TW200948759A - Process for producing isocyanate - Google Patents

Abstract

A process for producing an isocyanate without using phosgene. The process has none of various problems encountered in prior art techniques and enables an isocyanate to be stably produced in high yield for long. The process is for producing an isocyanate by subjecting a carbamic acid ester to pyrolytic reaction. The process includes: a step in which low-boiling ingredients are recovered as a gas-phase ingredient from a pyrolysis reactor where the pyrolytic reaction is conducted; a step in which a liquid-phase ingredient containing the carbamic acid ester is recovered through a bottom part of the pyrolysis reactor; and a step in which part or all of the liquid-phase ingredient is supplied to an upper part of the pyrolysis reactor.

Description

200948759 IX. Description of the invention: [Technical field to which the invention pertains] The present invention relates to a method for producing isocyanic acid vinegar. [Prior Art] Isocyanate is widely used as a raw material for the production of a polyurethane foam, a coating material, an adhesive, and the like. The main industrial manufacturing process for isocyanates is to react an amine compound with phosgene (phosgene method), and almost all of the world's production is produced by the phosgene method. However, the phosgene method has many problems. The first 'large use of phosgene 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 'in the phosgene method', a large amount of by-products are used as a by-product of highly corrosive gasification hydrogen, so a process for removing the vaporized hydrogen is required, and the produced heterogas acid S is mostly hydrolyzed. gas. Therefore, in the case of using the isogastric acid vinegar produced by the phosgene method, the weather resistance and heat resistance of the polyamino phthalate product may be adversely affected. In view of such a background, a manufacturing method of an isocyanate compound which does not use phosgene is desired. As an example of a method for producing an isocyanate compound which does not use phosgene, a method of thermal decomposition using a urethane is proposed. It has been known for a long time that an isocyanate and a hydroxy compound are obtained by thermal decomposition of an amino phthalic acid ester (for example, refer to the non-patent literature. The basic reaction is exemplified by the following formula: [Chemical 1] R (NHCOOR% - ♦ _CO ) a + a r. 〇 h 131506.doc 200948759 (wherein R represents an organic residue of a valence, R' represents a monovalent organic residue, and a represents an integer of 1 or more.) In the thermal decomposition reaction, various irreversible side reactions such as a thermal modification reaction of the carbamic acid g or a condensation reaction of isocyanic acid by the thermal decomposition are easily caused at the same time. For example, a reaction for forming a urea bond represented by the following formula (2), φ., () represents a reaction for producing a carbodiimide or, for example, by the following formula 丨4+ __) The reaction of producing isocyanates (see Non-Patent Documents 1 and 2). [化2] Lu

PHH Ο R - kc-0 一氓 + 卜 R—N=c=0 + 〇=ϊ〇=Ν—R __„R, VR R· R*—O—C—〇—R* ( 2〉 R— N«C=N-R+ c〇2 (3) R—N=c=〇

R (4) and the like, RAR in the above formula, indicating that the aliphatic succinyl group or the aromatic base group reduces such side reactions not only leads to a decrease in the yield or selectivity of the target isogastric acid, but also in the production of poly In the case of an anaerobic acid vinegar, it is difficult to carry out long-term operation such as precipitation of a solid substance and clogging of a reactor. The method of =:=: to produce an isocyanide method, which has heretofore been disclosed according to Patent Document 1 'aliphatic diamine phthalic acid vinegar and/or fat I31506.doc 200948759 formula urethane and/or fat The polyamino phthalic acid ester and/or the alicyclic polyamino phthalic acid ester are obtained by the following: in the presence of an oxime-alkylaminocarbamic acid g and an amine, an amine NH2 group: an amine Carbamate: alcohol ratio i: 〇·8~10: 0.25~50, at 160°C~3 00°C, in the presence or absence of a catalyst, the aliphatic primary diamine and/or Alternatively, the alicyclic primary diamine and/or the aliphatic primary polyamine and/or the alicyclic primary polyamine are reacted and the ammonia produced is removed as needed. The resulting diurethane and/or polycarbamic acid acetate can be converted to the corresponding diisocyanate and/or high functional polyisocyanate as needed. The detailed reaction conditions for thermal decomposition are not disclosed in this patent document. According to Patent Document 2, an aromatic diisocyanate and/or a polyisocyanate are produced through the following two steps. Specifically, in the second step, the aromatic primary amine and/or the aromatic primary amine and the oxime alkyl group are present in the presence or absence of a catalyst, and in the presence or absence of urea and an alcohol. The urethane is reacted to form an aryl dicarbamate and/or an aryl poly-amino carboxylic acid vinegar, and the ammonia produced is removed as needed. In the second step, an aromatic isocyanate and/or an aromatic polyisocyanate is obtained by thermal decomposition of an aryldicarbamate and/or an arylpolyamine phthalate. There are other publications relating to the use of compounds containing a few groups, for example, N-substituted amino carboxylic acid vinegar and/or diacetic acid vinegar, or monosubstituted or disubstituted urea, or monosubstituted polyurea or disubstituted polyurea. The disclosure of partial substitution of urea and/or diamine (see Patent Document 3, Patent Document 4, Patent Document Patent Document 6, and Patent Document 7). Patent Document 8 discloses a method of producing an aliphatic o-aryl urethane by reacting a (cyclo)aliphatic polyamine with urea and an aromatic hydroxy compound to produce 131506.doc 200948759. There are several known methods for the formation of corresponding isocyanates and alcohols by thermal decomposition of (cyclo)aliphatic and especially aromatic monoamine phthalic acid and diamine phthalic acid esters. A method carried out at a high temperature or a method carried out in a liquid phase at relatively low temperature conditions. However, in such methods, sometimes the reaction mixture may, for example, cause the above-mentioned side reactions, for example, formation of a sediment, a polymer-like substance, and clogging in the reactor and the recovery device or formation of a solid on the wall of the reactor. The object is therefore economically inefficient when the isocyanate is produced for a long period of time. Therefore, in order to improve the yield in the thermal decomposition of urethane carboxylic acid, for example, a chemical method such as the use of a special catalyst (refer to Patent Document 9, Patent Document 10) or a catalyst combined with an inert solvent (refer to Patent Document (1)) is disclosed. In the patent document 12, as a method for producing diisocyanate diacetate, there is disclosed a method of: in the presence of a dibasic toluene used as a solvent, and a toluene-reducing methyl vinegar and The thermal decomposition of '# /, methylene monoethyl carbamate in the presence of diphenyl dichloroheptyl complex. However, for the preparation of starting components, and for isolation, and purification of solvent and catalyst mixtures And any recycling does not disclose the economic efficiency of the method in detail. . . ' According to the method of Φ M α of Patent Document 13, the urethane can be used in the carbon stream without using a catalyst. In the chemical bed, the valley is easily decomposed into isocyanate and alcohol. According to the patent vinegar, for example, hexamethylene dialkylaminocarb, hydrazine 3 carbon, copper, brass, steel, chromium, cobalt Or quartz's Luo rules* In the presence of a gas permeable packaging material or in the absence of J3J506.doc 200948759, it is decomposed in the gas phase at a temperature of more than 3 Torr (TC) to form a diisocyanate hexane. According to Patent Document I4 The method is carried out in the presence of a gas image and/or a gas-form donor. However, the method cannot achieve a yield of more than 90% of diisocyanate. The reason is that the decomposition product is partially The bond is then ligated to form a urethane bond. Therefore, the purification of the diiso-acid hexamethylene vinegar by the steaming plant often causes the need to increase: rate = increase.

According to the disclosure of Patent Document 15, it is disclosed that "the lower case: at a lower temperature and at a lower temperature" under the reduced pressure 'in the presence or absence of a catalyst and/or a stabilizer' may be used without solvent A good yield decomposes the monoaminoformic acid vinegar. The decomposition products (monoisocyanate and alcohol) are removed from the boiling reaction mixture by evaporation, and are separately captured by condensation. The general form reveals a method of removing a portion of the reaction mixture to the outside of the system in order to remove by-products formed in thermal decomposition. Therefore, the by-product can be removed from the bottom of the reaction H, but remains attached to the above-mentioned fixation reaction| The problem of the wall surface has not solved the problem of long-term operation. Moreover, there is no disclosure about the industrial use of the removed reaction mixture (containing a large amount of useful components). According to the disclosure of Patent Document 16, fat Thermal decomposition of a family, alicyclic or aromatic polyurethane, at 150~35〇. 〇 and 〇〇〇1~2〇bar in the presence of an inert solvent, as a catalyst and auxiliary Gas The by-product formed in the presence or absence of hydrogen, an organic acid vapor, an alkylating agent or an organotin vapor can be continuously removed from the reactor, for example, 131506.doc 200948759, together with the reaction solution, At the same time, a corresponding amount of the new solvent or the recovered solvent is added. The disadvantage of this method is that, for example, the use of a refluxing solvent reduces the space-time yield of the polyisophthalic acid brewing' and, for example, requires a large amount of energy including solvent recovery. Furthermore, the auxiliaries used are volatile under the reaction conditions and can contaminate the decomposition products. Moreover, the amount of the residual portion of the polyisocyanate formed is relatively high, and the reliability of the economic efficiency and industrial method is high. According to the disclosure of Patent Document 17, there is disclosed a method of supplying a urethane carboxylic acid, such as an alicyclic diamine group, supplied along the inner surface of a tubular reactor in a liquid form in the presence of a high boiling point solvent. Formic acid vinegar 5_(ethoxylamino)-1-(ethoxymethylaminoguanidinomethylcyclohexane) is continuously thermally decomposed. The method has the production of (cyclic) aliphatic The isocyanic acid has a low yield and low selectivity. In addition, there is no disclosure about the continuity of the recovery of urethane with re-bonded or partially decomposed. The subsequent treatment with a solvent containing by-products and a catalyst is not described. According to the disclosure of Patent Document 18, there is disclosed a recycling method by converting a corresponding diamine into a diamine phthalate, and The urethane is thermally decomposed to produce a (cyclo)aliphatic diisocyanate. The process recycles the product from the carbamate decomposition step to the urethane by reacting with the oxime. The step of reducing the yield is minimized. The by-product which cannot be recycled is removed by separating the mixture of the urethane formation product, in which case, the valueless residue The composition is produced as a bottom product, and the difluorocarbamate has a lower boiling point 131,506.doc 200948759. All components are removed from the top of the column. However, this method has the disadvantage of using a large amount of energy. Therefore, the reason is that it is necessary to evaporate all the dicarbamate in the presence of a catalyst, and it is necessary to evaporate the dicarbamate at a certain temperature within the range of the decomposition temperature of the amino phthalate. . The isocyanate group formed in the useful product is often reacted with the urethane group of the residual component to form a by-product having a relatively high molecular weight which reduces the yield. According to the disclosure of Patent Document 19, there is disclosed a method of partially removing a valuable by-product from the system before performing thermal decomposition of the polyamino phthalate. The disadvantage of this method is that a part of the by-product removed to the outside of the system contains a polyurethane, and thus the yield of the isocyanate is sometimes lowered. Also, the thermal decomposition of the reaction mixture containing unreacted polyurethane, high-boiling polymer and other reusable by-products obtained in the thermal decomposition step of the polyurethane is not thermally decomposed. The ingredients are separated, continuously removed from the thermal decomposition unit and recycled directly or as needed to react with the alcohol and recycled to the ureic acid brewing step 'attempting to increase the yield of isocyanate, but sometimes in the urethane step The high-boiling polymer that is recycled to the system is precipitated in the urethanization reactor and slowly accumulates on the wall of the reactor, preventing long-term operation. Further, according to the disclosure of Patent Document 20, the reaction medium containing the urethane is heated to form a two-phase mixture having a gas capacity of more than 5% by weight, and the gas phase is continuously discharged from the reactor, and the liquid is self-contained. The method of continuously discharging the reactor 'is produced by continuous thermal cracking of the urethane to produce an isocyanate. In this method, the unthermally decomposed components of the reaction mixture containing unreacted polyurethane, high boiling point 131506.doc 200948759 polymer and other reusable value-added by-products are separated and autothermally decomposed. The apparatus is continuously removed, and is directly or optionally reacted with an alcohol, and recycled to the amino phthalate esterification step in an attempt to increase the yield of isocyanate Sa, but similarly to the above method, sometimes the amino phthalate is used. The high-boiling oligomers recycled to the system in the crystallization step are precipitated in the urethanization reactor and slowly accumulate on the wall of the reactor, hindering long-term operation.专利 Patent Document 2 1 discloses a method in which methyl carbamate obtained by reacting dimethyl carbonate with an amine in the presence of a basic catalyst is evaporated, introduced into a hot knife reactor, and thermally decomposed. The disadvantage of this method is that the unvaporized component is removed from the bottom of the evaporator when the amino citrate is evaporated, but the methyl methacrylate is contained in the removed component, so that the yield of the isocyanate is lowered. Further, since the vapor of methyl carbazate is transported at a high temperature, there is a tendency to easily cause a thermal modification reaction of methyl carbazate. [Patent Document 1] U.S. Patent No. 4,497,963, the disclosure of which is incorporated herein by reference. [Patent Document 2] U.S. Patent No. 4,429, 197, [Patent Document 3] U.S. Patent No. 4,388,238 [Patent Document 4] U.S. Patent No. 44305 05 [Patent Document 5] U.S. Patent No. 4, 480, 811 [Patent Document 6] U.S. Patent No. 4, 596, 678 [Patent Document 7] U.S. Patent No. 4,596, 679 [Japanese Patent Application No. 8] European Patent Application Publication No. 32-235 Patent Document 9] US Pat. No. 2692275 [Patent Document 10] US Pat. No. 3,374,941, US Pat. No. 3, </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> [Patent Document 14] U.S. Patent No. 4,613,466 [Patent Document 15] U.S. Patent No. 4,384,033 [Patent Document 16] U.S. Patent No. 4,388,246 [Patent Document 17] U.S. Patent No. 46,925 [Patent Document 18] European Patent Application No. 0354443 (Patent Document 19) US Pat. No. 5,380, 605, [Patent Document 20] Japanese Patent No. 3238201 [Patent Document 21] U.S. Patent Application Publication No. 5315034 [Non-Patent Document 1] Berchte der Deutechen Chemischen

Gesellschaft 'Volume 3, page 653, 1870 [Non-Patent Document 2] Journal of American Chemical Society, Vol. 81, p. 2138, 1959 I [Summary of the Invention] [Problems to be Solved by the Invention] As described above, Various studies have been carried out on the method of producing isocyanate without using toxic phosgene. However, the current situation is that there is a problem that it is difficult to continuously manufacture for a long period of time due to the formation of high-boiling by-products or the adhesion of the high-boiling by-products to the reactor, which has hardly been industrially implemented. SUMMARY OF THE INVENTION An object of the present invention is to provide a method for producing an isocyanate stably for a long period of time without any problems found in the prior art when an isocyanate is produced without using phosgene. 131506.doc -13· 200948759 [Technical means for solving the problem] The inventors of the present invention conducted an effort to study the above-mentioned trajectory of θ, and as a result, they were surprised to find that the urethane was subjected to 埶a L焉. ^ ^ In the method of producing a isocyanate by a hot knife solution, according to the self-heating decomposition, the liquid phase component recovered from the bottom of the reactor is supplied to the upper part of the thermal decomposition reactor #, G ^ m method. It does not cause the by-products to adhere to the reactor or block the reactor, and can be long and clear. Continuously operating for a long period of time, thereby completing the present invention, which is provided by the present invention, (1) a method for producing a hetero-subtraction (four), which is a method for producing an isocyanate by subjecting an amine to a decomposition reaction, and comprising the following steps: a step of recovering the thermal decomposition reaction of the thermal decomposition reaction and recovering the low-boiling component as a gas phase component; and recovering the liquid phase component containing the aminocarboxylic acid g from the bottom of the thermal decomposition reactor And a step of supplying a part or all of the liquid phase component to the upper portion of the thermal decomposition reactor. [2] The production method according to [1], wherein the urethane is supplied to the thermal decomposition reactor in a temperature range of (9) 艽 to 丨 8 〇 C. [3] The production method according to the above [1] or [2] wherein the amino phthalic acid ester is supplied as a liquid to the thermal decomposition reactor. [4] The production method according to any one of [1] to [3] wherein the amino acid S is an amino carboxylic acid ester produced by reacting a carbonate with an amine compound. [5] The production method according to the above [4], wherein the reaction for producing the amino phthalate ester is 131506.doc -14-200948759, and the thermal decomposition reactor may be different from the same. The reaction and the thermal decomposition reactor are selected from at least one reactor selected from the group consisting of a column reactor and a tank reactor. [6] The production method according to any one of [1] to [5] wherein the thermal decomposition reaction is carried out by a multi-stage distillation column selected from an evaporation can, a &lt;+&quot; A wind evaporator composed of a thin film evaporator and a falling film evaporator (a reactor composed of at least one reactor in the group).

[7] The production method according to any one of [1] to [6], wherein the reaction is carried out in a liquid phase. The method of any one of the above [4] to [7], wherein a part or all of the hydroxyl group is separated from the mixture containing the silkworm (4) produced by reacting the carbonic acid and the amine compound. The compound and/or a part or all of the carbonate is supplied to the thermal decomposition reaction apparatus. [9] The production method according to the item [8], wherein the separation is carried out by steaming separation. The distillation separation is carried out at 18 (TC or less).

