixture obtained in the step (11) Further, the same method as in the step (12) of the example was carried out. It is continuously discharged to the storage tank 8〇9 by the line Μ at about 1〇4 g/hr. The liquid system discharged by the line contains about 99. A solution of 8 wt% hexamethylene diisocyanate. The yield relative to hexamethylenediamine was 95%. The continuous operation was carried out on a dry day. The deposit was not found in the wall area of the film evaporation device 801. [Example 14] Step (14-1).  Preparation of iV, 7V-hexanediyl-bis-carbamic acid diphenyl ester To the diphenyl carbonate of Reference Example 1, ethylene bromide (H) was added to prepare carbonic acid containing 8% of iron as a metal atom. Phenyl ester. In addition to the supply of 丨37丨g (6 4 Q m〇l) the diphenyl carbonate, 940 g (l〇. 〇 mol) phenol and 232 g (2. The same procedure as in the step (U) of Example 1 was carried out, except that 0 mol of hexamethylenediamine. The solution after the reaction was analyzed by liquid chromatography, and the yield was 98. 9% yielded dihexyl-bis-carbamic acid diphenyl ester. . Step (14-2): Production of isocyanate by thermal decomposition of hydrazine, hydrazine-hexanediyl-bis-carbamic acid diphenyl vinegar, except that the mixture obtained in the step (14-1) is used instead of the step (ι_ι) The same procedure as in the step (1-2) of Example 1 was carried out, except for the mixture. 131505. Doc-139-200948760 is continuously discharged to the storage tank 8〇9 by line 92 at about 101 g/hr. The liquid system discharged by line 92 contains about 99. A solution of 8 wt% hexamethylene diisocyanate. The yield relative to hexamethylenediamine is 95. 2%. After 1 day of continuous operation, the operation was not found in the wall area of the thin film distillation apparatus 801. [Example 15] Step (15-1).  iV, hexamethylene-bis-carbamic acid diphenyl vinegar was produced. The diphenyl carbonate of Reference Example 1 was placed in an eggplant type flask having an internal volume of 1 〇L. A three-way cock was attached to the eggplant type flask, Attached with a spiral filler No.  a distillation column of 3 and a reflux tower connected to the distillate receiver, and a thermometer, vacuum-nitrogen replacement in the system, and distillation of purified diphenyl carbonate to obtain about one-fourth of the added amount. At the time of the museum's release, the flask was cooled to complete the purification. 1H-NMR measurement of the contents of the library was carried out, and the result contained about 99. 9 wt% diphenyl vinegar. also. The metal atoms contained in the German product, in terms of iron, diamond, nickel, zinc, tin, copper, and Qin, are the lower limit of detection (0. 001 ppm) or less. In addition to supply 1553 g (7. 3 mol) of diphenyl carbonate, 1175 g (12. 5 mol) phenol and 291 g (2. The same procedure as in the step (1-1) of Example 1 was carried out, except for 5 mol of hexamethylenediamine. The solution after the reaction was analyzed by liquid chromatography, and the yield was 95. 6% produces dihexyldiyl-bis-carbamic acid diphenyl ester. • Step (15-2): Production of isocyanate by thermal decomposition of hexamethylene-bis-amino phthalic acid diphenyl vinegar except that the mixture obtained in the step (15-1) is used instead of the step (1-1) The same procedure as in the step (1-2) of Example 1 was carried out, except for the mixture. 131505. Doc -140- 200948760 The liquid is continuously discharged to the sump 8〇9 by line 92 at about 99 _ 1 g/hr. The liquid system discharged from line 92 contains a solution of about 99% by weight of hexamethylene diisocyanate. The yield relative to hexamethylenediamine is 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 8〇1. [Example 16]. Step (16-1): Production of 坨#'-hexanediyl-bis-carbamic acid diphenyl ester To the diphenyl carbonate of Reference Example 1, iron (II) acetonitrile was added to prepare 13/❶ as a preparation. Diphenyl carbonate of metal atomic iron. In addition to supplying 1527 i mol of the monophenyl carbonate, 1 〇 81 g (u 5 m〇i) phenol, and g (23 mol) /, methylene monoamine, the steps of the embodiment (1 _ 1) The same method. The solution after the reaction was analyzed by liquid chromatography, and the yield was 94. 