[10] The production method according to any one of [1] to [9] wherein a part or all of the liquid phase component recovered from the bottom of the thermal decomposition reactor is in a temperature range of 5 & > c ～ 180 C Inside, it is supplied to the upper portion of the thermal decomposition reactor. The production method according to any one of the items [4] to [10] wherein, in comparison with the amine constituting the amine compound, i times or more of the carbonate is used in stoichiometric ratio. The production method according to any one of the preceding items, wherein the step of washing the high-boiling by-product attached to the thermal decomposition reactor with an acid is further included. [13] The method of producing the item [12], wherein the acid is an aromatic carbamide compound. [14] The compound represented by the following formula (5) in the production method # according to any one of the items [4] to [13], wherein the compound is represented by the following formula (5), 〇R1, and R1 (5&gt; Wherein: _ Rl represents an aliphatic group having a carbon number of 1 to 12 or an aromatic group having a carbon number of 6 to 12). [15] The method of producing the above [14], wherein the carbonic acid@ [16] The method of the present invention, wherein the metal atom is selected from the group consisting of iron, recorded, drilled, zinc, tin, copper, and titanium. [17] The method for producing a metal according to any one of [14] to [16], wherein the carbonated vinegar® has an aliphatic group or a carbon number of 5 to 7 carbon atoms. The method of any one of the above [4] to [17] wherein the amine compound is a compound represented by the following formula (6), [Chem. 4]

(6) (wherein: the fat R2 of the atom of oxygen having a carbon number of 1 to 20 is selected from the group consisting of an aromatic group selected from the group consisting of carbon, 131506.doc -16·200948759 and a carbon number of 6-20 One of the groups has an atomic valence equal to η, and η is an integer of 2 to 1 )). (9) The method for producing the above, wherein the amine compound is a diamine compound wherein η is 2 in the compound represented by the formula (6). [2] The production method according to any one of the items (1) to [19], wherein a low-boiling component which is produced by a thermal decomposition reaction and recovered as a gas phase component is supplied as a gas component to the distillation column. In the distillation column, a hydroxy compound derived from an amino phthalic acid ester is separated from an isocyanate derived from a urethane from the low boiling component. [21] The method according to any one of [1] to [20] wherein the low-boiling component formed by the thermal decomposition reaction and recovered as a gas component is separately recovered from the thin film evaporator. A hydroxy compound of a urethane and an isocyanate derived from an amino phthalate. [22] The production method according to any one of the preceding paragraph, wherein the isocyanate is separated from the liquid phase component by distillation. [23] The method of any one of [14] to [22] wherein the carbonic acid is enriched in the aliphatic group of the formula (5) wherein the carbon number of the R1 is 丨~丨2, Manufactured by the following steps (1) and (2), step (1): 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 Step (2): The step of separating the reaction mixture to obtain a dialkyl carbonate and a residual liquid. [24] The production method according to any one of [14] to [22] wherein the carbonic acid 131506.doc 17 200948759 is an aromatic group having a carbon number of 6 to i2 in the formula (5). Using the method of the following step (3) in addition to the above steps (1) and (2), the step (3): separating the carbonic acid base and the fragrance separated in the step (2) The group hydroxy compound A is reacted to obtain a diaryl carbonate, and the by-produced alcohol is recovered. [25] The method according to the above [23] or [24] wherein the carbonated vinegar comprises the following steps (4) and steps in addition to the step (1) and the step (2), or the steps (1) to (3). (5) The step of producing a carbonate, (4) ... reacting the residual liquid obtained in the step (7) with an alcohol to form an organic kick compound having a tin-oxygen-carbon bond and water, and self-reacting the step of the water; Step (7): a step of recycling the organotin compound having a kicking oxygen-carbon bond obtained in the step (4) as an organotin compound having an Ioxycarbon bond in the step (1).

[26] The production method according to the above [25], wherein the alcohol recovered in the step (7) is reused as the alcohol of the step (4). U7. The production method according to the above [24] or [25] wherein, when the base compound is an alcohol, the alcohol is used as the alcohol of the step (4), and when the (4) group compound is an aromatic warp compound, as the step (3) ) Aroma (4) Base A is used. The method for producing the amine group according to any one of the above [8] to [27], wherein the carbonate is reused as a carbonate. [29] The production method according to any one of [1] to [28] 131506.doc -18- 200948759 The thermal decomposition reaction of the acid ester is carried out in the absence of a solvent. [3] The production method according to any one of [4] to [29] wherein the amine compound is supplied to the reactor for reacting the caproamine compound to be reacted in a liquid state. The manufacturing method of the above item [4] to _zhong--, "the intermediate amine compound is supplied to the reactor for reacting the carbonated acid with the amine compound, and is used as a mixture with an alcohol, water, or carbonate. And proceed. [Effects of the Invention] According to the present invention, isocyanate can be produced without using phosgene, and can be continuously operated for a long period of time. [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 method for producing an isocyanate according to the present embodiment is a method for producing an isocyanate by thermally decomposing a urethane produced by reacting a carbonate with an amine compound in the absence of a solvent, and comprising the steps of: a thermal decomposition reaction thermal decomposition reactor for recovering a low boiling component as a gas phase component; a step of recovering a liquid phase component containing a urethane from a bottom of the thermal decomposition reactor; and the liquid phase The step of supplying 5 minutes or all of the components to the upper portion of the thermal decomposition reactor. &lt;Amino carboxylic acid vinegar&gt; The urethane used in the method for producing an isocyanate of the present embodiment is not particularly limited, and it is preferably used in the following formula (7): 131506.doc -19 · The urethane of 200948759. -Jh ? \ R3 彳NC-0 - is called \ /n (7) (wherein R3 represents an aliphatic group selected from carbon atoms containing 1 to 20 carbon atoms selected from carbon or oxygen; a group of a group consisting of an aromatic group having a carbon number of 6 to 2 G and having an atomic valence equal to η, and 瘳R4 representing a magnetic olefin containing an atom selected from carbon and oxygen, *. The aliphatic group having a rolling number of 1 to 20, an aromatic group having a carbon number of 6 to 20, and η is an integer of 1 to 1 Å). In the above formula (7), η is preferably a number selected from an integer of 2 or more, and more preferably a polycarbamate having η of 2. Examples of R3 in the formula (7) include a linear hydrocarbon group such as a methylene group, a dimethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group or an octadecyl group. Unsubstituted alicyclic hydrocarbon group such as cyclopentane, cyclohexane, cycloheptane, cyclooctane, bis(cyclohexyl)alkane; indenylcyclopentane, ethylcyclopentane, methyl ring Ether (each isomer), ethylcyclohexan (each isomer), propylcyclohexane (each isomer), butylcyclohexane (each isomer), pentylcyclohexane (each isomer), alkyl-substituted cyclohexyl or the like such as hexylcyclohexane (each isomer); dimethylcyclohexane (each isomer), diethylcyclohexane (each isomer) a dialkyl-substituted cyclohexanyl such as dibutylcyclohexane (each isomer); 1,5,5-trimethylcyclohexane, us triethylcyclohexane, 15 5 tripropylcyclohexane Burning (each isomer), 1,5,5-tributylcyclohexane (each isomer), etc., three-burning 13t506.doc -20· 200948759 base-substituted cyclohexane; toluene, ethylbenzene, propyl Monoalkyl substituted benzene such as benzene; diphenylene, diethylbenzene, dipropylbenzene, etc. A substituted phenyl group; diphenyl alkanes, and aromatic hydrocarbons such stupid. Among them, hexamethylene, phenylene, diphenylmethane, toluene, cyclohexane, xylene, methylcyclohexane, isophorone, and dicyclohexylmethylalkyl are preferably used. R4 which is represented by the above formula (7) may, for example, be methyl, ethyl, propyl (each isomer), butyl (each isomer), pentyl (each isomer), hexyl (various) Structure), heptyl (each isomer), octyl (each isomer), thiol (each isomer), thiol (each isomer), undecyl (each isomer) , dodecyl (each isomer), dodecyl (each isomer), tetradecyl (each isomer), pentadecyl (each isomer), cetyl ( Each isomer), heptadecyl (each isomer), octadecyl (each isomer), pentadecyl (each isomer, eicosyl (each isomer), etc. a cycloalkyl group such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclodecyl group or a cyclodecyl group; a methoxymethyl group, a methoxyethyl group (each isomer), a methoxy group; Propyl (each isomer), decyloxybutyl (each isomer), methoxypentyl (each isomer), methoxyhexyl (each isomer), methoxyheptyl ( Each isomer), methoxyoctyl (each isomer), methoxy fluorenyl (each , methoxy fluorenyl (each isomer), methoxy eleven base (each isomer), methoxy dodecyl (each isomer), methoxy tridecyl (each isomer), methoxytetradecyl (each isomer), methoxy pentene, aryl group (each isomer), methoxy hexadecyl group (each isomer), Methoxy seventeen bases (each isomer), methoxy ten-membered base (each isomer), methoxy 19-mercapto (isomer), ethoxymethyl, ethoxy Ethyl ethyl (each isomer), ethoxy propyl (each isomer), ethoxybutyl (each isomer), B 131506.doc -21 - 200948759 oxypentyl isomer) Ethoxyhexyl alpha isomers (each isomer), ethoxyoctyl (each isomer), ethoxylated thiol (: isomer), ethoxylated thiol (variety) Structure), ethoxyl-homosystem (each isomer), ethoxydodecyl group (each isomer), ethoxylated tridecyl group (each isomer), 6-oxyl Tetrasyl 9 (each isomer), [oxyl fifteen (each isomer), ethoxy hexadecane (isoisomer) ), ethoxy heptadecyl (each isomer), ethoxy octadecyl (each isomer), propoxymethyl (each isomer), propoxyethyl (variety) Structure), propoxypropyl (: isomer), propoxy butyl (each isomer), @oxypentyl (each isomer), propoxyhexyl (isomer) , propoxyheptyl (each isomer), propoxyoctyl (each isomer), propoxy fluorenyl (each isomer), propoxy fluorenyl (each isomer), C Oledecyl (each isomer), propoxydodecyl (each isomer), propoxytridecyl (each isomer), propoxytetradecyl (each Isomer), propoxypentadecyl (each isomer), propoxy hexadecyl (each isomer), propoxy heptadecyl (each isomer), butoxy A 2 φ (each isomer), butoxyethyl (each isomer), butoxypropyl (each isomer), butoxy butyl (each isomer), butoxy pentane Base (each isomer, butyoxyhexyl (each isomer), butoxyheptyl (each isomer), butoxy (each isomer), butoxy thiol (each isomer), butoxy thiol (each isomer), butoxy undecyl (each isomer), butoxy 12 Alkyl (each isomer), butoxytridecyl (each isomer), butoxytetradecyl (each isomer), butoxypentadecyl (each isomer) , butoxy hexadecyl (each isomer), pentoxymethyl (each isomer), pentoxyethyl (each isomer), pentoxypropyl (each isomer) , pentyloxybutyl (each isomer), 131506.doc • 22- 200948759 pentyloxypentyl (each isomer), pentyloxyhexyl (each isomer), pentyloxyheptyl (each Isomers), pentoxyoctyl (each isomer), pentyloxy fluorenyl (each isomer), pentyloxy fluorenyl (each isomer), pentyl undecyl (each Isomer), pentyl t-dozenyl (each isomer), &amp;oxytridecyl (each isomer) pentyl octadecyl (each isomer), pentyloxy Pentadecyl (each isomer) hexyloxymethyl (each isomer), hexyloxyethyl (each Isomers), hexyloxypropyl (each isomer), hexyloxybutyl (each isomer), hexyloxypentyl (each isomer) 'hexyloxyhexyl (each isomer) ), hexyloxyheptyl (each isomer), hexyloxyoctyl (each isomer), hexyloxyindenyl (each isomer), hexyloxyindenyl (each isomer), Hexyloxy-11 (each isomer), hexyloxy 12-6 (each isomer), [oxytridecyl (each isomer), hexyloxy 14-yard ( Each isomer), heptyloxymethyl, heptyloxyethyl (each isomer), propylpropyl (each isomer), heptoxybutyl (isoisomer) heptoxypentane Base (each isomer), heptyloxyhexyl (each isomer), heptyloxyheptyl (each isomer), heptoxyoctyl (each isomer), heptyloxycarbonyl group ( Each isomer), heptyloxyindenyl (each isomer), heptyloxy eleven base (each isomer), heptyloxy-12 (iso isomer), heptyloxy Trialkyl (each isomer), octyloxymethyl, octyloxyethyl (each isomer), octyloxypropyl ( Each isomer), octyloxybutyl (each isomer), octyloxypentyl (each isomer), octyloxyhexyl (each isomer), octyloxyheptyl (isoisomer) , octyloxyoctyl (each isomer), +oxycarbonyl (each isomer), octyloxy thiol (each isomer), octyloxy eleven (isoamyl) , octyloxydodecyl (each isomer), decyloxymethyl (each isomer), decyloxyethyl (each isomer), methoxy propyl (isomeric) )131506.doc •23· 200948759 == isomer), decyloxypentyl (each isomer), decyloxy: each isomer), decyloxyheptyl (isomeric) , oxime octyl (each isomer), fluorenyl thiol d, private, technical storm (each isomer), decyloxy thiol (isomer),

十一 十一 院 院 院 ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( Butyl (each isomer), decyloxypentyl (each isomer), decyloxyhexyl (isoisomer), decyloxyheptyl (each isomer), decyloxy (each isomer), ^oxyindenyl (each isomer), decyloxy group (each isomer), undecyloxymethyl, deca- alkoxyethyl (isomeric , undecyloxypropyl (each isomer), undecyloxybutyl (each isomer), deca- alkoxypentyl (each isomer), undecyloxy Hexyl (each isomer), undecyloxyheptyl (each isomer), undecyloxyoctyl (each isomer), undecyloxyindenyl (each isomer), Dodecyloxymethyl (each isomer), dodecyloxyethyl (each isomer), dodecyloxypropyl (each isomer), dodecyloxybutyl ( Each isomer), dodecyloxypentyl (each isomer), dodecyloxyhexyl (each isomer), dodecyloxy Heptyl (each isomer), dodecyloxyoctyl (each isomer), tridecyloxymethyl (each isomer), tridecyloxyethyl (isomeric , tridecyloxypropyl (each isomer), tridecyloxybutyl (each isomer), tridecyloxypentyl (each isomer), dodecyloxy Hexyl (each isomer), tridecanthoxyheptyl (each isomer), tetradecyloxymethyl (each isomer), tetradecyloxyethyl (each isomer), Tetradecanyloxypropyl (each isomer), tetradecyloxybutyl (each isomer), tetradecyloxypentyl (each isomer), tetradecyloxyhexyl (each Isomer), pentadecyloxymethyl, pentadecyloxyethyl (each 131506.doc -24· 200948759 (each isomer, oxypropyl (isomer), fifteen courtyard oxygen Phenyl butyl = =, / pentoxide pentyl (each isomer), hexadecane oxygen = structure, hexadecanoloxyethyl (isomer), hexadecane = Isomer), hexadecyloxybutyl (each isomer), 17-oxygen 2, and 17-oxide oxyethyl Structure), heptadecyloxypropyl (each isomer), octadecyloxymethyl (each isomer), octadecyloxyethyl (each isomer), etc. Base 'phenyl, methyl-phenyl (each isomer),

Each (tetra)phenyl (each isomer), butylphenyl (each isomer), pentylphenyl (each isomer), hexyl phenyl (each isomer), heptyl-phenyl (each isomer), octyl phenyl (each isomer), decyl phenyl (each isomer), decyl-phenyl (each isomer), dodecyl phenyl ( Each isomer), phenyl·phenyl (each isomer), phenoxy-phenyl (each isomer), cumyl-phenyl (each isomer), dimethyl-benzene Base (each isomer), diethyl phenyl (each isomer), dipropyl phenyl (each isomer), dibutyl-styl (isomer), dimercapto - stupid (each isomer), dihexyl-phenyl (each isomer), diheptyl-phenyl (each isomer), diphenyl stupyl (each isomer), diphenyl oxygen Base-phenyl (each isomer), methyl-ethyl-phenyl (negative), mercapto-propyl-phenyl (each isomer), mercapto-butyl-styl (each Isomers), methyl-pentyl-phenyl (each isomer), methyl-hexyl-styl (each isomer), methyl-heptyl-phenyl ( Isomers), methyl-octyl stupyl (each isomer), methyl-mercapto-phenyl (each isomer), methyl-mercapto-styl (isomer), hydrazine Base-dodecanyl-phenyl (each isomer), methyl-phenyl group, base (each isomer), mercapto-phenoxy-phenyl (each isomer), methyl Propyl phenyl-phenyl (each isomer), ethyl-propyl-phenyl (each isomer), 13I506.doc •25- 200948759 ethyl-butyl-phenyl (isomers), Ethyl-pentyl-phenyl (each isomer), ethyl-hexyl-phenyl (each isomer), ethyl-heptyl-phenyl (each isomer), ethyl-octyl- Phenyl (each isomer), ethyl-mercapto-phenyl (each isomer), ethyl-fluorenyl-benton (each isomer), ethyl-dodecanyl-phenyl ( Each isomer), ethyl-phenyl-phenyl (each isomer), ethyl-phenoxy-phenyl (each isomer), ethyl-isopropylphenyl-phenyl (variety) Structure), propyl butyl phenyl (each isomer), propyl-pentyl-phenyl (each isomer), propyl-hexyl-phenyl (each isomer), propyl-g Base-benzene (each isomer), propyl-octylphenyl® (each isomer), propyl-mercapto-phenyl (each isomer), propyl-fluorenyl-phenyl (each isomer) ), propyl-phenyl-phenyl (each isomer), propyl-phenylphenylphenyl (each isomer), butyl-pentyl-phenyl (each isomer), butylhexyl Phenyl (each isomer), butyl-heptyl-phenyl (each isomer), butyl-octyl-phenyl (each isomer), butyl-mercapto-phenyl (variety) Structure), butyl nonylphenyl (each isomer), butyl-phenyl-phenyl (each isomer), butylphenoxy-phenyl (each isomer), pentyl- Hexyl-phenyl (each isomer), pentyl-heptyl ❹ ❹ = group (each isomer), pentyl-octyl-phenyl (each isomer), pentyl-fluorenyl. phenyl (each isomer), pentyl-phenyl-phenyl (each isomer), pentyl-phenoxy-phenyl (each isomer), hexyl-heptyl-phenyl (each isomer) ), hexyloctyl-phenyl (each isomer), hexyl-phenyl-phenyl (each isomer), hexylphenoxy-phenyl (each isomer), tridecyl-phenyl ( each Isomers), triethyl-phenyl (each isomer), tripropyl-phenyl (each isomer), tributyl-phenyl (each isomer), dimethyl-ethyl .Phenyl (each isomer), dimethyl-propyl-phenyl (each isomer), dimethyl.butyl-phenyl (each isomer), dimethyl-pentyl-benzene Base (each isomer), dimethyl-hexyl-phenyl (each isomer), two 131506.doc •26·200948759 ❹ 甲基 methyl-heptyl-phenyl (each isomer), dimethyl -O-octyl-phenyl (each isomer), monodecyl-fluorenyl-phenyl (each isomer), dimethyl nonylphenyl (each isomer), dimethyl-dome Alkyl-styl (each isomer), dimethyl-phenyl-phenyl (each isomer), dimethyl-phenoxy-phenyl (each isomer), dimethyl-iso Propyl-phenyl (each isomer), ethylmethylphenyl (each isomer), monoethyl-propyl-phenyl (each isomer), diethyl-butyl- Phenyl (each isomer), diethyl-pentyl-phenyl (each isomer), diethylhexyl-phenyl (each isomer), diethyl-heptyl-phenyl (each Isomers), diethyl-octyl-phenyl (each isomer), diethyl-nonylphenyl (each isomer of diethyl-mercapto-phenyl (each isomer) , diethyl-phenylphenyl (each isomer)-ethyl-p-oxy-phenyl (each isomer), diethyl-cumylphenyl-phenyl (each isomer), Dipropyl-methyl-phenyl (each isomer), dipropyl-ethyl-phenyl (each isomer), dipropyl-butylphenyl (each isomer) Pentyl-phenyl (each isomer), dipropyl-hexyl phenyl (each isomer), monopropyl-heptyl-phenyl (each isomer), dipropyl phenyl phenyl (each isomer), dipropyl-phenoxy-phenyl (each isomer), dibutylsulfonyl-phenyl (each isomer), dibutyl-ethyl-phenyl (each Isomers), dibutyl-propyl-phenyl (each isomer), dibutyl-pentylphenyl (each isomer), dibutyl-hexyl-phenyl (each isomer) , dibutyl-phenyl-phenyl (each isomer), dibutyl-phenoxy-phenyl (each isomer), dipentyl-methyl-phenyl (each isomer), two -ethyl-phenyl (each isomer), dipentylpropyl-phenyl (each isomer), dipentyl-butyl-phenyl (each isomer), dihexyl_methyl -phenyl (each isomer), dihexyl-ethyl-phenyl (each isomer, methyl-ethyl-propyl-phenyl (each isomer), methyl-ethylbutylphenyl ( Each 131506.doc 27- 200948759 ❹ 异构 isomer), methyl-ethyl-pentyl-phenyl (each isomer), mercaptoethylhexyl-phenyl (isomer), thiol- Ethyl-heptyl-styl (each isomer), mercapto-ethyl-octyl-phenyl (each isomer), methyl-ethyl-nonylphenyl (each isomer), Methyl-ethyl-fluorenyl-phenyl (each isomer), methyl-ethyl-phenoxy-phenyl (each isomer), methyl-ethyl-cumylphenyl-phenyl (each isomer), methyl-propyl-butyl-phenyl (each isomer), methyl-propyl fluorenyl _ phenyl (each isomer), methyl propyl-hexyl _ Phenyl (each isomer), methyl-propyl-heptyl-phenyl (each isomer), methyl-propyl-octyl-phenyl (each isomer), methyl-propyl ·Ren Base-phenyl (each isomer), f-propyl propyl sulfhydryl _ phenyl (each isomer), methyl-propyl-phenoxy-phenyl (each isomer), methyl-propyl -Phenylphenyl-phenyl (each isomer), methyl-butyl-pentylphenyl (each isomer), methyl-butyl-hexyl-phenyl (each isomer), Methyl-butyl-heptyl-phenyl (each isomer), methyl-butyl-octylphenyl (each isomer), methyl-butyl-phenoxy-phenyl (variety) Structure), methyl-butyl-cumenyl-phenyl (each isomer), methyl-pentyl-hexyl-phenyl (each isomer '), methyl-pentyl-heptyl Phenyl (each isomer), methyl-pentyl-octyl-phenyl (each isomer) methyl*pentyl-benyloxy-phenyl (each isomer), mercapto-hexyl -heptyl-phenyl (each isomer), ethyl-propyl-butyl-phenyl (each isomer), ethyl-propyl-pentyl-phenyl (each isomer), B Propylhexyl-phenyl (each isomer), ethyl-propyl-heptyl-phenyl (each isomer), ethyl-propyl-octyl-phenyl (each isomer), Ethyl-propyl-fluorenyl-stupyl , ethyl-propyl-phenoxy-phenyl (each isomer), ethyl-propyl cumene-phenyl (each isomer), ethyl butyl-pentyl _Phenyl (each isomer), ethyl-butylhexyl-phenyl (each isomer), ethyl-butylheptylphenyl I31506.doc -28 - 200948759 (each isomer), ethyl -butyl-octyl-phenyl (each isomer), ethylbutyl-phenoxy-phenyl (each isomer), ethyl-pentyl-hexyl-phenyl (each isomer) , ethyl-pentyl-heptyl-phenyl (each isomer), ethyl-pentyl-phenoxy-phenyl (each isomer), propyl-butyl-phenyl (isoisomer) , propyl butyl-pentyl-phenyl (each isomer), propyl butyl hexyl phenyl (each isomer), propyl-butyl-heptyl-phenyl (variety) Structure), propyl-butylphenoxy-phenyl (each isomer), propyl-pentyl-hexyl-phenyl (each isomer), propyl-pentyl-phenoxy- An aromatic group such as a phenyl group (each isomer). It is preferable that the alkyl group constituting the group is an alkyl group selected from the number of integers of 5 to ι 2 or an aryl group constituting the number of carbon atoms of the group selected from an integer of 6 to 12 More preferably, the pentyl group (each isomer), the hexyl group (each isomer), the heptyl group (each isomer), the octyl group (each isomer), the number of carbon atoms of the group is selected from An alkyl group having an integer number of 5 to 7, a phenyl group, a methylphenyl group (each isomer), or the like, and the number of carbon atoms of the group is selected from an integer of 5 to 7 and the number of anatom atoms is In the case of a base or an aryl group of 4 or less, sometimes the 'anthracene point of the amine group 曰 曰 不 is not enough to be in the thermal decomposition reaction conditions of the following amino carboxylic acid vinegar, the urethane will It is distilled off in the gas phase, and it is difficult to separate it from the odorous acid or the like. Further, when the number of carbon atoms is 8 or more, the difference between the boiling point of the hydroxy compound formed in the thermal decomposition reaction and the boiling point of the isocyanate is small, and separation is inhibited. As such a polyalkyl carbamic acid ester, for example, n, n, hexyldiyl bis-amino phthalic acid dipentyl ester (each isomer), N, N, - hexanediyl _ double _Dihexyl carbazate (each isomer), hydrazine, hydrazine, hexyldiyl bis-amino phthalic acid dihept vinegar (each isomer), dipentyl-4,4'-adenine Base-dicyclohexylaminocarboxylic acid brewing 131506.doc •29- 200948759 (each isomer), dihexyl-4,4′-methylene-dicyclohexylcarbamate (each isomer), Diheptyl_4,4'-methylene-dicyclohexylamino decanoate (each isomer), 3-(pentyloxycarbonylamino-indenyl)_3,5,5-trimethyl Ethyl cyclohexylaminocarbamate (each isomer), 3-(hexyloxycarbonylamino-methyl)-3,5,5-trimethylcyclohexylcarbamate hexyl ester (isomers) , 3-(heptyloxycarbonylamino-methyl)-3,5,5-trimethylcyclohexylcarbamic acid heptyl ester (each isomer), toluene-dicarbamic acid dipentyl ester (each Isomers), toluene-dihexyl dicarboxylate (each isomer), diheptyl toluene-diamine phthalate (each isomer), ^ Ν, Ν'·(4,4'- Yttrium diphenyl )-diamyldiamine decanoate, N,N,-(4,4,-methylene-diphenyl)-dicarbamic acid dihexyl ester, N,N,-(4,4,- Amino decanoic acid ester such as methylene-diphenyl)-diaminocarbamate, N,N,-hexanediyl-bis-amino phthalic acid diphenyl ester, N, N, - Dikis-bis-aminocarbamic acid di(methylphenyl) ester (each isomer), diphenyl-4,4·-methylene-dicyclohexylaminocarboxylic acid, bis(methylphenyl) -4,4··methylene-dicyclohexylcarbamate (each isomer), 3-(phenoxyaminoamino-methyl)_3,5,5-trimethylcyclo Hexylamine phenyl carbazate (each isomer), 3-((methylphenoxy)carbonylamino-indenyl)-3,5,5-trimethylcyclohexylaminocarboxylic acid (methylbenzene) Ester (each isomer), methyl-monocarbamic acid diphenyl δ (each isomer), toluene-diaminocarbamic acid di(methylphenyl) ester (each isomer), Ν,Ν'-(4,4'-methylene_diphenyl)-diphenyl diuret, hydrazine, Ν'-(4,4'-methylenediphenyl)-diamine An aryl carbamate such as bis(methylphenyl) carboxylate or the like. The amino phthalic acid vinegar can be produced by a well-known method, for example, by reacting an amine compound with carbon monoxide, oxygen, and an aliphatic alcohol or an aromatic hydroxy compound to produce an amine bismuth vinegar. Compound 131506.doc • 30- 200948759 A method for producing a urethane by reacting a substance, a gland with an aliphatic alcohol or an aromatic radical compound, or a method of reacting a carbonated acid with an amine compound to produce an aminocarboxylic acid. The method is preferably a production method in which a carbonated acetal is reacted with an amine compound. As the carbonate, a carbonate represented by the following formula (8) can be used. 〇 R5, human R5(8) φ (wherein R5 represents a linear or branched aliphatic group having (4) an aliphatic group or an aromatic group having a carbon number of 6 to 20). Examples of R5 include a methyl group, an ethyl group, a propyl group (each isomer), a butyl group (each isomer), a group (each isomer), and a group (each isomer) Base (each isomer), octyl (each isomer), thiol (each isomer), thiol (each isomer), undecyl (each isomer), dodecyl (each isomer), tridecyl (each isomer), tetradecyl (each isomer), pentadecyl (each isomer), hexadecyl (each isomer) , heptadecyl (each isomer), octadecyl (each isomer), nonadecyl (each isomer), eicosyl (each isomer) and the like alkyl; cyclopentane Ring, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl, cyclodecyl, etc.; methoxymethyl, methoxyethyl (each isomer), methoxypropyl (each Isomers), methoxybutyl (each isomer), 'methoxypentyl (each isomer), methoxyhexyl (each isomer), methoxyheptyl (isoisomer) , methoxyoctyl (each isomer), methoxy thiol (each isomer), Oxythiol (each isomer), methoxy deca-alkyl (each isomer), methoxydodecyl (each isomer), decyloxytridecyl (different 131506) .doc -31 · 200948759 Structure), methoxytetradecyl (each isomer), decylpentadecyl (each isomer), methoxy cetyl (each isomer) , methoxyheptadecyl (each isomer), methoxy octadecyl (each isomer), methoxy pentadecyl (each isomer), ethoxymethyl, Ethoxyethyl (each isomer), ethoxypropyl (each isomer), ethoxybutyl (each isomer), ethoxypentyl (each isomer), ethoxy Hexyl group (each isomer), ethoxyheptyl group (each isomer), ethoxyoctyl group (each isomer), ethoxylated thiol (each isomer), ethyl hydrazino group (each isomer), ethoxy undecyl (each isomer), ethoxy dodecyl (each isomer), ethoxylated trialkyl (isomer), B Oxytetradecyl (each isomer), ethoxypentadecyl (each isomer) Ethyl hexadecyl (each isomer), ethoxyheptadecyl (each isomer) ethoxy octadecyl (each isomer), propoxymethyl (variety) Structure), propoxyethyl (each isomer), propoxypropyl (each isomer), 'propoxybutyl (each isomer), propoxypentyl (isoisomer) , propoxyhexyl (each isomer), propoxyheptyl (each isomer), propoxyoctyl (isoindole), propoxy thiol (each isomer) , propoxy fluorenyl (each isomer), propoxy undecyl (each isomer), propoxydodecyl (each isomer), propoxy 13-6 (each Isomers), propoxyl-14 (each constitutive), propoxy pentylene (each isomer), propoxy hexadecane (each isomer), propoxy Heptadecyl (each isomer), butoxymethyl (each isomer), butyl I-ethyl (each isomer), butoxypropyl (iso-isobutyloxybutyrate) Base (each isomer), butoxypentyl (each isomer), butoxyhexyl (each isomer) , butoxyheptyl (each isomer), butoxyoctyl (: isomer), butoxy thiol (each isomer), butoxy thiol (isomeric I31506.doc • 32- 200948759), butoxy11-decyl (each isomer), butoxy 12-base (each iso-oxyl tridecyl (isomer), butoxy-tetradecyl (each r, different gifts, butoxy pentadyl groups (each isomer), butoxy hexyl hexyl iso- 1 =, pentoxymethyl (each isomer), pentoxy ethyl ( Each isomeric bis, methoxy propyl (each isomer), pentoxy butyl (each isomer), valeric amyl (each isomer), pentoxy hexyl (each isomer)戍oxyheptyl (each isomer), oxime octyl (each isomer), pentyloxy fluorenyl (isoindole: thiol (isoisomer), pentyloxy-- Affiliation (each isomeric eleven (each isomer), 4-oxytridecyl (each isomer), pentyloxytetradecyl (each isomer), pentyloxy Pentavalent (each isomer), hexyloxymethyl (each isomer), oxyethyl (each isomer), hexyloxypropyl (isomeric) ), hexyloxybutyl (each isomer), hexyloxypentyl (each isomer), hexyloxyhexyl (each isomer), hexyloxyheptyl (each isomer), Oxyoctyl (each isomer), hexyloxy fluorenyl (each isomer), hexyloxy fluorenyl (each isomer), hexyloxy 11-yard (each isomer), Hexyloxydodecyl (each isomer), hexyloxytridecyl (each isomer), hexyloxytetradecyl (each isomer), heptoxycarbonyl (variety) 2), heptyloxyethyl (each isomer), heptoxypropyl (each isomer), heptyloxybutyl (each isomer), heptyloxypentyl (each isomer) ), heptyloxyhexyl (each isomer), heptyloxyheptyl (each isomer), heptyloxyoctyl (each isomer), heptyloxycarbonyl (each isomer), g Oxycarbonyl group (each isomer: p-heptyloxy undecyl (each isomer), heptyldodecyl (isoisomer) heptyloxydodecyl (each isomer), Octyloxymethyl (each isomer) octyloxyethyl (each isomer), octyloxypropyl group (each isomer Buxin 1 31506.doc -33- 200948759 oxybutyl (each isomer), octyloxypentyl (each isomer), octyloxy group (each isomer), octyloxyheptyl (variety) Structure), octoxyoctyl (each isomer), octyloxy thiol (each isomer), octyloxy fluorenyl (each isomer), octyloxy undecyl (variety) Structure), octyloxydodecyl (each isomer), decyloxymethyl (each isomer), decyloxyethyl (each isomer), methoxypropyl (variety) Structure), oxiranyl butyl (each isomer), decyloxypentyl (each isomer), decyloxyhexyl (each isomer), decyloxyheptyl (each isomer) , oxime octyl (each isomer), decyloxy fluorenyl (each isomer: oxy fluorenyl (each isomer), decyl undecyl (each isomer),癸oxymethyl (each isomer), oxiranyl ethyl (each isomer), methoxy propyl (each isomer), decyloxy butyl (each isomer), oxime Pentyl (each isomer), nonyloxyhexyl (each isomer), nonyloxyheptyl (each isomer), helium Octyl (each isomer), decyloxy group (each isomer), decyloxy group (each isomer), undecyloxymethyl, undecyloxyethyl (each Isomers) undecyloxypropyl (each isomer), undecyloxybutyl (each isomer), undecyloxypentyl (each isomer), undecyloxy Hexyl group (each isomer), undecyloxyheptyl (each isomer), undecyloxyoctyl (each isomer), undecyloxyindenyl (each isomer) , dodecyloxymethylundecyloxyethyl (each isomer), dodecyloxypropyl (each isomer), dodecyloxybutyl (each isomer), Dodecyloxypentyl (each isomer), dodecyloxyhexyl (each isomer), dodecyloxyheptyl (each isomer) 'dodecyloxyloctyl (each isomer), tridecyloxyindenyl (each isomer), tridecyloxyethyl (each isomer), tridecyloxypropyl (each isomer), thirteen Alkoxybutyl (each isomer), tridecane 131506.doc •34- 200948759 oxypentyl (each isomer), tridecyloxyhexyl (each isomer), tridecyloxyheptyl (each isomer), tetradecyloxymethyl (each isomer), fourteen Alkoxyethyl (each isomer), tetradecyloxypropyl (each isomer, tetradecyloxybutyl (each isomer), tetradecyloxypentyl (isoisomer) Tetradecyloxyhexyl (each isomer), pentadecyloxymethyl (each constitutive), fifteen oxyethyl (each isomer), fifteen pit gas base C = Each isomer), pentadecyloxybutyl (each isomer), pentadecyloxypentylhydrazine (each isomer), hexadecyloxymethyl, hexadecanyloxyethyl (each isomer), hexadecanyloxypropyl (each isomer), hexadecanyloxybutyl (each isomer), heptadecyloxymethyl (each isomer), ten Heptadecyloxyethyl (each isomer) heptadecyloxypropyl (each isomer), octadecyloxymethyl (each isomer: oxime oxyethyl (each isomer) ), etc., phenyl, methyl-phenyl (isomeric), ethyl-phenyl (variety) , propyl-phenyl (each isomer), butyl-phenyl (each isomer), pentyl-phenyl (each isomer), hexyl-phenyl (each isomer), Heptyl-phenyl (each isomer: e-octyl-phenyl (each isomer), mercapto-phenyl (each isomer), mercapto-phenyl (each isomer), twelve Alkyl-phenyl (each isomer), phenylphenyl (each isomer), phenoxy-phenyl (each isomer), iso-phenylphenyl (each isomer), Monomethyl-phenyl (each isomer), diethyl-phenyl (each isomer), dipropyl phenyl (each isomer), butyl phenyl (each isomer) ), dipentyl phenyl (each isomer), dihexyl-phenyl (each isomer), diheptyl phenyl (each isomer), diphenyl phenyl (each isomer) ), diphenyloxyphenyl (each isomer), methyl-ethyl-phenyl (each isomer), methyl-propyl-phenyl (each isomer), methyl-butyl -phenyl (each isomer), methyl-pentyl-phenyl 131506.doc -35- 200948759 (each isomer), methyl-hexyl-styl (each isomer), Alkyl heptyl (each isomer), fluorenyl-octyl-phenyl (each isomer), methyl fluorenyl (each isomer), methyl-mercapto-phenyl (each Isomers), methyldodecyl-phenyl (each isomer), methyl-phenyl-phenyl (each isomer), methyl-p-oxy-phenyl (each isomer) ), methyl-cumyl-phenyl (each isomer), ethyl-propyl-phenyl (each isomer), ethyl-butylphenyl (each isomer), ethyl -pentyl-phenyl (each isomer), ethyl-hexylphenyl (each isomer), ethyl 'heptyl-phenyl (each isomer), ethyl-octyl-phenyl ( Each isomer), ethyl-mercapto-phenyl (each isomer), ethyl-fluorenyl-phenyl (each isomer), ethyl-dodecyl-phenyl (isoisomer) , ethyl-phenylphenyl (each isomer), ethyl-phenoxy-phenyl (each isomer), ethyl cumylphenyl (each isomer), propyl -butyl-phenyl (each isomer), propylpentylphenyl (each isomer), propyl-hexyl-phenyl (each isomer), propyl-heptylphenyl (variety) Structure , propyl-octyl-phenyl (each isomer), propyl-hydrazino group (each isomer), propyl-mercapto-phenyl (each isomer), propylphenylbenzene Base Φ (each isomer), propyl-phenoxy-phenyl (each isomer), butyl-fluorenyl-phenyl (each isomer), butyl-hexyl-phenyl (variety) Structure), butylheptylphenyl (each isomer), butyl-octyl-styl (each isomer), butyl-fluorenyl-styl (isomer), butyl·•癸Base-phenyl (each isomer), butylphenylphenyl (each isomer), butyl-phenoxy-phenyl (each isomer), amylhexyl-phenyl (isoisomer) , pentyl-heptyl-phenyl (each isomer), amyloctyl phenyl (each isomer), pentyl-fluorenyl-phenyl (each isomer), amyl benzene Base-phenyl (each isomer), pentyl-phenoxy-phenyl (each isomer), hexyl-heptyl-phenyl (each isomer), hexyl-octyl-phenyl (each Isomer), hexyl benzene benzene 131506.doc -36- 200948759