5% yields 恳#'_hexanediyl-bis-carbamic acid diphenyl ester. • Step (16-2): Production of isocyanate by thermal decomposition of diphenyl bis-bis-carbamic acid diphenyl ester except that the mixture obtained in the step (16-1) is used instead of the step ο — In addition to the materials, the same method as in the procedure of Example 2) was carried out. From line 92 to about 95. 1 g/hr was continuously discharged to the storage tank 8〇9. The liquid system discharged by line 92 contains about 99. A solution of 8 wt% hexamethylene diisocyanate ruthenium. The yield relative to the hexamethylenediamine was 88%. The continuous operation was carried out for 1 day, and as a result, no deposit was observed in the wall area of the thin film distillation apparatus 8〇1. [Example 17] 131505. Doc -141- 200948760 •Step (17-1): #, Manufacture of hexamethylene-bis-amino phthalic acid diphenyl vinegar In addition to supply 1350 g (6. 3 mol) diphenyl carbonate and 79 〇 g (8 4 m 〇 1) benzene test 'supply 244 g (2. 1 mol) hexamethylenediamine and 197 g (2. The same procedure as in the first step (1-1) of Example 1 was carried out except that a mixture of 1 mol)* phenol was used instead of the hexamethylenediamine. The solution after the reaction was analyzed by liquid chromatography, and the yield was 99. 0% produces hexamethylene-bis-carbamic acid diphenyl vinegar. . Step (17-2): producing an isocyanate by using a thermal decomposition of dihexyldiamine-diphenylphosphonate, except that the mixture obtained in the step (17-1) is used instead of the step (1_丨) The same method as the step (1_2) of Example 1 was carried out except for the mixture. The liquid is continuously discharged from the line 92 at about 1 〇 6 g/hr to the sump 8 〇 9 ^ The liquid system discharged from the line 92 contains about 99. A solution of 8 wt% hexamethylene diisocyanate. The yield relative to the hexamethylenediamine was 97%. The continuous operation was carried out for 1 day. The surface area of the thin film distillation apparatus 8〇1 was not found to be attached.实施 [Example 18] • Step (18-1): Production of bis(3- mercaptobutyl) hexamethylenedicarboxylate The apparatus shown in Fig. 16 was used. In the state where the line G4 is closed, 1660 g (7.) is received by the sump 1601 via the line G1. 8 mol) diphenyl carbonate was supplied to a sus-made reaction vessel 1604 with a baffle of 5 l, and the sump 1602 was passed through a line 〇2, which was 1175 g (12. 5 mol) of phenol was supplied to the reactor made of SUS. The reaction 131505. Doc -142- 200948760 The temperature of the liquid in the device 1604 is adjusted to about 50 ° C, and the sump 1603 is 291 g (2. A mixture of 5 mol) hexamethylenediamine and water was supplied to the reactor 1604 at about 2 g/hr. After the completion of the reaction, the pressure inside the reactor 1604 was reduced to 10 kPa, and water was removed. The water is condensed in the condenser 1607 and discharged through the line. The solution after the reaction was analyzed by liquid chromatography, and the yield was 99. 0% yielded dihexyl-bis-carbamic acid diphenyl ester. The line G4' is opened and the reaction liquid is transported via line G4 to the sump ® 1605. . Step (18-2): using a thermal decomposition of hexamethylene-bis-amino phthalic acid diphenyl ester to produce isocyanate, except that the mixture obtained in the step (18-1) is used instead of the step (丨_丨) The same procedure as in the step (?_2) of Example 1 was carried out except for the obtained mixture. The heating area of the film evaporation apparatus 801 with respect to the reactor capacity is larger than the reactor 1 604 of FIG. The liquid is continuously discharged q to the sump 809 by line 92 at about 1 〇 4 g/hr. The liquid system discharged from line 92 contains about 99. A solution of 8 wt% hexamethylene diisocyanate. The yield relative to hexamethylenediamine is 96. 