Base-phenyl (each isomer), hexyl-phenoxy-phenyl (each isomer), trimethyl-phenyl (each isomer), triethyl phenyl (each isomer) ), tripropyl-phenyl (each isomer), tributyl-phenyl (each isomer), dimercapto-yl-phenyl group (each isomer), dimethyl-propyl -phenyl (each isomer), dioxime = phenyl group (each isomer), dimethyl-pentyl-phenyl (each isomer), di-n-hexyl-phenyl (each Isomers), dimethyl-heptyl-phenyl (each isomer), bis-f-octyl-phenyl (each isomer), dimethyl-indenyl-phenyl (isoisomer) , dimethyl fluorenyl-phenyl (each isomer), dimethyl-dodecyl 'stupyl (each isomer), dimethyl-phenyl-phenyl (isomeric) , dimethyl phenyloxy-phenyl (each isomer), dimethyl-cumylphenyl-phenyl (each isomer), diethyl-methyl-phenyl (isomeric) , diethyl-propyl-phenyl (each isomer), diethyl-butyl-phenyl (each isomer), diethylpentyl-phenyl (each isomer), Diethyl-hexyl Base-phenyl (each isomer), diethylheptyl-phenyl (each isomer), diethyl-octyl-phenyl (each isomer), diethyl-indenyl · Phenyl (each isomer), diethyl-fluorenyl-phenyl (each isomer), diethyl-phenyl-phenyl (each isomer), diethyl-phenoxy-benzene Base (each isomer), diethyl-cumyl-phenyl (each isomer), dipropylmethyl-phenyl (each isomer), dipropyl-ethyl-phenyl (each isomer), dipropyl-butyl-phenyl (each isomer), dipropyl-pentyl-phenyl (each isomer), dipropyl-hexyl-phenyl (different Structure), dipropyl-heptyl-phenyl (each isomer), monopropyl phenyl-phenyl (each isomer), dipropylphenoxy-phenyl (each isomer) ), dibutyl-fluorenyl-phenyl (each isomer), dibutylethyl-phenyl (each isomer), dibutyl-propyl·phenyl (each isomer), Dibutyl-pentyl-phenyl (each isomer), dibutyl-hexyl-phenyl (each isomer), two 131506.doc -37- 200948759 ❿ 丁基 butyl-phenyl-phenyl ( each Structure), = phenyloxy stupyl (each isomer), dipentyl methyl-phenyl (each isomer), dipentylethyl stupyl (each isomer), Dipentyl-propyl·phenyl (each isomer), dipentyl-butylphenyl (each isomer), dihexylmethylphenyl (each isomer), dihexylethyl Phenyl (each isomer), methyl-ethyl-propyl-phenyl (each isomer), methyl-ethyl-butyl-phenyl tomb (each isomer), f-based Methyl-nonylphenyl (each isomer), methyl-ethyl-hexylphenyl (each isomer), methylethyl-heptyl-phenyl (each isomer), methyl-B P-octylphenyl (each isomer), methyl-ethyl-fluorenyl-phenyl (each isomer), methyl-ethyl-fluorenyl-phenyl (each isomer), ? —Ethyl-phenoxy-phenyl (each isomer), methyl-ethyl-isopropylphenyl-phenyl (each isomer), ? Propyl butyl phenyl (each isomer), methyl propyl-pentyl phenyl (each isomer), methyl propyl hexyl phenyl (each isomer), methyl -propyl-heptyl-phenyl (each isomer), methyl-propyl-octyl-phenyl (each isomer), methyl-propyldecyl-phenyl (each isomer) , methyl propyl-fluorenyl-phenyl (each isomer), methyl-propyl-phenoxy phenyl (each isomer), methyl-propyl-isopropylidene-phenyl (each isomer), methyl-butyl-pentyl-phenyl (each isomer), methyl-butylhexyl-phenyl (each isomer), methyl-butylheptylphenyl (each Isomerized) methylbutyl-octyl-styl (each isomer), methyl-butylphenoxy-phenyl (each isomer), methyl-butyl-cumylbenzene Base (each isomer), methyl-pentyl-hexyl phenyl (each isomer), methyl-pentylheptyl phenyl (each isomer), methyl pentyl octyl • Phenyl (each isomer), methyl-pentyl-phenoxy L isomer), methyl-hexyl-heptyl-phenyl (different (tetra) b &amp; propyl-butyl _ Phenyl group Ethylpropyl valyl 131506.doc -38- 200948759 base-phenyl (each isomer), ethyl-propyl-hexyl-phenyl (each isomer), ethyl-propyl-heptyl Phenyl (each isomer), ethyl-propyl-octyl·phenyl (each isomer), ethyl-propyl-fluorenyl-phenyl (each isomer), ethyl propylbenzene Oxy-phenyl (each isomer), ethyl-propyl-isopropylidene-phenyl (each isomer), ethyl-butyl-pentyl-phenyl (each isomer), Ethyl-butyl-hexyl-phenyl (each isomer), ethyl-butyl-heptyl-phenyl (each isomer), ethyl-butyl-octyl-phenyl (isoisomer) , ethyl butyl phenoxy-phenyl (variety)

Structure), ethyl·pentyl-hexyl-phenyl (each isomer), ethylpentylheptyl-phenyl (each isomer), ethyl-pentyl-phenoxy-phenyl ( Each isomer), propyl-butyl-phenyl (each isomer), propyl-butylpentylphenyl (each isomer), propyl-butyl-hexyl-phenyl (variety) Structure), propyl-butyl-heptyl-phenyl (each isomer), propyl-butyl-phenoxy-phenyl (each isomer), propyl-pentyl-hexyl-benzene A group (each isomer), a propyl-pentyl-phenoxyphenyl group (each isomer), and the like. Among these, 'preferably, methyl, ethyl, propyl (each isomer), butyl (each isomer), pentyl (each isomer), hexyl (each isomer), The number of carbon atoms T constituting the group such as heptyl group (each isomer) and octyl group (each isomer) is an alkyl group selected from the integer number of 1 to 20. Among these, an alkyl group having 1 to 12 carbon atoms or an aromatic group having 6 to 12 carbon atoms is preferred, and an alkyl group having 5 to 7 carbon atoms or a carbon number of 5 to 7 is more preferred. Aromatic group. As such a carbonic acid-hydrazine, it can be exemplified by monoethyl pentanoate (each isomer), dihexyl carbonate (each isomer), diheptin carbonate (each isomer), diphenyl vinegar, carbonic acid (methylphenyl) ester. Preferably, the carbonic acid S is preferably in the range of 0_ppm~i()%, more preferably 〇.〇〇1 ppm~5k_, and further preferably 〇〇〇2 -39· 131 200948759 ppm~3 /. The range contains metal atoms. Further, the metal atom may exist as a metal ion or as a metal atom. As the metal atom, a metal atom which may be a divalent or tetravalent atomic valence is preferable, and among them, one selected from the group consisting of iron, cobalt, nickel, zinc, tin, copper, and titanium or a plurality of metals is more preferable. The present inventors have surprisingly found that when a carbonate containing a metal atom in a concentration within the above range is used, the modification reaction of the resulting urethane is suppressed in the reaction between the carbonate and the amine compound. Effect. The mechanism for exerting such an effect is not clear, but the inventors have speculated that the reason may be that the metal atom is coordinated with the urethane bond of the urethane formed in the reaction (_NHC) 〇〇_), the urethane bond is stabilized, and a side reaction represented by the above formula (2), the following formula (9), or the like is suppressed, for example. [化7] O-R,

R and R' each independently represent an alkyl group or an aromatic group. (9) (In the formula: ❹ In addition, in the following reaction (IV) containing an aminocarboxylic acid aromatic condensate, it is also concluded that the metal atom inhibits the modification reaction of the amino carboxylic acid aryl sulfonate, and the mechanism may be the same as above. It is expected that the carbonated vinegar and the amine compound are mixed to produce a mixture, and the same effect can be obtained by adding the above-exemplified metal atom to the above-mentioned range in the above-mentioned range, but the inventors of the present invention conducted an effort and found that only Adding a metal atom to a mixture of carbonic acid and an amine compound, 131506.doc •40·200948759 It is difficult to obtain the above effects. The reason for such a result is not clear, but the inventors have speculated that the reason may be that When the carbonated vinegar contains a metal atom, the carbonate is coordinated to the metal atom. In contrast, when a metal atom is added to the mixture of the carbonated acid and the amine compound, the metal atom and the amine are compared with the interaction between the metal atom and the cesium carbonate. The interaction of the compounds is large' so the metal atoms are firmly coordinated to the amine compound, and it is difficult to equip the amine formed. The urethane bond of the carbamate. The carbonate of the present embodiment is preferably produced by the following method. The carbonic acid produced by the method contains the above-exemplified ones in the above preferred range. In the case of a metal atom, the carbonated vinegar may be used as it is. When the amount of the metal atom contained in the carbonated vinegar is less than the above range, the metal atom may be added in other manners, for example, as an organic acid such as an acetate or a cyclic acid salt. Salt 'gasification, acetonitrile acetone complex is added. X, when it is more than the above range', for example, solvent cleaning, steam purification, crystallization, removal by ion exchange tree, use of integrator A method of removing the resin or the like, and reducing the amount of the metal atom to the above range. Further, the metal atom contained in the above range in the carbonated acid is substantially broken; t is reacted with the carbonic acid-amine compound There is no _ role in the process. Therefore, it should be clearly distinguished from the following catalyst for the manufacture of amino carboxylic acid vinegar. The amount of metal atom contained in the bismuth carbonate is intended to be well known to the county. ' For example, according to the form of the sample or the metal component contained: Dong, and from the atomic absorption analysis method, the inductance conversion method, the inductance surface type electropolymer mass analysis method, the labor X-ray analysis method, the analytic ray photoelectron spectroscopy method , electron beam micro analyzer, secondary ion mass = I3I506.doc •41 · 200948759 Analytical method and other methods to choose. The carbonate 'in the case of the carbonate is dicaptanyl carbonate' is better to use It is produced by the following steps (1) and (2). When the carbonate is a diaryl carbonate, the method comprising the steps (1) to (3) is used to produce the 0 step (1): (carbonic acid) a dialkyl ester formation step) a step of reacting an organotin compound having a tin-oxygen-carbon bond with carbon dioxide to obtain a reaction mixture containing dialkyl acetonate;

Step (2): (dialkyl carbonate separation step) a step of separating the dialkyl carbonate from the reaction mixture and obtaining a residual liquid; Step (3): (diaryl carbonate production step) to make the step (2) The dialkyl carbonate separated in the reaction with the aromatic hydroxy compound A to obtain a diaryl carbonate, which is a step of recovering the by-produced alcohol. Further, the following steps (4) and (5) may be carried out in addition to the steps (1) and (2) or the steps (1) to (3). Step (4th plant (organic tin compound regeneration step), the residual liquid obtained in the step (B) is reacted with an alcohol to form an organotin compound having a tin antimony carbon bond and water, and the step of removing the water from the reaction system Step (7): (recycling and recycling step) The organotin compound having a tin-oxygen-carbon bond obtained in the step (4) is reused as an organotin compound having a kick-oxygen-carbon bond in the step (1). Preferably, a tin atom is used as the organotin compound used in the step (1), a dialkyl tin compound. The so-called dialkyl tin compound means an organotin compound bonded with two alkyl groups. 131506.doc -42- 200948759 The example of the di-tin-based tin compound is exemplified by a base tin compound selected from the group consisting of the following formula (10) and a four-soil compound represented by the following formula (11). a compound selected from at least one of the group consisting of a group of alkane compounds.

(10) R and Han respectively indicate that the linear or branched carbon number is an alkyl group of 丨~12; X and X each independently represent a group consisting of an alkoxy group, a decyloxy group and a halogen atom. At least one substituent; a and b are integers of 〇~2, respectively, a+b=2; c and d are integers of 〇~2, respectively, c+d=2).

X3 R10 I | 9 R8· Sn--〇-sn-R”h .^ R9, X4 (wherein R, R, R1G and R&quot; respectively represent linear or branched carbon An alkyl group of 1 to 12; X3 and X4 represent at least one substituent selected from the group consisting of an alkoxy group, a decyloxy group, and a halogen atom; 131506.doc -43- 200948759 e, f, g, h An integer of 〇~2, respectively, e+f=2, g+h=2). As the dialkyl tin catalyst represented by the above formula (10), and the following, the formula (11) Examples of the r8 and R9Hrh of the tetraalkyldistannoxane compound represented by the formula include methyl group, ethyl group, propyl group (each isomer), butyl group (each isomer), and pentyl group (each Isomers), hexyl (each isomer), heptyl (each isomer), octyl (each isomer), thiol (isomeric), thiol (each isomer), ten The number of the atomic atoms constituting the group such as a dialkyl group (each isomer) is an alkyl group of an aliphatic hydrocarbon group selected from the integer number of 1 to 12, etc. More preferably, the number of carbon atoms constituting the group is selected from the group consisting of A linear or branched alkyl group of an integer number of ~8 may also be used. Although the number of carbon atoms in the group is a secondary-base tin compound which is an alkyl group other than the above-described range, the fluidity may be deteriorated or the productivity may be impaired. Further, in consideration of the ease of acquisition in industrial production, Preferred are n-butyl group and n-octyl group. X3 as a dialkyltin compound represented by the above formula (10) and X3 as a tetraalkyldistannoxane compound represented by the formula (11) And X4, 0 represents at least one substituent selected from the group consisting of an alkoxy group, a decyloxy group and a halogen atom. When the group is an alkoxy group and/or a methoxy group, it is preferred to constitute The number of carbon atoms in the group is a group selected from the integer number of 〇~12. As an example of this, exemplified are methoxy, ethoxy, propoxy (iso areomer), butoxy (isoisomer) , pentyloxy (each isomer), hexyloxy (each isomer), heptyloxy (each isomer), octyloxy (each isomer), decyloxy (isomeric) Alkoxy group consisting of a linear or branched saturated alkyl group and an oxygen atom, an ethoxy group (each isomer), an ethoxy group, a propyl group醯oxy, butanoxy, pentyloxy, dodecyloxy, etc. are saturated by linear or branched chains. 13l506.doc 200948759 'halogen, bromine and the like are considered for use as carbonate carbons. The number of oxyalkyl groups composed of oxyalkyl groups, carbonyl groups and oxygen atoms in the range of 4 to 8 is considered to be a better example in consideration of fluidity or solubility, and base 0 is used as a formula. (10) Examples of the diterpenyl tin compound represented by dimethyl-dimethoxy tin, dimethyl-diethoxy tin, Meike kick (each isomer), dimethyl-dibutyl Oxytin (each isomer-monopropyl milk isomer), dimethyl-dihexyltin (each isomer), bis-yl-diheptyltin (each isomer) , dimethyl-dioctyl tin (all isoindoles), monomethyl-dimethoxy tin (each isomer), dimethyl dioxetane (each isomer), dibutyl Base-dimethoxytin (each isomer), dibutyl ethoxy tin (each isomer), dibutyldipropoxide (each isomer), ^ butyl-dibutyl Oxytin (each isomer), dibutyltin dipentoxide (each isomer) Monobutyl-monobutyltin (each isomer), dibutyl·diheptyltin (each isomer), dibutyl-dioctyl tin (each isomer), dibutyl Dimethoxytin (each isomer), dibutyl _: decyl tin oxide (different #'diyl-dimethoxy tin (each isomer), dioctyldiethoxy Kick (each isomer), dioctyl-dipropoxytin (each isomer), dioctyl-dibutoxytin (each isomer), dioctyl-dipentyloxytin ( Each isomer), dioctyldihexyltin (each isomer) 'dioctyl-diheptyl tin oxide (each isomer), dioctyl-dioctyl tin (isoisomer , dioctyl-dimethoxytin (each isomer), dioctyl-dimethoxytin (each isomer), etc., dialkyl-dialkyloxy tin, dimercapto-di Ethyl tin oxide, dimethyl dipropylene oxide kick (each isomer), dimethyl-dibutyloxy tin (each isomer), dimethyl-pentanyloxy 131506.doc -45- 200948759 Tin (each isomer), dimethylglycolate (dodecyloxy) tin (each isomer), diyl-diethyl oxytin ( Each isomer), dibutyl-dibutyl sulphide! Butyloxytin (each butyl tin hydride (each isomer), dibutyl dimethyl ketone tin (each isomer), _., butyl bis(dodecyloxy) tin (isomeric

It is: tin oxytin (each isomer), dioctyldipropionyloxy (n-isomer), dioctyl-dibutyl oxytin (each isomer), dioctyl pentoxide Dixyl-di-oxo tin oxide, dimethyl-tin dichloride, dimethyl, etc., such as tin (each isomer), dioctyl-di(dodecanoxy)tin (each isomer) Soil I / stinky tin, monobutyl di-tin sulphide (polyisomers, dibutyl bromide (isoisomers), dioctyl-di-stannized tin (isomers), two Dialkyl-di-tin-tin such as octyl-di-tin (each isomer), etc. Among them, dimethyltin dimethoxide and dimethyl-diethoxy oxide are preferred. Base tin, monomethyl-dipropoxytin (each isomer), dimethyl-dibutoxytin (each isomer), dimethyl-dipentyloxytin (isomeric) , dimercapto _ hexyl hexoxide (each isomer), dimethyl-diheptyloxy tin (each isomer), monomethyl bis octyl tin (each isomer), dimethyl Di-n-stannyl tin (each isomer), di-n-yl 'dimethoxy tin (each isomer), dibutyl-dimethoxy tin (each isomer), dibutyl- Ethoxytin (each isomer), dibutyl-dipropoxytin (each isomer), dibutyl-dibutoxytin (each isomer), dibutyl-dipentoxide Base tin (each isomer), dibutyl-dihexyl tin (each isomer), dibutyl-diheptyloxy tin (each isomer), dibutyl-dioctyl tin (each isomer), dibutyl-dimethoxytin (each isomer), dibutyl-dimethoxytin (each isomer), dioctyl-dimethoxytin (each Isomers), dioctyl-diethoxytin (each isomer), dioctyl-dipropoxytin (isomeric 131506.doc -46- 200948759

, dioctyldibutoxide (each isomer), dioctyl-dipentyloxytin (each isomer), dioctyl-dihexyloxytin (each isomer) , dioctyl-diheptyl tin oxide (each isomer), dioctyl-dioctyloxy tin (each isomer), dioctyl-dimethoxy tin (each isomer), two a dialkyl-dialkyloxy tin such as octyl-dimethoxytin (each isomer), more preferably dibutyl-dipropoxytin (each isomer), dibutyl- Dibutoxytin (each isomer), dibutyl-dipentyloxytin (each isomer), dibutyl-dihexyloxytin (each isomer), dibutyl-diheptane Oxytin (each isomer), dioctyl-dipropoxytin (each isomer), dioctyl-dibutoxytin (each isomer), dioctyl-dipentyloxy a dialkyl-dialkyloxy tin such as tin (each isomer), dioctyl-dihexyltin (each isomer), or dioctyl-diheptyloxytin (each isomer), Further preferred are dibutyl-dibutoxytin (each isomer), dibutyl-dipentyloxytin (each isomer), dibutyl-dihexyloxy lock Each isomer), tributyl-diheptyltin (each isomer), dibutyl-dioctyl tin (each isomer), dioctyldibutoxytin (isomeric) , dioctyl-dipentyloxytin (each isomer), dioctyl-dihexyltin (each isomer), dioctyl-diheptyloxy tin (isomeric) Dioctyl-dioctyl tin (each isomer). The dialkyltin compound represented by the above formula (ίο) behaves as a monomer structure' but may also be a multimeric structure or an associate. Examples of the tetraalkyldialkoxydistannoxane represented by the formula (11) include 1,1,3,3·tetramethyl-1,3-dimethoxydistannoxane. , 113 L tetramethyl 1,3-diethoxydistannoxane, ijj, % tetramethyl^3-dipropoxydistannoxane (each isomer), H33·tetramethyl _ 13_Dibutoxy-stannoxane (each isomer), 1,1,3,3-tetramethyl-oxime, 3-dipentyloxydistannoxane 131506.doc -47- 200948759 (each Isomer), 1,1,3,3-tetramethyl-1,3-dihexyloxystannane (each isomer), 1,1,3,3-tetradecyl-1, 3-diheptyloxydistannoxane (each isomer), 1,1,3,3-tetradecyl-1,3-dioctoxydistannoxane (each isomer), 1, 1,3,3-tetramethyl-1,3-dimethoxyoxystannane (each isomer), 1,1,3,3-tetramethyl-1,3-dioxyloxy Cyclooxane (each isomer), 1,1,3,3-tetrabutyl-1,3-dimethoxydistannoxane (each isomer), 1,1,3,3-tetra Butyl-1,3-diethoxydistannoxane (each isomer), 1,1,3,3-tetrabutyl-1,3-dipropoxydistannoxane (isomeric , 1,1,3,3-tetrabutyl-1,3-dibutoxydistannoxane (each isomer), 1,1,3,3-tetrabutyl-1,3- Dipentyl pentoxane (each isomer), 1,1,3,3-tetrabutyl-1,3-dihexyloxystannane (each isomer), 1,1, 3,3-tetrabutyl-1,3-diheptyloxydistannoxane (each isomer), 1,1,3,3-tetrabutyl-1,3-dioctyloxydithion Alkanes (each isomer), 1,1,3,3-tetrabutyl-1,3-dimethoxyoxystannane (each isomer), 1,1,3,3-tetrabutyl -1,3-dimethoxy distannoxane (each isomer), 1,1,3,3-tetraoctyl-1,3-dimethoxydistannoxane (each isomer) 1,1,3,3-tetraoctyl-1,3-diethoxydistannoxane (each isomer), 1,1,3,3-tetraoctyl-1,3-dipropane Oxydistanoxane (each isomer), 1,1,3,3-tetraoctyl-1,3-dibutoxydistannoxane (each isomer), 1,1,3, 3-tetraoctyl-1,3-dipentoxydistannoxane (each isomer), 1,1,3,3-tetraoctyl-1,3-dihexyloxydistannoxane ( Each isomer), 1,1,3,3-tetraoctyl-1,3-diheptyloxytin Oxane (each isomer), 1,1,3,3-tetraoctyl-1,3-dioctoxydistannoxane (each isomer), 1,1,3,3-tetraxin Base-1,3-dimethoxy distannoxane (each isomer), 131506.doc -48- 200948759 Dibasic tris- 3 dioxo-di-n-oxygen (each isomer) Oxime oxy-oxygen, U, 3,3, methyl 1,4-3 = two (isoforms), methyl ketone oxy 2: (isomers), U, 3, 3 -tetramethyl-tris-tris-dipentyloxy-di-tin-oxygen production (each isomer U,3,3·tetramethyl-U·bis(dodecyloxy)ditin=❹

G (each isomer), U, 3,3_tetrabutyl-indole, 3•diethyl decyl sulphide (each isomer), 1,1,3,3·tetrabutyl _ 1,3_dipropene oxydioxazolidine (each isomer), 1,1,3,3-tetrabutyldibutoxy dianoxane (each isomer), 1,1 , 3,3-tetrabutyldipentyloxydistannoxane (each isomer), 1,1,3,3-tetrabutylbis(dodecyloxy)distannoxane (various Structure), 1,1,3,3-tetraoctyldiethoxynonantaxane (each isomer), 1,1,3,3-tetraoctyl-i,3_dipropene Oxydistanoxane (each isomer), 1,1,3,3-tetraoctyl-ι, 3-dibutoxy dianoxane (each isomer), 1,1,3 ,3-tetraoctyl-i,3-dipentyloxydistannoxane (each isomer), 1,1,3,3-tetraoctyl-i,3-di(dodecyloxy) 1, 1,3,3,tetraalkyl-1,3-dimethoxyoxydistannoxane, etc., yunhong tetramethyl-1,3-di Gas distannoxane, ι,ι,3,3-tetramethyl-indole, 3-dibromodistannoxane, 1,1,3,3-tetrabutyl-1,3-dioxide, tin oxychloride Alkane ), 1,1,3,3 -tetrabutyl-1,3 -------------------------------------------------------- Tin, breast (each isomer), 1,1,3,3-tetraalkyl, etc., l,i,3,3-tetraoctyl-1,3-dibromodithioxanthine (each isomer) _ι,3-two paintings of distannoxane. Among these, 1,1,3,3-tetramethyl_ι,3·dimethoxyditin 131506.doc •49- 200948759 oxane, 1,1,3,3-four F-yl-1,3-diethyl fluorenyl stannane, smectic tetramethyl-1,3-dipropoxydistannoxane (each isomer), hydrazine, ι, 3, 3·4 Methyl _ i'3 - dibutoxy oxoxane (each isomer), 1,1,3,3-tetradecyl-1,3-dipentyloxydithionate (isomeric , 1,1,3,3-tetradecyl_ι,3-dihexyloxystannane (each isomer), 1,1,3,3-tetradecyl-1,3- Diheptyloxydistannoxane (each isomer), i'1,3,3·tetramethyl-1,3-dioctoxydistannoxane (each isomer), 1,1, 3,3-Tetramethyl-hydrazine, 3-dioxaoxydistannoxane (isomethyl-1,3-dimethoxyoxydi-1,3-dimethoxyditin-i, 3 - —* Ethoxyditin*1,3-propoxyditin&quot;1,3-Dibutoxyditin~1,3-dipentyloxyditin•1,3-dihexyloxy Di-tin-1,3-1,3-diheptyloxydishrazin, 3-dioctyloxyditin, 3-dimethoxydioxy-1,3-di Oxydixime, 3- methoxy di tin 1,3- ethoxydi tin &quot;1,3- -* propoxyditin • 1,3-butoxy bis tin • 1,3 - Dipentyloxytin•1,3-hexyloxyditin), 1,1,3,3-tetra-1,1,3,3-tetrabutyl 1,1,3,3-tetrabutyl 1,1,3,3-tetrabutyl 1,1,3,3-tetrabutyl 1,1,3,3-tetrabutyl 1,1,3,3-tetrabutyl 1,1,3 , 3-tetrabutyl 1,1,3,3-tetrabutyl 1,1,3,3-tetrabutyl 1,1,3,3-tetrabutyl 1,1,3,3-tetraoctyl 1,1,3,3-tetraoctyl 1,1,3,3_tetraoctyl 1,1,3,3-tetraoctyl 1,1,3,3-tetraoctyl 1,1,3, 3-tetraoctylstannane (each isomer), oxyalkylene (each isomer), oxyalkylene (each isomer), oxy-fired (each isomer), oxyalkylene (each isomer) , oxane (each isomer), oxyalkylene (each isomer), oxyalkylene (each isomer), oxyalkylene (each isomer), oxyalkylene (each isomer), oxyalkylene (each Isomers), oxane (each isomer), oxyalkylene (each isomer), oxyalkylene (each isomer), oxyalkylene (each isomer) , oxane (each isomer), oxane (each isomer), 131506.doc -50· 200948759 1,1,3,3-tetraoctyl-u-diheptyloxydistannoxane Isomer), 1,1,3,3-tetraoctyl 4,3-dioctoxydistannoxane (each isomer), 1,1,3,3-tetraoctyl 4,3- 1,1,3'3-tetraoctyl-i,3-dimethoxyoxystannane (each isomer), etc. 1,1, 3,3-four-yard base _ 1,3-alkaline-oxy-tin-oxygen, of which 1,1,3,3-tetrabutyl-1,3-dibutoxy-di-tin is further preferred. Oxane (each isomer), 1,1,3,3-tetrabutyl-I,3-dipentyloxydistannoxane (isomers), 1,1'3,3·tetradecene Base-i,3-dihexyloxystannane (each isomer), 1'1,3,3-tetrabutyl-I,3-diheptyloxydistannoxane (each isomer) , 1,1,3,3-tetrabutyl-i,3-dioctoxydistannoxane (each isomer), 1,1,3,3·tetraoctyl-!,3-di Butoxy-distannoxane (each isomer), 1,1,3,3-tetraoctyl-i,3-dipentyloxydistannoxane (isomers), 1,1,3 , 3-tetraoctyl _ι,3-dihexyloxystannane (each isomer), 1,1'3,3-tetraoctyl_ι,3-diheptyloxydistannoxane (each isomer), 1,1,3,3-tetraoctyl-, 3-dioctyloxydistannoxane (each isomer). The tetraalkyldialkoxydistannoxane represented by the above formula (11) exhibits a monomer structure, but may also be a multimeric structure or an associate. It is known that 'usually an organotin compound is liable to form an association structure, for example, a two-base tin-tin lanthanum oxytin to form a dimer structure, or a tetraalkyl-di- oxy-distannoxane to form a two- or three-molecular association. In the case of a trapezoidal structure, even if the state of the association changes, it is common for the manufacturer to express the compound in a monomer structure. Further, one of the above-mentioned base tin compounds may be used singly or in combination of two or more kinds. 131506.doc 51 200948759 As a method for producing a dialkyltin compound, the disclosed production method (WO 2005/^^9, etc.) can be preferably utilized. This step is a step of producing a bis-tin-based tin compound from a dialkyltin oxide and an alcohol. The alcohol used in the present embodiment is methanol, ethanol, propanol (each isomer), butyrate (each isomer), pentanol (each isomer), and hexanol (each isomer) An alcohol such as heptanol (each isomer), octanol (each phosgen), decyl alcohol (each isomer), or decyl alcohol (each isomer) can preferably use a carbon atom constituting the alcohol. The number is an alcohol selected from the number of integers from 1 to 12. The dialkyl oxide used in the alkyltin alkoxide synthesis step is a dialkyltin oxide represented by the following formula (12). /R12 \ ~rSn-θ']- V r13 / η (1 2) (wherein R12 and R13 each independently represent a linear or branched carbon number as a base). Examples of RU and R13 include a methyl group, an ethyl group, a two group (each isomer), a butyl group (each isomer), a pentyl group (each isomer), and a hexyl group (each isomer). , heptyl (each isomer), octyl (each isomer), thiol (each isomer), thiol (each isomer), undecyl (each isomer), twelve An alkyl group (each isomer) or the like, which is an aliphatic hydrocarbon group having 1 to 12 carbon atoms. More preferably, it is a linear or branched saturated alkyl group having 1 to 8 carbon atoms, and more preferably n-butyl group or n-octyl group. 131506.doc -52· 200948759 Dehydration of an alcohol with a dialkyltin oxide, while removing the formed water to the outside of the system, to obtain a tetraalkyldialkoxydistannoxane and/or a secondary compound tin Second burned oxide. The temperature at which the reaction is carried out is, for example, in the range of 8 Torr to 18 (rc), in order to distill off the generated water to the outside of the system, the reaction temperature also depends on the reaction pressure, but preferably 10 (rc~18 (rc, Increasing the reaction rate 'The reaction temperature is preferably a 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 10 (TC to 160). The range of °c. The reaction pressure can remove the generated water to the pressure outside the system, and also depends on the reaction temperature, and is carried out at 20~1×106 Pa. The reaction time of the dehydration reaction is not particularly limited, and is usually 0.001 to 50. In an hour, it is preferred that 〇〇1 to 1 〇h is better for '0 '1 2 hours. The reaction can be terminated by transferring the desired sulphur-based tin oxide composition to the right. The reaction can be carried out by measurement. It is confirmed by the amount of water outside the system, and the reaction liquid can also be sampled and confirmed by the method. u is the mixture of the present embodiment produced in the step (1), and it is confirmed that the following composition can be obtained to complete the reaction, that is, the above reaction. Alkane obtained in The molar ratio of the tetraalkyl oxydioxyn oxysulfide and the bismuth tin oxide to the oxide contained in the stannane oxide compound is 〇: 100 in terms of the molar % of the two. ~80:20 range, more preferably 1〇: 9〇~7〇: 3虹 range of the rainbow. The alcohol used can be used directly in the coexistence state, and the alcohol can be removed according to the situation. Use. Because it has the advantage of reducing the reaction of other steps, it is better to remove the alcohol as much as possible. The method of removing is preferably using the well-known removal method using steaming, and the steaming used in the steaming hall. The well-known fog device can be used. As a better steaming device 131506.doc -53- 200948759, since it can be removed in a short time, the thin film distillation device can be preferably used. The form of the dehydration reaction reactor is not It is particularly limited that a low-boiling reaction mixture containing a well-known trough-like, columnar reactor β water can be discharged from the reactor in a gas form by distillation, and may contain a tin-alkaxane or alkyl group produced. High boiling of tin alkoxide mixture The point reaction mixture is discharged from the lower part of the reactor as a liquid. As such a reactor, for example, a stirring tank, a multi-stage stirring tank, a distillation column, a multi-stage distillation column, a multi-tubular reactor, a continuous multi-stage distillation column, a method of filling a column, a thin film evaporation state, a reactor having a support inside, a forced circulation reactor, a falling film evaporator, a falling drop evaporator, a fine flow phase reactor, and a bubble column, and Various methods, such as a combination of methods, etc., in order to effectively balance the equilibrium toward the side of the formation, it is preferred to use a column reactor, and it is preferred to rapidly transfer the formed water to the gas phase. A structure in which the gas-liquid contact area is large. A continuous method using a multi-tubular reactor, a multi-stage steaming tower, and a packed column filled with a filler may be employed, but the second-burning tin oxide used in this step may be used. It is usually in the form of a solid, and therefore it is preferred to carry out the first step in a trough reactor, followed by a method of increasing the content of the dialkyltin dialkoxide in the column reactor. If the adverse effects are not caused, the materials of the reactor and the piping may be any known materials, and SUS304, SUS316, SUS316L, etc. are relatively inexpensive, so that it can be used as needed, and a measuring instrument such as a flow meter or a thermometer can be added. Well-known processing devices such as a reboiler, a pump, and a condenser; the heating can be performed by a well-known method such as steam addition, a device, or the like, and a well-known method such as natural cooling, cooling water, or brine can be used for cooling. 131506.doc •54· 200948759 Step (1) is a step of producing a carbonate by reacting a dialkyltin compound produced by the above method with gaseous carbon dioxide. This step preferably uses the disclosed carbonic acid. Process for the production of esters (WO 03/055840, WO 04/014840, etc.). The alkyl tin compound supplied to this step may be supplied by an alkyl stane alkoxide synthesis step at the time of startup; sometimes it may be a dialkyl tin compound production step from the following step (4) in continuous production. It is supplied via step (5). 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 dialkylstannane oxide is reacted in a liquid state. When the dialkylstannoxide is a solid, in order to make the dialkylstan alkoxide liquid, a method of forming 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, which is preferably in the range of normal pressure to 1 MPa, and more preferably in the range of normal pressure to 0.6 MPa. The reaction temperature also depends on the pressure of the reaction, but is preferably in the range of -40 ° C to 80 ° C. If the fluidity during transportation is considered, it is preferably 〇 ° C to 80 ° C. The range is normal temperature (for example, 2 〇. (:) ~ 80. (: The reaction time is in the range of several seconds to 100 hours, and if productivity is considered, it is preferably several minutes to 10 hours. The reactor can be used. A well-known tank reactor or a tower reactor is used. Further, 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), Efficiently reacting, it is better to expand the gas-liquid interface to expand the contact area between gas and liquid. So expand 131506.doc -55- 200948759 atmospheric liquid interface and #/5 temple*,,. __