5°/. . The continuous operation was carried out for one day. The deposit was not found in the wall area of the thin film distillation apparatus 8〇1. [Example 19] Cleaning of the reactor The cleaning operation of the thin film distillation apparatus 801 in which the deposit was accumulated was carried out in Example 6. The film evaporation chamber 8〇1 was heated to 18 Torr.匸, the inside of the film evaporation chamber 801 is an atmospheric nitrogen atmosphere. It is supplied by line 81 at about 12 〇〇 g/hr, and is discharged from line 83, and the liquid phase component is recovered to storage tank 131505 via line 94. Doc -143· 200948760 810 ° This operation was carried out for 1 hour, and as a result, no deposit was observed inside the thin film distillation apparatus 801. [Example 20] to [Example 27] The operation of Example 6 was continuously carried out. The cleaning operation was carried out in the same manner as in Example 19 using various cleaning solvents every one day, and the results are shown in the table! . [Comparative Example 1] • Step (A-1): Production of iV, AT-hexanediyl-bis-amino phthalic acid diphenyl ester The reaction was carried out using an apparatus as shown in Fig. 14. In the state in which the line E4 is closed, 1979 g (9.) is carried out from the storage tank 14〇1 via the line E1. 2 mol) of diphenyl carbonate was supplied to a SUS reaction vessel 1404 with a baffle of internal volume, and 13 16 g was passed from the storage tank 1402 via line E2. 0 mol) phenol was supplied to the reactor of the SUS. The temperature of the liquid in the reactor 1404 is adjusted to about 5 〇〇c, which is 325 g (about 190 g/hr) from the sump 14〇3 via the line E3'. 8 mol) of the hexamethylenediamine is supplied to the reactor 1404. The solution after the reaction was analyzed by liquid chromatography, and the yield was 99. 3% yielded diphenyl bis-amino phthalate. . Step (A-2): Isocyanate was produced by thermal decomposition of dihexyl-bis-carbamic acid diphenyl ester, followed by a reaction as shown in Fig. 14. The SUS reactor 14〇4 was heated to 220. (:, decompress the reactor 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). The vaporization of the gas phase component is carried out 131505. Doc 200948760 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 continuous multi-stage steaming tower 14〇5 has a liquid temperature of 150 ° C at the bottom of the column and a pressure of about 15 kPa at the top of the column. The gas distilled from the top of the continuous multi-stage distillation column 802 is condensed by the line in the condenser 1407 and continuously discharged by the line E7. The liquid phase component is discharged from the line E9 of the continuous multi-stage steaming tower 405 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 liquid in the lower portion of the column via the line El 1 and the reboiler 1412. The liquid temperature at the bottom of the continuous multi-stage distillation column 1406 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 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 the storage tank 1411 is about 304 g. The liquid system contains about 99. A solution of 8 wt% hexamethylenediyl q-isocyanate. The yield relative to the hexamethylenediamine is 64. 5%. [Comparative Example 2]. Step (B-1): Production of jV, AT-(4,4'-methylene-diphenyl)-dicarbamic acid diphenyl ester The reaction was carried out using a device as shown in Fig. 15. In the state where the line F4 is closed, 1527 g (7.) is received by the sump 1501 via the line F1. 1 mol) diphenyl carbonate and 50. 5 g (0. A mixture of 2 mol) zinc acetate 2 hydrate was supplied to a SUS reaction vessel 1504 with a baffle having an internal volume of 5 L. From the storage tank 1502 via line F2, 1146 g (1. 2 mol) phenol 131505. Doc -145· 200948760 was supplied to the SUS reactor. The temperature of the liquid in the reactor 1504 is adjusted to about 50 ° C, and 456 g (2.) is passed from the storage tank 1503 via the line F3. 3 mol) 4,4'-decylenediphenylamine was supplied to the reactor 1504 at about 200 g/hr. The solution after the reaction was analyzed by liquid chromatography, and the yield was 98. 3% yield iV, iVf-(4,4'-fluorenylene-diphenyl)-diphenyl dicarboxylate. • Step (B-2): Production of isocyanate by thermal decomposition of W-(4,4'-methylene-diphenyl)-diamino phthalic acid diphenyl ester followed by using a device as shown in FIG. Carry out the reaction. The SUS reactor 1504 was heated to 220 ° C to decompress the reactor into 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 the 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 F6 and the reboiler 1 507. Continuous multi-stage steaming tower 丨 5〇6 © $ bottom The liquid temperature is 200 ° C, the top pressure is 60 kPa. The gas taken from the top of the continuous multi-stage steaming tower 1506 is condensed in the condenser 1505 via the line F5, and continuously discharged from the line F7. By the line! ? 6 discharge liquid phase components. To the middle section of a continuous multi-stage distillation column 1509 filled with Dixon packing (6 mm φ) with an inner diameter of about 5 cm and a column length of 2 m, continuously fed by the line? The liquid phase components discharged in 6 are subjected to distillation separation of the liquid phase components. The heat necessary for the distillation separation is supplied by circulating the liquid in the lower portion of the column via the line F11 and the reboiler 1510. Continuous multi-stage distillation column 丨 509 tower bottom liquid temperature 131505. Doc 200948760 is 210 ° C, the top pressure is about 2. 5 kPa. The gas distilled from the top of the continuous multi-stage distillation column 1509 is condensed in the condenser 15A through the line F10, and continuously discharged through the line F12. The liquid phase component is discharged from the line fii. The liquid phase component discharged from the line Fi4 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 technical length of 2 m. Distillation separation of phase components. The heat necessary for the vaporization separation is supplied by circulating the liquid in the lower portion of the column via the line F16 and the reboiler 1513. The liquid temperature at the bottom of the continuous multi-stage distillation column 15 12 is 220 ° C, and the pressure at the top of the column is about 〇. 5 kPa. The gas taken from the fourth of the continuous multi-stage distillation column 1512 is condensed in the condenser bn via the line, and is discharged via the line F17. The liquid discharged from F17 is about 7 〇 g, which contains about 99. 9 wt% of 4,4,-diphenylmethane diisocyanate. The yield relative to 4,4'-methylenediphenylamine was 56. 0%. [Comparative Example 3] • Step (C-1): Production of hexamethylene-bis-amino phthalic acid diphenyl vinegar g The reaction was carried out using a device as shown in Fig. 7. In the state where the line 74 is closed, 2454 g (ll.) will be passed from the storage tank 7〇1 via the line 71. 5 mol of diphenyl carbonate was supplied to a SUS reaction vessel 704 with an internal volume of 5 [with a baffle plate. The temperature of the liquid in the reactor 7〇4 was adjusted to about 80 C, and the diphenyl carbonate was melted, and 372 g (3.) was passed from the storage tank 7〇3 via the line 73. 2 mol) hexamethylenediamine was supplied to the reactor 704 at about 1 〇〇 g/hr. The solution after the reaction was analyzed by liquid chromatography, and the yield was 77. 5% yields dihexyl-bis-carbamic acid diphenyl ester. 131505. Doc-147-200948760 The line 74 is opened and the reaction liquid is transported via line 74 to the sump 705. • Step (C-2): Isocyanate was produced by thermal decomposition of dihexyl-bis-carbamic acid diphenyl ester. The reaction was carried out using a apparatus as shown in Fig. 8. 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 contains about 99. A solution of 8 wt% hexamethylene dihydrochloride ® isocyanate. The yield relative to hexamethylenediamine is 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 washing operation was carried out in the same manner as in Example 13, and the results are shown in Table 1. [Table 1] Table 1 Cleaning operation implementation results