If a tower reactor is used, it is better to utilize

Pall ring, Beri saddie, Intalox saddle, Dix〇n paeking, McMahon Packing, Heli pack Filler towers of various fillers such as Sulzer Packing and MeUapak. If the adverse effects are not caused, the materials of the reactor and the piping can be any known materials, and SUS304, SUS316, SUS316L, etc. are relatively inexpensive, so that they 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; the heating may be performed by a well-known method such as steam or a heater, and cooling may also use natural cooling and cooling water. A well-known method such as salt water. The reaction is usually an exothermic reaction, so that it can be cooled, or it can be cooled by the exotherm of the reactor or heated if it is required to be subjected to a carbonation reaction. A well-known method such as a method using a sleeve or a method using an internal coil can be employed for the cooling and heating of the reactor. One of the oxidized carbon gas and the sulphur-based tin oxide composition supplied to the reactor may be supplied to the reactor separately, or may be previously mixed before being supplied to the reactor. It can be supplied from multiple parts of the reactor. The end of the reaction can be determined, for example, by U9Sn-NMR analysis. 131506.doc • 56· 200948759 Next, a reaction liquid containing cesium carbonate was obtained from the carbon dioxide bonded body of the above-mentioned dioxide tin oxide obtained by the following method. ❹ The reaction conditions are 1HTC~·. The range of C is 'in order to improve: the speed is high, and the reaction temperature is preferably high temperature. On the other hand, there are cases where an adverse reaction such as decomposition occurs at a high temperature, and sometimes the yield is lowered, so 12 Gt is preferable. The range of ~18G °C, the reaction time is the range of Qi hour ~ 1 〇 hour 'reaction pressure is M MPa ~ 2 〇 slightly, preferably 2 〇 MPa ~ H) MPa range. The reaction can be terminated after the desired carbonated vinegar is formed in the reactor. The progress of the reaction can be confirmed by the following method: sampling of the reaction (4) in the reactor, and analyzing the produced carbonated vinegar by a method such as 1 Η or gas chromatography. For example, a carbon dioxide bond of a two-base tin-oxide oxide and/or a di-alkali (tetra) oxide contained in a carbon dioxide bond of a dialkyl tin oxide oxide and/or a dialkyl tin alkoxide. When the molar number of the body is generated by 10% or more, the reaction can be terminated. When the yield of the carbonic acid is increased, the reaction is continued until the value is above the contact. The reactor can be used with a well-known reactor, which can be preferably simultaneously. Use a tower reactor, tank type and reaction. If the right side does not cause adverse effects, the material of the reactor and the path can be any known material. Among them, just 04 or SUS316L is relatively inexpensive, so that it can be preferably used. As needed, a condensate! : Additional measuring instruments such as flow meters and thermometers, reboilers, pumps, and well-known processing devices; heating can use steam, heaters, etc., such as well-known water, but also natural cooling, cooling water, and salt. The step (7) in the embodiment is a step of separating and recovering the carbonate in the reaction solution containing the carbonic acid from the package 131506.doc • 57· 200948759 obtained in the above step (1), and obtaining a residual liquid. The separation method can suitably utilize a well-known method or apparatus. A preferred method is to use a steaming plant for separation. = The reaction solution carried out in the above step (1) is subjected to batch or semi-batch or continuous distillation to obtain a carbonate and a residual liquid. The preferred distillation method is as follows: the reaction liquid is supplied to a steamer, and the carbonated vinegar is separated as a gas phase component from the upper part of the steaming museum to the outside of the system, and the residual liquid is used as a liquid-formed self-steaming device. The bottom is discharged. The temperature of this step is also determined by the range of the carbonated vinegar f or the pressure negative ^ normal temperature (9) such as the size of the scratch, sometimes the tin compound in the residual liquid will be modified at high temperature, or the reverse reaction of the carbonic acid s 曰It is reduced, so it is better to have a range of room temperature (for example, 汕C) 150C. The pressure also depends on the type of carbonated vinegar or the degree of the reaction to carry out the reaction. The reaction is usually carried out under normal pressure to reduced pressure. If productivity is considered, it is preferably 1 〇〇 Pa 〜 8 〇 The best is the range of 100 Pa to 50 KPa. The time can be from 0.01 hours to 10 hours. If the reaction is carried out at a high temperature for a long period of time, the tin compound contained in the reaction solution may be modified or the carbonated vinegar may be reduced by a reverse reaction, so G is preferably G. .G1 hour ~ 〇. 5 hours range, the best is the range of hours, hours. The steaming hall can use the well-known steaming museum, and can also use the tower steaming device, the trough type steamer, or a plurality of steaming museum groups. Further, a preferred vaporizer-type thin film evaporator and a thin film vaporizer are preferably a thin film evaporator having a steaming tower and a thin film evaporation museum. If it does not cause adverse effects, the material of the steaming machine and the pipeline can be any well-known material, among which SUS304 or s remuneration 6, _ mess, etc. are relatively cheap \3l506.doc -58- 200948759, so it can be used well . If necessary, additional measuring instruments such as flow meters and thermometers, and well-known processing devices such as reboilers, pumps, and condensers can be added. Heating can be performed by well-known methods such as steam and heaters. Cooling can also use natural cooling, cooling water, and brine. And other well-known methods. The step (3) is a step of reacting the dialkyl carbonate separated in the step (2) with the aromatic trans group compound A to obtain a diaryl carbonate, and recovering the alcohol formed as a by-product. Here, the aromatic hydroxy compound is a compound corresponding to the compound ruler 1〇11, and the compound is a group of R1〇 (R1 represents the above-defined aromatic group) represented by the above formula (8). '〇 denotes an oxygen atom) is added to a hydrogen atom. Specifically, examples of the aromatic hydroxy compound A which is preferably used include phenol, methylphenol (each isomer), ethylphenol (each isomer), and propylphenol (isomeric). , monobutyl substituted phenols such as butyl phenol (each isomer), amyl phenol (each isomer), hexyl phenol (each isomer), diterpene (individually), Diethylbenzene (each isomer), dipropyl benzene (diterpene structure), mercaptoethyl phenol (each isomer), methyl propyl phenol (isomers), A Disubstituted phenols such as butyl phenol (each isomer), decylpentyl phenol (each isomer), ethyl propyl phenol (each isomer), ethyl butyl phenol (each isomer) , trimethyl phenol (each isomer), triethyl phenol (each isomer), dimercaptoethyl phenol (each isomer), dimethyl propyl phenol (isomers), Trisubstituted phenols such as dimethyl butyl phenol (each isomer), naphthol (each isomer), and the like. The step (3) in the present embodiment is a step of reacting a component mainly containing a carbonated sugar in the step (2) with an aromatic hydroxy compound A to obtain a carbonic acid 131506.doc-59-200948759 diaryl vinegar. A method of obtaining an alkyl aryl carbonate or a diaryl carbonate from a carbonic acid dialkyl vinegar and an aromatic hydroxy compound has been proposed in the prior art. In the present embodiment, these techniques can be preferably used. The reaction of the step (3) comprises a reaction between the carbonate and the aromatic radical compound and a heterogeneous reaction of the carbonic acid obtained by the brewing exchange reaction. The purpose of the exchange reaction is to balance the reaction, and to promote the reaction favorably, it is preferred to carry out the reaction while discharging the alcohol formed by desorption in the transesterification reaction. In this case, preferably, in the step (3) The aromatic hydroxy compound used has a boiling point higher than the boiling point of the alkyl group constituting the alkyl carbonate obtained in the step (2). In particular, when the steps of the steps (1) to (3) are repeated, and the second embodiment is continuously carried out, it is preferred that the boiling point of the alkyl alcohol is lower than the standard boiling point of the aromatic hydroxy compound, and the difference in boiling point is better. It is 2. Oh, if you consider the ease of separation, then it is better to 10 . As an example of the dialkyl carbonate used in the step (3), for example, dimethyl carbonate, diethyl carbonate, dipropylene carbonate (each isomer), dibutyl carbonate (each isomer) is used. ), diamyl carbonate (each isomer), dihexyl carbonate (each isomer), diheptyl carbonate (each isomer), dioctyl carbonate (each isomer), diterpene carbonate (each isomer), carbonic acid dimer (each isomer), dicyclopentanyl carbonate, dicyclohexanol carbonate, bicycloglycolic acid carbonate (each isomers wide carbonic acid two-base vinegar, carbonic acid two Phenylethyl vinegar (each isomer), dipropyl carbonate is called isomer), bis(phenylbutyl) vinegar (different), diacid-(chlorobenzyl) vinegar (isomeric) , bis(methoxy) vinegar (each isomer), bis(methoxymethyl) carbonate, bis(methoxyethyl) carbonate (each I31506.doc 200948759 isomer) ), bis(chloroethyl) vinegar (each isomer), di(cyanoethyl) carbonate (each isomer), methyl ethyl carbonate, methyl propyl carbonate (isomeric) ), Vinegar, methylbutyl carbonate (including isomers), ethylpropyl carbonate vinegar (different structure thereof), ethyl butyl acetate (including isomers), ethylene carbonate stuffed, propylene carbonate and the like. The carbonate used may be one type or a mixture. In the present embodiment, it is preferable to use an alcohol having a standard boiling point of a carbonate-constituting alcohol higher than a standard boiling point of water, and a hospital base having a carbon number of 4 to 12. An alcohol, an alkenyl alcohol having a linear or branched alkenyl group having 4 to 12 carbon atoms, a cycloalkyl alcohol, or an aralkyl alcohol. In order to advantageously advance the reaction carried out in the step (3), if it is considered to remove the alcohol formed by the reaction of the step (3), it is further preferred that the standard boiling point is lower than the standard boiling point of the aromatic hydroxy compound used in the step. Alcohol. Namely, a dialkyl carbonate composed of an alcohol having a standard boiling point higher than water and having a lower boiling point than the aromatic hydroxy compound is preferred. The amount of the aromatic mercapto compound used in the step (3) is stoichiometrically relative to the amount of the dialkyl carbonate separated in the step (2) and used in the step (3). Use within the range of Oi times ~ 1〇〇〇〇. The reaction in the step (3) is mainly an equilibrium reaction, so that the amount of the aromatic hydroxy compound is more favorable, and if the amount of use is increased, the reactor becomes large, and thereafter the separation of the product requires a larger distillation column or the like. It is preferably in the range of 1 to 1000 times, more preferably in the range of 200 times, with respect to the dialkyl carbonate. The compound to be supplied to the step (3) is mainly a dialkyl carbonate or an aromatic compound, and if necessary, a catalyst, and impurities which do not particularly adversely affect the reaction can be mixed. 131506.doc -61 - 200948759 These feed materials may include alcohols, alkyl aryl carbonates, and diaryl carbonates as products, and the reaction is a reaction. When the concentration of the product is too high, the reaction rate of the raw material may be poor (four). The ratio of the amount of the carbonated acetal to the aromatic mercapto compound to be supplied may vary depending on the kind and amount of the catalyst, and the reaction conditions. Usually, it is preferably the dialkyl carbonate relative to the feedstock. The aromatic 羟基 molar ratio is 0.01 to 1000 times the range to supply 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 0 001 to 50 hours, preferably 0. (Π~1 () hour, better The reaction temperature is the temperature in the reactor, which varies depending on the type of the raw material compound used, that is, the dialkyl carbonate and the aromatic hydroxy compound, and is usually 5 〇 t to 35 (rc, preferably Hxrc 〜 2). β χ is carried out within the range of the thief, and the reaction pressure may be reduced according to the type of the raw material compound used or the reaction temperature, etc., and may be reduced, normal pressure, or added, usually in the range of 1 G pa to 2 G. In the present embodiment, it is not necessary to use a solvent for the purpose of facilitating the reaction operation, etc., and an appropriate inert solvent such as an ether, an aliphatic hydrocarbon, an aromatic hydrocarbon, a southern aliphatic hydrocarbon, or a tooth may be used. Aromatic hydrocarbons and the like are used as a reaction; and the Qiqi JX can coexist an inert gas such as nitrogen or helium argon as a substance inert to the reaction in the reaction system, and also accelerates the formation of the low 4 points. Product for the purpose, self-connected Continued under the multi-stage steaming tower 4, the organic gas of the inert gas or the low flame point inert to the reaction is introduced into the gas. 13I506.doc -62- 200948759, when the reaction of the step (3) is carried out, A catalyst can be added. As described above, by S1, it is possible to obtain a balanced bias reaction system for the reaction of carbonic acid by the carbonic acid, and the reaction rate is slow. When the method of producing a diaryl carbonate, in order to improve the above, several proposals have been made. This embodiment makes it possible to preferably use a well-known method. The amount of the catalyst used in the present embodiment depends on the catalyst used. The type of the reactor, the type of the reactor, the type of the carbonated carboxylic acid and the aromatic radical compound or the reaction ratio thereof, the reaction temperature, the reaction pressure, and the like are different from those of the carbon compound and the compound (4) as the raw material for the feed. The ratio of the total weight is usually used at 0 0001 to 50% by weight. Further, in the case of using a solid catalyst, a catalyst amount of 0.01 to 75 vol% is preferably used with respect to the volume of the reactor of the reactor. As A plurality of metal-containing catalysts are known in connection with a catalyst for accelerating the reaction rate. In the present embodiment, a well-known transesterification catalyst can also be used. The carbonate and the aromatic hydroxy compound are reacted. In the method of producing a mixture comprising an alkyl aryl carbonate and/or an alkyl aryl carbonate and a diaryl carbonate, as such a catalyst, for example, a Lewis acid such as a transition metal dentate or a compound which purifies a Lewis acid is proposed. a tin compound such as an organotin alkoxide or an organotin oxide, a salt of an alkali metal or an alkaline earth metal, a burned oxide, a wrong compound, a metal complex such as copper, iron, or the like, and a titanate. a compound of a mixture of a Lewis acid and a protic acid, a compound of Sc, Mo, Mn, Bi, Te, etc., iron acetate or the like. The formation of the carbonic acid aroma can be produced only in the reaction of the vinegar and can be produced by the heterogeneous reaction of the alkyl aryl carbonate formed by the transesterification reaction. Here, 131506.doc -63 - 200948759 A non-homogeneous reaction means a reaction of forming a dialkyl carbonate and a diaryl carbonate from an alkyl aryl carbonate of two molecules. The alkyl aryl carbonate further reacts with the aromatic hydroxy compound, and also causes the reaction to become a diaryl carbonate, and the heterogeneous reaction is faster. Therefore, when the diaryl carbonate is obtained, the alkyl aryl carbonate is uneven. The diaryl carbonate was obtained. Either reaction is an equilibrium reaction. In the transesterification reaction for producing an alkyl aryl carbonate, the reaction is carried out while discharging the alkyl alcohol, and in the unevenness step, it is advantageous to carry out the reaction while discharging the dialkyl carbonate. Therefore, the preferred reaction conditions are different in each stage. In the case of continuous reaction, it is necessary to carry out the reaction in two stages, and in the case of batchwise, it may be carried out successively in the same reactor. Therefore, the catalyst for catalyzing the heterogeneous reaction can be stored together with the above-mentioned transesterification catalyst. More examples of such catalysts can also be proposed. As such a catalyst, for example, a Lewis acid and a transition metal compound capable of generating a Lewis acid, a polymer tin compound 'to pass SR X (=〇) 〇H (wherein χ is selected from ❹ Μ* ΤΙ, R is selected from the group consisting of a compound represented by a monovalent hydrocarbon group, a mixture of a Lewis acid and a protonic acid, a lead catalyst, a titanium or zirconium compound, a tin compound, a compound such as Sc, Μ, Μ, Bi, and Te. The step of unevenness is a step of obtaining a dialkyl carbonate and a diaryl carbonate by synthesizing the alkyl aryl carbonate obtained in the transesterification step. As described above, when the transesterification reaction is carried out, a heterogeneous catalyst may be added to carry out the transesterification reaction simultaneously 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, a diaryl carbonate may be obtained simultaneously with the alkyl aryl carbonate I31506.doc • 64· 200948759, and in this case, it may be directly implemented. Uneven reaction. The heterogeneous reaction is also a step of obtaining an alkyl aryl carbonate by transesterification of a dialkyl carbonate with an aromatic hydroxy compound as described above, and in order to favorably promote the equilibrium reaction, while discharging the alcohol The second method of reaction is more advantageous. The heterogeneous reaction is also limited by the balance. Therefore, in order to proceed favorably, one of the dialkyl carbonate and the diaryl carbonate formed by the heterogeneous reaction is discharged to the outside of the system for reaction. The method is more advantageous. In the present embodiment, it is preferred that the alkoxy group or the aryl group be selected so that the boiling point of the dialkyl carbonate is lower than that of the diaryl carbonate, and the dialkyl carbonate is discharged to the system. The outer side is subjected to an uneven reaction. The discharged dialkyl carbonate can be used in the step before returning to the heterogeneous reaction. If it is desired to increase the production amount of the diaryl carbonate, 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. There are also many examples of such catalysts. As such a catalyst, for example, a Lewis metal acid and a transition metal compound capable of generating a Lewis acid, a polymer tin compound, and a formula RX(=0)0H (wherein X is selected from Sn and Ti, r is proposed) a compound represented by Hf hydrocarbon group, a mixture of a Lewis acid and a protonic acid, a wrong catalyst, a compound of a chin or a wrong compound, a tin compound, a compound such as Sc, Mo, Mn, Bi, or Te. As the heterogeneous reaction catalyst of the present embodiment, the same catalyst as the transesterification catalyst used in the vinegar exchange step can be used. The alkyl aryl carbonate alkyl aryl carbonate used in the heterogeneization step. Examples of the alkyl aryl carbonate include methylphenyl carbonate, ethylene carbonate 131506, doc-65·200948759 phenyl phenyl ester, propyl phenyl carbonate (each isomer), and butyl phenyl carbonate (each Isomers), allyl phenyl carbonate (each isomer), amyl phenyl carbonate (each isomer), hexyl phenyl carbonate (each isomer), heptyl phenyl carbonate (isomeric , octyl phenyl phenyl carbonate (each isomer), decyl carbonate (ethyl phenyl) (each isomer), decyl phenyl (butyl phenyl) ester (each isomer), Methyl acetal carbonate (each isomer), ethyl toluene acetonate (each isomer), propyl cresyl carbonate (each isomer), butyl phenyl phenyl carbonate (each isomer), Benzyl carbonate toluene (each isomer), methyl phthalic acid carbonate (isomeric products), methyl (trimethylphenyl) carbonate (each isomer), methyl carbonate ( Gas phenyl) ester (each isomer), methyl (nitrophenyl) carbonate (each isomer), methyl (methoxyphenyl) carbonate (each isomer), carbonic acid (acridinyl) vinegar (each isomer), ethyl cumyl carbonate (each isomer), methyl (phenylnonylphenyl) carbonate (each isomer), ethyl carbonate Toluene ester (each isomer), benzyl cresyl carbonate (each isomer), and the like. These alkyl aryl carbonates may be used alone or in combination of two or more. φ In the above-mentioned carbonic acid aryl esters, in the present embodiment, the alcohol constituting the aryl aryl carbonate has a boiling point higher than that of water, and is selected from the following alcohols: constituting an alkyl aryl carbonate The boiling point of the alcohol is lower than the boiling point of the aromatic hydroxy compound constituting the alkyl aryl carbonate. For example, the alkyl alcohol having a linear or branched number of alkyl groups of 4 to 12 has a linear chain or a branched alkenyl alcohol having 4 to 12 alkenyl groups, a cycloalkyl alcohol, or an aralkyl alcohol; in order to favorably promote the heterogeneous reaction, it is considered to remove the carbonic acid formed by the heterogeneous reaction. The monoalkyl ester is preferably a dialkyl carbonate having a boiling point lower than that of the diaryl carbonate obtained by the heterogeneous reaction. As such an optimum combination, 131506.doc -66· 200948759 exemplifies an alcohol, an alkoxy group corresponding to a metal compound having a metal-carbon-oxygen bond represented by the above formula (9) and formula (1). The alcohol and the dialkyl carbonate 6-blind alcohol are selected from the group consisting of pentanol (each isomer), hexanol (each isomer), and heptanol (each isomer). The compound is selected from the group consisting of phenol and carbamide. The compound supplied to the unevenness step is mainly an alkyl aryl carbonate, and if necessary, the catalyst can be mixed with impurities which do not particularly adversely affect the reaction. In the case where the catalyst is used in the present embodiment, the amount of the catalyst depends on the type of the catalyst to be used, the type of the reactor, the type or amount of the alkyl aryl carbonate, the reaction temperature, the reaction temperature, and the like. The ratio is usually 0.0001 to 50% by weight, based on the weight of the carbonated aromatic vinegar as a raw material to be supplied. Further, in the case of using a solid catalyst, it is preferable to use a catalyst amount of 〇1〇75% by volume relative to the empty column volume of the reactor. These feedstocks may contain alcohols, aromatic hydroxy compounds, diaryl carbonates, etc., and the reaction is reversible. Therefore, when the concentration is too high, the reaction rate of the raw materials may be lowered. Not good. The reaction time of the heterogeneous reaction varies depending on the reaction conditions or the type or internal structure of the reactor, and is usually 0.001 to 50 hours, preferably 〇1 to 1 Torr, more preferably 0.05 to 5 hours. The reaction temperature varies depending on the type of the aryl carbonate to be used, and it is usually carried out at a temperature of from 50 ° C to 350 ° C, more preferably from 100 ° C to 280 ° C. Further, the reaction pressure varies depending on the type of the raw material compound to be used, the reaction temperature, etc., and may be any of reduced pressure, normal pressure, and pressurization 'usually in the range of 10 Pa to 20 MPa, and 131506.doc -67- Line 200948759. In the present embodiment, the unevenness step -^^ γ does not require the use of a solvent for the purpose of facilitating the reaction, and an appropriate inert solvent such as an ether, an aliphatic hydrocarbon or an aromatic gun is used. Classes, halogenated aliphatic hydrocarbons, i-chemical aromatic hydrocarbons, etc., ^ ^ ^. Further, it is possible to coexist an inert gas such as nitrogen gas, gas gas or chlorine gas as a substance having a reaction amount of = in the reaction system, and to produce a low-boiling by-product formed by phase addition, from the continuous ❹ multistage steaming tower below, The above-mentioned inert gas or a low-melting organic compound inert to the reaction is introduced as a gas. After the completion of the heterogeneous reaction, the catalyst, the carbonated vinegar, the aromatic sulfhydryl compound, and the alcohol are separated by a well-known method to obtain a diaryl carbonate. The form of the reactor to be exchanged in the vinegar exchange step and the unevenness step is particularly limited, and the method of using a buffer tank, a multi-stage tank, a multi-stage distillation tower, and the like, and the like are used. Various methods are well known. These reactors can also be used in either batch or continuous mode. In order to effectively balance the equilibrium (4), it is preferred to use a multi-stage steaming tower, and it is particularly preferable to use a continuous method of a multi-stage steaming tower. The multi-stage steaming tower refers to a distillation column having a plurality of stages in which the number of theoretical plates of distillation is two or more, and may be any I if it is capable of continuous steaming. As such a multi-stage distillation column, for example, a slab type of a blister sheet, a perforated tray, a valve tray, a countercurrent tray, or the like, or a Lacy ring, a Lexin ring, and a ball are used. Ring, arc saddle packing, saddle ring packing, Dickson packing, net saddle packing, spiral packing, wire mesh corrugated packing, orifice corrugated packing, etc. 131506.doc -68- 200948759 Ο 填充 之 之 填充 填充 方式Any one can be used as a user of a multi-stage distillation column. Further, it is also preferable that the laminate portion and the filler-filled portion are combined to form a laminate-filled mixing tower. When a continuous process is carried out using a multi-stage steaming tower, the starting material and the reaction material are continuously supplied to a continuous multi-stage distillation column in which the liquid phase or gas is present in the presence of a metal-containing catalyst. - a liquid phase undergoes a transesterification reaction between two substances, and/or a heterogeneous reaction 'at the same time' from the manufacture of a high boiling reaction mixture comprising an alkyl aryl vinegar and/or a diaryl carbonate from the lower part of the distillation column The liquid is discharged, and on the other hand, a low-boiling reaction mixture containing the by-product formed is continuously discharged in a gaseous form by distillation from the upper portion of the distillation column to produce a diaryl carbonate. The above description shows the production example of the diaryl carbonate using the dialkyltin compound. In addition to the above steps (1) to (3), the following steps (4) and (5) can be carried out. Step (4): a step of reacting the residual liquid obtained in the step (2) with an alcohol to form an organotin compound having a tin-oxygen-carbon bond and water 'removing the water from the reaction system. Step (5): The organotin compound having a tin-oxygen-carbon bond obtained in the step (4) is reused as the step of the organotin compound having a tin-oxygen-carbon bond in the step (1). Step (4) A step of reacting the residual liquid obtained in the step (2) with an alcohol to regenerate the dialkyltin compound. The alcohol used in this step is decyl alcohol, ethanol, propanol (each isomer), butanol (each isomer), pentanol (each isomer), hexanol (isomeric 131506.doc -69-200948759), heptanol (each isomer), octanol (each isomer), decyl alcohol (each isomer), sterol (each isomer) and other alcohols, can be preferably used The number of carbon atoms constituting the alcohol is selected from the group consisting of an integer of 1 to 12, and more preferably the same alcohol as used in the alkyltin alkoxide synthesis step described above. It is preferred that the dehydration reaction is also carried out under the same conditions as in the above alkyl tin 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. The reaction solution can also be sampled and confirmed by the method of n9Sn-NMR. In order to produce the mixture of the present embodiment in the step (1), it is confirmed that the following composition is obtained, that is, the tetraalkyldane contained in the alkyl tin alkoxide composition obtained by the above reaction is completed. The molar ratio of oxydistannoxane to dialkyltin dialkoxide, in combination with the moir/❶ of the two, is '0: 100 to 80: 20', and more preferably 1 〇: A composition ranging from 90 to 70:30. The alcohol to be used may be used as it is in a coexistence state, or may be used by distilling off the alcohol depending on the case. It has the advantage of reducing the inverse φ of the other steps, so it is better to remove the alcohol as much as possible. The removal method preferably uses the well-known distillation removal, and the steaming station used for the distillation can use the well-known steaming equipment. As a preferred steaming device, 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, the dialkyltin oxide as a solid is usually not used, so the reactor is less restrictive. Namely, the form of the reactor for the dehydration reaction is not particularly limited, and a well-known groove-like or column-shaped reactor can be used. The low-boiling reaction mixture containing water is discharged from the reactor by gas distillation, and the alkyl stannate is oxidized by 13 15 〇6, (J〇q -70-200948759 or sulphur tin 16 oxide mixture) The high-boiling reaction mixture is discharged from the lower part of the reactor as a liquid. As such a reactor, for example, a mixing tank, a multi-stage mixing tank, a steaming tower, a multi-stage steaming tower, a multi-tubular reactor, continuous Multi-stage steaming tower, packed tower, thin film evaporator, reactor with support inside, forced circulation reactor, falling film evaporator 'drop drop evaporator, fine flow phase reactor, bubble column reactor Various methods, such as a method of combining these methods, etc., in which the balance is effectively biased toward the side of the formation system, it is preferable to use a tower reactor, and the water formed by the better crucible is rapidly transferred to the gas. A structure in which the gas-liquid contact area is large. Particularly preferred is a continuous method in which a multi-tubular reactor and a multi-stage distillation packed column with a filler are used. If no adverse effects are caused, the reactor and the piping are material It can be any known material, such as SUS304 or SUS3!6, SUS3]. It is cheaper, so it can be used well. It can be attached with measuring instruments such as flow meters and thermometers, reboiler, condenser, etc. A well-known treatment device; heating can be carried out by a well-known method such as a base gas or a heater, and a well-known method such as natural cooling, cooling water, or brine can be used for cooling. The dialkyl tin compound produced in the above step (4) By the step (human) (reusing the step and then using the bismuth tin oxide used in the step (1), the step 5 is the organic compound having the tin-oxygen-carbon bond obtained in the step (4). The tin compound is further used as the organotin compound having a tin-oxygen-carbon bond in the step (1). As the amine compound used in the production method of the present embodiment, an amine compound represented by the following formula (13) is used. Rs(nh2) η (13) (wherein π represents an aliphatic group selected from the group consisting of carbons and oxygen atoms (4) and an aromatic group having a carbon number of 6 to 20 Group of people One base 'and has an atomic valence equal to η, and η is an integer from 1 to 10.) It is preferable that 11 is 1 to 3 in the above formula (13), and a good η is 2 An amine compound. Examples of such a polyamine compound include hexamethylenediamine, methylene bis(cyclohexylamine) (each isomer), cyclohexanediamine (each isomer), and 3-amino group. Aliphatic diamines such as methyl-3,5,5·trimethyl lutyl hexylamine (each isomer), phenyldiamine (each isomer), and methylidene diamine (isomeric) An aromatic diamine such as 4,4,_methylenediphenylamine. Among them, hexamethylenediamine, 4,4-methylenebis(cyclohexylamine) (each isomer), cyclohexane II are preferably used. An aliphatic monoamine such as an amine (each isomer) or 3-aminomethyl-3,5,5-trimethylcyclohexylamine (each isomer), wherein hexamethylenediamine, 4 is further preferably used. 4,-methylenebis(cyclohexylamine), 3-aminomethyl-3,5,5-trimethylcyclohexylamine. The amine compound is preferably supplied to the reactor for producing the urethane in a liquid helium state. In general, the amine compound exemplified above is mostly solid at normal temperature (for example, 20 C). In this case, the amine compound may be heated to a melting point or higher to be supplied as a liquid, but if it is too high When an amine compound is supplied at a temperature, a side reaction such as a heat modification reaction may be generated by heating. Therefore, it is preferred to use the amine compound as a mixture with an alcohol, water or a carbonate of I31506.doc • 72·200948759. It is supplied in a liquid state at a relatively low temperature. Ο ❿ The reaction conditions vary depending on the compound of the reaction, and the ratio of the amine group of the amine compound is in the stoichiometric ratio so as to increase the reaction rate, so that the reaction is completed earlier, preferably The amount of the carbonate relative to the amine group of the amine compound is an excess amount, and in view of the size of the reactor, it is preferably in the range of 2 to 100 times, and more preferably in the range of 25 to 3 times. The reaction temperature is usually normal temperature (2 (rc) to 2 〇 (the range of rc, in order to increase the reaction rate, it is preferably a high temperature, and on the other hand, it may cause an adverse reaction at a high temperature, and therefore it is preferably 5 (rc). ～15 (the range of rc. For the fixed reaction temperature, a well-known cooling device and heating device may be provided in the above reactor. Further, the reaction pressure may be reduced or decreased depending on the kind of the compound to be used or the reaction temperature. Any of pressure and pressure is usually carried out in the range of 〇2〇~ΐχ 1〇6 Pa. There is no particular limitation on the reaction time (the residence time in the case of the continuous method), and it is usually 0.001 to 50 hours, preferably It is 〇.〇1 ίο小时' is more preferably G1~5 hours. It is also possible to use a reaction liquid, for example, to confirm the formation of a desired amount of aryl carbamate by liquid chromatography, and to terminate the reaction. In the 'optional use of catalysts, such as tin, antimony, steel, titanium and other organometallic compounds or inorganic metal compounds, metallurgical, soil-based metal alkoxides, clock, nano, unloading, about, pin, ethanolate Butanolate (each isomer) Initiative catalysts, etc. The actual 7-state towel 'does not have to use a reaction solvent to make the reaction operation easy to be different. I: &quot;7 use a suitable solvent' such as hexane (each isomer), heptane (each substance) ), etc.: 冓 壬 壬 壬 各 各 各 各 各 各 各 各 各 各 各 各 各 各 各 各 各 各 各 各 各 各 各 各 各 各 各 各 ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( Each isomer), dibutylbenzene (each isomer smoke and topographical substituted aromatic hydrocarbons; f alcohol, ethanol, propanol tr: family), butanol (different, alcohol, Isobutanol (each isomer), cut (each isomer), heptanol (each isomer), octanol (alcohols such as isomers. Μ * (each isomer), 壬Alcohols (each isomer) and other alcohols such as 'chlorine, di-benzene (each isomer), bromobenzene'), chloronaphthalene, naphthalene, nitrobenzene, and odor (isophthalene naphthalene, etc.) Substituting t compounds by halogen or nitro; biphenyl, substituted biphenyl, diphenyl methyl, three

Polycyclic hydrocarbon compounds such as ruthenium, osmium, and bis-phenylene (each isomer); cumbersome, methyl benzene (each isomer), ethyl benzene (each isomer), butyl phenol ( Each isomer), amyl phenol (each isomer), dimethyl phenol (each isomer), diethyl benzene (each isomer), dibutyl benzene (each isomer) : an aromatic hydrocarbyl compound such as dipentylbenzene (each isomer); an aliphatic hydrocarbon such as cyclohexane, cyclopenta, cycloxinine or ethylcyclohexan; cyclohexanol, cyclopentanol And cycloaliphatic alcohols such as cyclooctanol; methyl ethyl ketone, acetophenone, etc.; dibutyl phthalate, dioctyl phthalate, benzyl butyl phthalate, etc. Examples; ethers such as diphenyl ether and diphenyl sulfide; and thioethers; sulfoxides such as dimercaptosulfoxide and diphenyl sulfoxide are used as reaction solvents. These solvents may be used singly or as a mixture of two or more. Further, a dialkyl carbonate which is used in excess with respect to the amine group of the amine compound is also suitably used as a solvent for the reaction. The reaction apparatus used in carrying out the reaction is not particularly limited, and a well-known reactor can be used. For example, a previously known reactor such as a stirred tank, a pressurized agitation tank, a reduced-type stirring tank, a column type reactor, a distillation column, a packed column, and a thin film still can be suitably used in combination. The material of the reactor 131506.doc 74- 200948759 There are also no special restrictions, you can borrow poorly known materials. For example, it is also possible to use glass, stainless steel, carbon &amp; + &amp; everyone, HasteHoy, or apply a glass to the substrate, or to carry out iron fluoride. Lun (registered trademark) coated. &lt;Removal of hydroxy compound&gt; The above example does not contain a reaction liquid obtained by a reaction of a carbonated acetal with an amine compound, and the reaction liquid can be directly supplied to the heat of the carbamic acid.

In the reactor to be decomposed (hereinafter referred to as a thermal decomposition reactor), the amino group (tetra) may be purified from the reaction liquid and supplied to the thermal decomposition reactor 1 to be thermally decomposed by the amino group The isocyanate formed by the reaction will be subjected to radicalization. The reaction of the alcohol (and the alcohol-based compound) to form the amino formate vinegar is to increase the reaction efficiency of the thermal decomposition reaction. It is preferred to remove the radical from the reaction solution before the thermal decomposition reaction. Compound (alcohol and/or aromatic hydroxy compound). In the present embodiment, the urethane may be purified and supplied to the thermal decomposition reactor by the following method: using the hydroxy compound and/or carbonic acid from the reaction solution by distillation a method of distilling a low-boiling component such as a reaction solvent in the case of an ester and/or a reaction solvent, or a method of purifying a solvent which is inert to a urethane and has a low solubility to a urethane Or a well-known method such as purification by crystallization. Among these methods, 'if it is easy to handle the operation, etc., it is preferred to carry out the low-boiling component such as the reaction solvent when the hydroxy compound and/or the carbonate and/or the reaction solvent are used by distillation. Method for Distillation 0 131506.doc • 75- 200948759 As a device for separating a hydroxy compound or a carbonate from the reaction liquid by distillation, a well-known distillation apparatus can be used. For example, a method using a distillation column, a multi-stage distillation column, a multi-tubular reactor, a continuous multi-stage distillation column, a packed column, a thin film evaporator, a falling film evaporator, a falling-drop evaporator column, and the like a method of combining, and the like. The conditions for carrying out the distillation separation also depend on the kind of the compound contained in the reaction liquid, and it is preferably in the range of normal temperature (20 C) to 180 ° C, and sometimes causes an adverse reaction at a high temperature, so it is preferably 5 (TC to 15 (the range of TC) is a fixed reaction temperature, and a well-known cooling device and a heating device can be provided in the above reactor. Further, the pressure varies depending on the kind of the compound contained in the reaction liquid or the reaction temperature, and may be Any of decompression, normal pressure, and pressurization is usually carried out in the range of 2 〇 to 1 χ 1 〇 6. Especially in the case of this distillation separation, when it is operated at a high temperature for a long period of time, 'this sometimes occurs. The thermal modification reaction of the amino phthalate contained in the reaction liquid lowers the yield of the amino phthalate, so it is preferred to reduce the pressure as close as possible to the degree of decompression that can be achieved by the distillation apparatus. The temperature range is a temperature range sufficient for vapor phase distillation of the compound to be removed from the reaction liquid, and the amino phthalate or the mixture containing the urethane after distillation separation may be used. As a liquid In the temperature range that exists, 'select the temperature as low as possible. The main purpose of the steaming operation is to separate the radical compound (alcohol and/or aromatic warp group compound) from the reaction liquid. It is preferred to use the reaction liquid. In the case of the carbonate and the reaction solvent contained in the solvent, the reaction solvent is also separated because the following thermal decomposition reaction is carried out in the state containing the carbonate and/or the reaction solvent, and it is sometimes necessary to generate The step of separating the isocyanate or the hydroxy compound, 131506.doc -76- 200948759 complicates the operation. When the hydroxy compound and/or carbonate are separated and recovered in the reaction, and the reaction solution contains a solvent, it is preferred to separately The solvent is reused, and the base material is reused as a hydroxy compound (alcohol and/or aromatic warp compound) in the carbonate production step, and the carbonated vinegar is used as a carbonate for the production of urethane, and the solvent is reused. When a urethane is used as a solvent for producing a urethane and a urethane is used for the production of a urethane, when the catalyst contains a catalyst or a catalyst residue, The catalyst contained in the reaction liquid or the amino carboxylic acid vinegar is used as a catalyst for the hot knife reaction, or the catalyst can be removed from the reaction liquid or the amine phthalic acid vinegar, especially using an organic catalyst. In some cases, the reaction from the catalyst may be caused during the thermal decomposition reaction, and the yield may be lowered. Therefore, in this case, it is preferred to carry out the thermal decomposition reaction after removing the catalyst. The method M is a better method, which is a method of neutralizing the towel by an organic acid or a mineral acid in a homogeneous phase or a heterogeneous phase. The catalyst is preferably a mono- and di-acid, a hospital base. Or aryl sulfonic acid and phosphoric acid, ion exchange resin, activated carbon, etc., the catalyst is removed, and the amino acid is solidified at a low temperature, and sometimes a thermal modification reaction occurs at a temperature, so at room temperature ((10) It is preferably carried out within the scope of the preparation of the urethane. It is preferred to continue after the step of producing the amide formic acid, while maintaining the temperature at which the amino carboxylic acid vinegar formed from the reaction solution of the amide formic acid is not precipitated. Implementation. In the case where the solvent and/or the hydroxy compound and/or the carbonate are separated from the reaction liquid in the step of producing the amino carboxylic acid vinegar, it is preferred to carry out the above separation operation after removing the catalyst from the reaction liquid.疋131506.doc -77 200948759 &lt;Transportation of carbamate&gt; Amino phthalate-containing reactant obtained by reaction of a carbonate with an amine compound (hereinafter referred to as "reactant") or from The reaction solution is supplied to the thermal decomposition reactor by removing the urethane-containing mixture (hereinafter referred to as a residue) of the base compound by the above method. The urethane is liable to form a chlorine bond between molecules by constituting an ester group of an amino phthalate, and thus mostly has a relatively high melting point. When transporting a melamine carboxylic acid having a higher melting point, for example, it may be transported to a deformer for pulverizing or processing the solid amide phthalate, or to heat the urethane to two. The amino phthalate is transported in a liquid form at the temperature of the melting point. However, in the case of transporting the shaped aryl aryl phthalate, it often causes clogging of the transport line, or in order to stably transport a certain amount when the shape of the urethane is uneven. A urethane requires a complicated device 'or a step of controlling the shape of the urethane to a certain range. Therefore, the reactant or the residue is preferably transported in a liquid state.时 When the reactant or the residue is transported in a liquid state, it is preferable to heat to a higher temperature in consideration of solidification during transportation, but the reaction is often generated if it is transported at an excessively high temperature. The thermal modification reaction of the urethane contained in the liquid or the residue is therefore preferably in the range of 3 〇〇 c 2 to 2 Torr, more preferably 50 ° C to 180 °. It is preferably transported at a temperature ranging from 80 ° C to 150 ° C. &lt;Thermal decomposition reaction of urethane&gt; Next, the production of isocyanate by thermal decomposition reaction of urethane is described. 131506.doc -78- 200948759 The thermal decomposition reaction in the present embodiment is a reaction between an isocyanate and a hydroxy compound (alcohol or an aromatic hydroxy compound) corresponding to the formation of an amino phthalate. The reaction temperature is usually in the range of loot to 35 (rc), in order to increase the reaction rate, preferably high temperature, and on the other hand, sometimes at a high temperature, it may be caused by a urethane and/or an isocyanate as a product. The side reaction as described above is therefore preferably in the range of 15 (TC to 3 〇〇t. In order to fix the reaction temperature, a well-known cooling device and a heat treatment device can be provided in the above reactor. X, the reaction pressure is based on The type of the compound to be used or the reaction temperature may be any of a pressure reduction, a normal pressure, and a pressurization, and it is usually carried out in the range of 20 to 1×10 6 Pa. The reaction time (the residence time in the case of the continuous method) is not The limit is usually 〇.〇〇1~1〇〇, preferably 0.005~50 hours, more preferably 〇.〇1~hour. Keep the urethane at a temperature for a long time. In some cases, a side reaction as described above may occur. Further, the isocyanuric acid produced by the thermal decomposition reaction sometimes causes a side reaction as described above. Therefore, the amino phthalate and the The time the isocyanate is kept at the station temperature Preferably, the thermal decomposition reaction is preferably carried out in a continuous process as short as possible. The continuous process means that the mixture containing the urethane is continuously supplied to the reactor for thermal decomposition reaction. a method of continuously discharging the produced isocyanate and hydroxy compound from the thermal decomposition reactor. The low-boiling component formed by the thermal decomposition reaction of the amine odorous formic acid vine in the continuous method is preferably used as a gas phase component. The upper part of the thermal decomposition reactor is recovered, and the residue is recovered as a liquid phase component from the bottom of the thermal decomposition reactor. All the compounds present in the thermal decomposition 131506.doc •79·200948759 reactor can also be used as gas phase components. Recycling, by dissolving the liquid phase component in the thermal decomposition reactor, and dissolving the polymer compound formed by the side reaction caused by the amino carboxylic acid vinegar and/or the isocyanate to prevent the adhesion of the polymer compound And the effect of accumulating in the thermal decomposition reactor. The thermal decomposition reaction of the urethane produces an isocyanate and a trans-base compound At least one of the compounds is recovered as a gas phase component. The recovery of which compound as a gas phase component depends on the thermal decomposition reaction conditions. Here, the phrase "by urethane" is used in the present embodiment. The low-boiling component formed by the thermal decomposition reaction corresponds to a hydroxy compound and/or isocyanate produced by the thermal decomposition reaction of the amino carboxylic acid vinegar, especially in the case of performing the thermal decomposition reaction. A compound which can be used as a gas. A method of recovering a liquid phase component containing a urethane and/or a carbonate by recovering an isocyanate and a hydroxy compound formed by a thermal decomposition reaction as a gas phase component In the method, the isocyanate and the hydroxy compound can be separately recovered by using a thermal decomposition reactor. The recovered gas phase component containing isocyanate is preferably supplied in a gas phase to a device for purifying and separating the isogastric acid. . The liquid phase component containing the amine group and/or the carbonate is recovered from the bottom of the thermal decomposition reactor, and part or all of the liquid phase component is supplied to the upper portion of the thermal decomposition reactor to make the aminocarboxylic acid Again: owing to thermal decomposition reaction. Here, the upper part of the thermal decomposition reactor, for example, when the thermal decomposition reactor is a distillation column, refers to the number of theoretical plates from the bottom of the tower to the second and above, and the heat is 131506.doc. -80· 200948759 When the reactor is a thin film distiller, it means the part above the heat transfer part. 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 kept at 50 ° C to 180 ° C, more preferably 7 ° ° (: ~ 17). 〇°0:, more preferably 1〇〇.匚~150. (3. Transportation. When the liquid phase component contains a carbonate, the carbonate can be separated and recovered from the liquid phase component, and the solution is The phase component is supplied to the thermal decomposition reactor. The carbonate recovered and recovered can be preferably reused. As described above, it is preferred that the liquid phase component is from the thermal decomposition reactor in the thermal decomposition reaction. The bottom is recovered because the polymer formed by the side reaction caused by the urethane and/or isocyanate can be obtained by allowing the liquid phase component to be present in the thermal decomposition reactor. The by-product is dissolved and discharged as a liquid phase component from the thermal decomposition reactor, thereby reducing the adhesion of the polymer-like compound and accumulating in the thermal decomposition reactor. Part or all of the liquid phase component is supplied to The upper part of the Q of the thermal decomposition reactor, the amino phthalate The thermal decomposition reaction is carried out once, and if this step is repeated, a polymer-form by-product may be accumulated in the liquid phase component. In this case, part or all of the liquid phase component may be removed from the reaction system to reduce polymerization. The accumulation of the by-products of the material or the concentration is maintained at a fixed concentration. The hydroxy compounds and/or carbonates contained in the gas phase component and/or the liquid phase component obtained in the above thermal decomposition reaction can be separately separated and recovered and reused. And 5, the trans-base compound can be reused as the I-based D of the step (7) for producing carbonated vinegar, and the 'carbonate can be reused as a raw material for producing the amino phthalate. 131506.doc 200948759 The thermal decomposition reactor Form and i special..., will be restricted, for efficient recycling