Thin film distillation apparatus temperature Cleaning solvent Cleaning solvent supply amount Cleaning time Result Example 20 200 ° C 2,6-Dimethylphenol 100 g/Hr 2 hours 实施 Example 21 210. . 2,4,6-Trimethylphenol 800 g/Hr 2 hours 〇 Example 22 250 ° C 2-Phenylphenol 1000 g/Hr 3 hours 〇 Example 23 280 ° C 2,4-(α,α- Dimethylbenzyl)phenol 1200 g/Hr 1 hour 〇 Example 24 2001: 4-ethoxyphenol 1100 g/Hr 2 hours 〇 Example 25 270. . 4-dodecylphenol 1300 g/Hr 1 hour 〇 Example 26 2001: Salicylic acid 800 g/Hr 2 hours 〇 Example 27 220 〇C Benzoic acid 800 g/Hr 4 hours 〇 Comparative Example 4 200° C-n-decane 1000 g/Hr 4 hours 〇Comparative Example 5 200°C Naphthalene 1000 g/Hr 4 hours X Comparative Example 6 180°C 1-Phenylphenol 1000 g/Hr 4 hours X 〇: After washing operation, Found attachments X: After the cleaning operation, the deposits were found 131505.doc -148- 200948760 [Industrial Applicability] The isocyanate production method of the present invention can efficiently produce isocyanate without using highly toxic phosgene, and thus the present invention The manufacturing method is very useful in the industry and has a high commercial value. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a conceptual view showing a continuous production apparatus of a carbonate according to an embodiment of the present invention. Fig. 2 is a conceptual view showing an apparatus for producing an aromatic carbonate according to an embodiment of the present invention. Fig. 3 is a conceptual view showing an apparatus for producing an aromatic carbonate according to an embodiment of the present invention. Fig. 4 is a view showing an embodiment of the present invention. A conceptual diagram of an alcohol purification unit. Fig. 5 is a conceptual view showing a diaryl carbonate purification apparatus according to an embodiment of the present invention. Fig. 6 is a view showing the outline of 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 aryl 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. 131505.doc -149- 200948760 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 amino aryl phthalate according to an embodiment of the present invention. [Explanation of main component symbols] (Fig. 1) 1, 2, 3, 4, 5, 6, lines 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17 101 ' 107 Distillation column 102 Tower reactor 103, 106 thin film distillation unit 104 autoclave 105 carbon removal tank 111, 112, 117 regenerators 121, 123, 126, 127 condenser 131505.doc -150- 200948760 (Fig. 2) 21, 22, 23 , 24, 25 201 202 203 204 205, 206 line preheater continuous multi-stage distillation tower condenser reboiler storage tank (Figure 3)

31, 32, 33, 34, 35 301 302 303 304 305 > 306 (Fig. 4) Line Preheater Continuous Multistage Distillation Column Condenser Reboiler Storage Tank

41, 42 , 43 , 44 , 45 401 402 403 404 405 , 406 ( Fig. 5 ) Line preheater continuous multi-stage distillation tower condenser reboiler storage tank 51, 52, 53, 54, 55 501 line preheater 131505. Doc 151 - 200948760 502 503 504 505, 506 (Fig. 6) Continuous multi-stage distillation column condenser reboiler storage tank 61 ' 62 ' 63, 64, 65 Ο 601 602 603 604 605 > 606 line preheater continuous multi-stage distillation tower Condenser reboiler sump (Fig. 7) 71, 72, 73, 74 701, 702, 703, 705 line tank 704 (Fig. 8) Stirring tanks 81, 82, 83, 84, lines 85, 86, 87, 88 ' 89 801 802 '803 808 , 809 , 810 803 ' 806 804 ' 807 Thin film distillation unit continuous multi-stage distillation column sump condenser reboiler 131505.doc -152- 200948760

(Fig. 9) 90, 91, 92, 93 94, 95, 96, 97, 98, 99 901 902 903 904 905, 906 (Fig. 10) 1001 1002 1003 1004 1005, 1006 Al, A2, A3, A4, A5 ( Figure 11) 1101 1102 1103 1104 1105, 1106 Bl, B2, B3, line preheater continuous multi-stage distillation tower condenser reboiler storage tank preheater continuous multi-stage distillation tower condenser reboiler storage tank line preheater continuous multi-stage distillation Tower condenser reboiler sump line 131505.doc -153 - 200948760 B4, B5 (Fig. 12) Thin film distillation unit continuous multi-stage distillation column condenser reboiler line 1201 1202, 1205 ' 1208 1203 ' 1206 , 1209 1204 ' 1207 ' 1210 Cl, C2, C3,

C4, C5, C6, C7, C8, C9, CIO, C11, C12, C13, C14, C15, C16, C17, C18 (Figure 13)

1301, 1304, 1307 1302, 1305, 1308 1303, 1306, 1309

Dl, D2 ' D3, continuous multi-stage distillation tower condenser reboiler line D4, D5, D6, D7, D8, D9, D10, D11, D12, D13, D14, D15 (Fig. 14) 1401, 1402, storage tank 1403 ' 1409 , 1410 -154- 131505.doc 200948760 1404 1405 , 1406 1407 , 1410 1408 , 1412 El , E2 , E3 , Stirring tank continuous multistage distillation tower condenser reboiler line E4, E5, E6, E7, E8, E9, E10, El 1, E12,

E13 (Fig. 15) 1501, 1502, 1503 sump 1504 1506, 1509, 1512 1505, 1508, 1511 1507, 1510, 1513 Stirring tank Continuous multi-stage distillation column Condenser Reboiler

FI, F2, F3, lines F4, F5, F6, F7, F8, F9, F10, FI1, F12, F13, F14, F15, F16, F17, F18 (Fig. 16) 1601, 1602, 1603 Storage tanks 1606 131505. Doc -155- 200948760 1604 Stirring tank 1605 Column 1607 Condenser G1, G2, G3, Line G4, G5, G6 ❹ ❿ 131505.doc 156-

Claims (1)

200948760 X. Patent Application Range: 1. A method for producing 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 a reaction mixture of an aryl aryl phthalate derived from an aryl group of a diaryl carbonate, an aromatic hydroxy compound derived from a diaryl carbonate, and a diaryl carbonate; transporting the reaction mixture to a thermal decomposition reactor, wherein The thermal decomposition reactor is connected to the reactor which performs the reaction of the diaryl carbonate with the amine compound by a pipe; and the isocyanate is obtained by subjecting the amine aryl phthalate to thermal decomposition reaction. 2. The method of claim 1, further comprising the step of acid cleaning the high-boiling by-product attached to the thermal decomposition reactor. 3. The production method according to claim 1, wherein the reaction of the diaryl carbonate with the amine compound is carried out under the conditions that the stoichiometric ratio of the diaryl carbonate to the amine group constituting the amine compound is 1 or more. 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. 5. The production method according to claim 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 aryl carbonate ArOCOOAr (Ar represents an aromatic group, and 〇 represents oxygen A structure in which a hydrogen atom is added to ArO based on an atom. 6. The production method of claim 1, wherein the reaction mixture is supplied as a liquid to the thermal decomposition reactor. The method of claim 6, wherein the reaction mixture is supplied to the thermal decomposition reactor at a temperature ranging from 1 ° C to 180 ° C. 8. The production method of claim 1, wherein the reaction mixture is continuously supplied to the thermal decomposition reactor. 9. The production method according to claim 1, wherein the low boiling component generated in the thermal decomposition reaction is recovered as a gas phase component from the thermal decomposition reactor. The liquid phase component is recovered from the bottom of the reactor. 10. The production method of claim 9 wherein the recovery of the gas phase component and the recovery of the liquid phase component are carried out continuously. 11. The method of claim 9, 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 containing the diaryl carbonate is contained. The ingredients are recovered from the bottom of the reactor. 12. The method of claim 丨i, further comprising the step of: separating the isocyanate-containing gas phase component recovered from the thermal decomposition reactor by the distillation column to recover the isocyanate; and recovering the isocyanate recovered from the thermal decomposition reactor The gas phase component is supplied to the distillation column in the gas phase. 13. The method of claim 1, wherein the liquid 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. 14. The production method according to claim 9, wherein the isocyanate g obtained by the hot knife 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 of claim 14, wherein the liquid recovered from the bottom of the reactor 131505.doc 200948760 phase component contains isocyanate and aryl carbamate, and some or all of the isocyanate is separated from the liquid phase component, leaving one part remaining Or all of it is supplied to the upper part of the reactor. 16. The method of claim 14, wherein the isocyanate is recovered by distillation separating the isocyanate-containing mixture recovered from the thermal decomposition reactor. 17. The production method according to claim 1, wherein the type of the reactor for performing the reaction of the diaryl carbonate with the amine compound is the same as or different from the type of the thermal decomposition reactor, and the diaryl carbonate and the amine compound are carried out. The reactor for the reaction and the thermal decomposition reactor are at least one selected from the group consisting of a column reactor and a tank reactor. 18. The method of claim 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 method of claim 1, wherein the reaction of the diaryl carbonate with the amine compound is carried out in the presence of a catalyst. 20. The method of claim 1, wherein the thermal decomposition reaction is carried out in a liquid phase. 21. The method of claim 1, wherein the diaryl carbonate is a compound represented by the following formula (1): [Chemical Formula 1] 〇r1'〇Xo^1 (1) (wherein R1 represents a carbon number It is an aromatic group of 6 to 12). The method of claim 21, wherein the diaryl carbonate contains 金属 〇〇 ppm ppm to 10% of a metal atom. 23. The method of claim 22, wherein the metal atom is selected from one or more of the group consisting of iron, nickel, cobalt, zinc, tin, copper, and titanium. 24. The method of claim 1, wherein the diaryl carbonate is produced by the steps comprising the following steps (丨) to (3): Step (1): having a tin-oxygen-carbon bond The organotin compound is reacted with carbon dioxide to obtain a reaction mixture containing dialkyl carbonate; step (2): separating the reaction mixture to obtain a dialkyl carbonate and a residual liquid; and step (3): separating the step (2) The carbonated vinegar is reacted with the aromatic trans-based compound A to obtain a diaryl carbonate, and the alcohol formed as a by-product is recovered. 25. The method of claim 24, wherein the aromatic hydroxy compound a is an aromatic hydroxy compound having 6 to 12 carbon atoms. 26. The method of claim 24, wherein the diaryl carbonate is manufactured by further comprising the steps of the following steps and the step (5): Step (4): the residue obtained in the step (2) The liquid reacts with the yeast to form an organotin compound having a tin-oxygen-carbon bond and water, and the water is removed from the reaction system; Step (5): the tin-oxygen-carbon bond obtained in the step (4) is obtained. The organotin compound is reused as the organotin compound 131505.doc 200948760 having a tin-oxygen-carbon bond in the step (1). 27. The method of claim 24, 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 9, 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. Λ 29. As requested by the manufacturer or method of 24, from the autothermal decomposition reactor Separating and recovering the aromatic mercapto compound from the recovered liquid phase component or gas phase component, the aromatic mercapto compound as the aromatic mercapto compound A of the step (3), or the family of the reaction solvent The base compound is reused. 3. The method of manufacture of the applicant, wherein the amine compound is a polyamine compound. The method of claim 3, wherein the amine compound is represented by the following formula (2): [Chem. 2] R 2 * (nH 2 ) n (2) (wherein R represents a selected from the group consisting of Carbon, negative 甩I % 曰 之 之 atomic carbon number is 1~20 month 曰 aliphatic base, and carbon number is 6~20 Fang Fanyou correct, heart party loan base group A 'having an valence equal to η; η is an integer from 2 to 1〇). Wherein the amine compound is a diamine compound of the formula (2), wherein the compound is the same as the method of the method of claim 31, the method of claim 1, wherein the amine compound is supplied to the carbonate. When the reactor is reacted with the amine compound, it is carried out in a liquid state. 3. The production method of claim 1, wherein the amine compound is supplied to the reactor for reacting the carbonate with the amine compound, It is carried out in the state of a mixture of an alcohol, water, or a carbonate. 13I505.doc