The milk phase component is preferably a well-known distillation apparatus. For example, the expansion includes a distillation column, a multi-stage distillation column, and a multi-tubular reactor: a distillation column, a packed column, a thin film evaporator, a counter having a support inside, a forced circulation reactor, a falling film evaporator, Any of the well-known methods, such as the manner of the reactor, and the manner in which the reactors are combined. From the viewpoint of rapidly removing low-boiling components from the reaction system, it is preferred to use a tubular reactor, and more preferably a tubular thin film evaporator, a tubular falling film evaporator or the like, preferably = It is a structure in which the generated low-boiling component is rapidly transferred to the gas phase with a large gas-liquid contact area. If the urethane or the hydroxy compound as a product, the sulphuric acid vinegar or the like is not adversely affected, the material of the thermal decomposition reactor and the piping may be

Any material known in the art, among which SUS304 or SUS316, SUS316L, etc. are relatively inexpensive, can be preferably used. &lt;Cleaning of Thermal Decomposition Reactor&gt; In the present embodiment, the thermal decomposition reaction of the amino phthalic acid ester is, for example, represented by the above formula (2), formula (3), formula (4), and the like. When a by-product of the side reaction, such as a by-product of the thermal decomposition reaction, is thermally decomposed by the above method, it may adhere to the thermal decomposition reactor during long-term operation. When these compounds adhering to the thermal decomposition reactor are accumulated to some 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 decompose the thermal reactor to perform cleaning or the like. The present inventors have surprisingly found that the compound attached to the thermal decomposition reactor is easily dissolved in an acid. Based on this knowledge, consider the following method: when the high-boiling substance adheres to the thermal decomposition reaction, the wall of the thermal decomposition reaction is cleaned with acid, and the dissolved material is high (four), and the reactor is removed from the age. This completes the cleaning of the thermal decomposition reactor (especially the wall surface). According to this method, the thermal decomposition reactor can be cleaned without disintegration, and the wall surface of the thermal decomposition reactor can be cleaned, so that the operation stop time of the thermal decomposition reactor can be greatly shortened, and the isocyanate production efficiency is high. The acid to be used as the cleaning solvent is not particularly limited as long as it dissolves the polymer-form by-product, 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 phenol, an enol, a thiophenol, a quinone, an anthracene or an aromatic sulfonamide. Acid, phenols. Examples of such a chemical substance include: citric acid, acetic acid, propionic acid, n-butyric acid, isobutyric acid, valeric acid, isovaleric acid, 2-mercaptobutyric acid, pivalic acid, caproic acid, isohexanoic acid, 2-ethylbutyric acid, 2,2-dimethylbutyric acid, heptanoic acid (each isomer), octanoic acid (each isomer), citric acid (each isomer), citric acid (each isomer) ), undecanoic acid (each isomer), dodecanoic acid (each isomer), tetradecanoic acid (each isomer), hexadecanoic acid (variety)

Structure), acrylic acid, crotonic acid, methacrylic acid, ethylene acetic acid, mercaptoacrylic acid, angelic acid, cis acid, decyl acetic acid, undecylenic acid (di-structure), etc., saturated or unsaturated aliphatic monocarboxylic acid Acid compounds, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid (each isomer), suberic acid (each isomer), azelaic acid (each isomer) , azelaic acid (each isomer), maleic acid, fumaric acid, methyl maleic acid, methyl antibutene II 131506. Doc -83· 200948759 A saturated or unsaturated aliphatic dicarboxylic acid such as acid, glutaconic acid (isomer), itaconic acid or allylmalonic acid, i,2,3·propanetricarboxylic acid, a saturated or unsaturated aliphatic dicarboxylic acid compound such as hydrazine, 2,3-propene tricarboxylic acid, 2,3·didecyl butyl hydride, 2,3-tridecanoic acid, benzoic acid, methyl benzoate ( Each isomer), ethyl benzoate (each isomer), propyl benzoate (each isomer), dinonyl benzoate (each isomer), trimethyl benzoate (isomeric) An aromatic monocarboxylic acid compound such as phthalic acid, isophthalic acid, terephthalic acid or methyl isophthalic acid (each isomer), 1, 2, 3 -Aromatic tricarboxylic acid compounds such as benzotriazole® acid, 1,2,4-benzenetricarboxylic acid, 13,5-benzenetricarboxylic acid, phenol, methyl phenol (each isomer), ethyl phenol ( Each isomer), propyl-phenol (each isomer), butyl-phenol (each isomer), pentyl-phenol (each isomer), hexyl-p-phenol (each isomer), Heptyl-phenol (each isomer), octyl-phenol ( Isomers), mercapto-phenol (each isomer), mercapto-phenol (each isomer), dodecyl-phenol (each isomer), phenylphenol (each isomer), Monosubstituted phenols such as phenoxyphenol (each isomer), cumyl-phenol (each isomer), dimethylphenol (each isomer), diethyl benzene (different) Structure), dipropyl-benzoin (each isomer), dibutyl-benzoin (each isomer), dipentyl-phenol (each isomer), dihexyl-phenol (isomeric) , diheptyl-phenol (each isomer), dioctyl-phenol (each isomer), dimercapto-phenol (each isomer), dimercapto-phenol (each isomer) , di(dodecyl)-phenol (each isomer), diphenyl-phenol (each isomer), diphenoxyphenol (each isomer), dicumyl-phenol (each Isomers), methyl ethyl phenol (each isomer), methyl-propyl-phenol (each isomer), mercapto-butyl-phenol (each isomer), methyl Pentyl-phenol (each isomer), 131506. Doc 84· 200948759 Mercapto-hexyl-phenol (each isomer), methyl-heptyl-phenol (each isomer), methyl-octyl-phenol (each isomer), methyl-mercapto - phenol (each isomer), mercapto-mercapto-p-phenol (each isomer), methyl-dodecyl-p-phenol (each isomer), methyl-phenyl-phenol (each Isomers), methyl-phenoxyphenol (each isomer), methyl-isopropylphenyl-phenol (each isomer), ethyl-propyl-phenol (each isomer), B Base-butyl phenol (each isomer), ethyl-pentyl phenol (each isomer), ethyl-hexyl-phenol (each isomer), ethyl heptyl phenol (each isomer) , ethyl-octyl phenol (each isomer), ethyl-mercapto-phenol (each isomer), ethyl-mercapto-phenol (each isomer), ethyl-dodecyl _Phenol (each isomer), ethyl-phenyl-phenol (each isomer), ethylphenoxyphenol (each isomer), ethyl-cumylphenol-phenol (each isomer) ), propyl-butyl-phenol (each isomer), propyl-pentyl-phenol (each isomer), propyl- Hexyl-phenol (each isomer), propyl-heptyl-phenol (each isomer), propyl-octylphenol (each isomer), propyl-mercapto-phenol (each isomer) ), propyl-mercapto-p-phenol (each isomer), propyl-dodecylphenol (isomeric Q), propyl-phenyl-phenol (each isomer), propyl- Phenoxyphenol (each isomer), propyl-isopropylphenyl-phenol (each isomer), butyl-pentylphenol (each isomer), butyl-hexyl-phenol (isomeric , butyl-heptyl-phenol (each isomer), butyl-octyl-phenol (each isomer), butyl-mercapto-phenol (each isomer), butyl-fluorenyl - phenol (each isomer), butyl-dodecyl-phenol (each isomer), butyl-phenyl-phenol (each isomer), butyl-phenoxyphenol (isomeric , butyl-cumyl-phenol (each isomer), pentyl-hexyl phenol (each isomer), pentyl-heptyl-phenol (iso-isomer), pentyl- Octyl-phenol (each isomer), amyl-mercapto-phenol (each isomer), pentane 131506. Doc -85 - 200948759 thiol-phenol (each isomer), pentyl-dodecyl-phenol (each isomer), pentyl-phenyl phenol (each isomer), pentyl -phenoxyphenol (each isomer), pentyl-cumyl-phenol (each isomer), hexylheptyl-phenol (each isomer), hexyl-octyl-phenol (variety) Structure), hexyl-mercapto-phenol (each isomer), hexyl-mercapto-phenol (each isomer), hexyl-dodecyl-phenol (each isomer), hexyl-phenyl- Phenol (each isomer), hexyl-phenoxybenzene (each isomer), hexyl-cumyl-phenol (each isomer), heptyl-octyl-phenol (each isomer) , heptyl-fluorenyl-phenol (each isomer), heptyl-mercapto-phenol (each isomer), heptyl-dodecyl-phenol (each isomer), heptyl-benzene Base-phenol (each isomer), heptyl-phenoxyphenol (each isomer), heptyl-isopropylphenyl-benzene (each isomer), octyl-fluorenyl-benzene Each isomer), octyl-decyl-phenol (each isomer), octyl-dodecyl-phenol (each isomer), octyl-phenyl-phenol (each isomer), octyl-phenoxyphenol (each isomer), octyl-isopropylphenyl-phenol (each isomer) , fluorenyl-fluorenyl-benzone (each isomer), decyl-dodecyl-p-phenol (isomeric saccharide), mercapto-phenyl-phenol (isomer), sulfhydryl -phenoxyphenol (each isomer), mercapto-isopropylphenyl-benzene (each isomer), twelfth-phenyl-phenol (each isomer), dodecyl- Disubstituted benzenes such as phenoxyphenol (each isomer), dodecamidyl-cumyl-benzene age (each isomer), trimethyl _ _ _ (isomer), three Ethyl-benzophenone (each isomer), tripropyl-benzene (each isomer), tributyl-phenol (each isomer), tripentyl-phenol (each isomer), three Hexyl-phenol (each isomer), triheptyl-phenol (each isomer), dioctyl-benzene (each isomer), tridecyl-benzene (iso-isomer), thirteen Pyridyl-phenol (each isomer), tris(dodecyl)-phenol (isomeric 131506. Doc -86 - 200948759 ), triphenyl-phenol (each isomer), triphenyloxyphenol (each isomer), triisopropylphenyl-phenol (each isomer), dimethyl Ethyl-phenol (each isomer), dimercapto-propyl-phenol (each isomer), dimethyl-butyl-poly(individual isomer), dimercapto-pentyl-benzene Age (each isomer), dimethyl-hexylbenzene (each isomer), dimethyl-heptyl-phenol (each isomer), dimethyl-octyl-phenol (each isomer) ), dimethyl-indenyl-phenol (each isomer), dimethyl-indenyl phenol (each isomer), dimethyl-dodecyl-phenol (each isomer), two Methyl-phenyl-phenol (each isomer), dimethyl-phenoxybenzene® (each isomer), dimethyl··cumyl-phenol (each isomer), two Ethyl-methyl-phenol (each isomer), diethyl propyl-phenol (each isomer), diethyl-butyl-phenol (each isomer), diethyl-pentyl - phenol (each isomer), diethyl-hexyl-phenol (each isomer), diethyl-heptyl-phenol ( Isomers), diethyl octyl-phenol (each isomer), diethyl-mercapto-phenylene (each isomer), diethyl-mercapto-benzene (each isomer) ), diethyl dodecyl phenol (each isomer), diethyl-phenyl phenol (each isomer), Φ diethyl phenoxy phenol (each isomer), two Ethyl-cumyl-phenol (each isomer), dipropyl-fluorenyl-benzoic acid (each isomer), dipropyl-ethyl phenol (each isomer), dipropyl - butyl-phenol (each isomer), dipropylpentyl-phenol (each isomer), dipropyl-hexyl-phenol (each isomer), dipropyl-heptyl-benzene ( Each isomer), dipropyl-octyl-benzene (each isomer), dipropyl-fluorenyl-phenol (each isomer), dipropyl-nonylphenol (each isomer) ), dipropyl-dodecylphenol (each isomer), dipropyl-phenyl-phenol (each isomer), dipropyl-phenoxyphenol (each isomer), two Propyl-isopropylphenyl-phenol (each isomer), dibutylmethyl-phenol (each isomer), 131506. Doc -87 - 200948759 Dibutyl-ethyl-phenol (each isomer), dibutyl-propyl-phenol (each isomer), dibutyl-pentyl-benzene (each isomer) , dibutyl·hexyl-phenol (each isomer), dibutyl-heptyl-benzene (each isomer), dibutyloctylphenol (each isomer), dibutyl-fluorenyl - phenol (each isomer), dibutyl-mercapto-phenol (each isomer), dibutyl-dodecyl-phenol (each isomer), dibutyl-phenyl-phenol ( Each isomer), dibutyl-phenoxyphenol (each isomer), dibutyl-cumyl-phenol (each isomer), dipentyl-methyl-phenol (isomeric , dipentyl-ethyl-phenol (each isomer), dipentyl propyl-phenol (each isomer), dipentyl-butyl-phenol (each isomer), two Pentyl-hexyl gastric phenol (each isomer), dipentyl-heptyl-phenol (each isomer), dipentyl-octyl-phenol (each isomer), dipentyl-indenyl group _ Phenol (each isomer), dipentyl-indenyl-phenol (each isomer), dipentyl-dodecyl-benzene (each isomer), dipentyl phenyl-phenol (each isomer), dipentyl-p-oxyphenol (each isomer), dipentyl-cumyl-phenol (variety) Structure), dihexyl-fluorenyl-phenol (each isomer), dihexyl-ethyl-phenol (each isomeric Φ), dihexyl-propyl-phenol (each isomer), dihexyl- Butyl-phenol (each isomer), dihexyl-pentyl-phenol (each isomer), dihexyl-heptyl-phenol (each isomer), dihexyl-octyl·phenol (isomeric) , dihexyl-fluorenyl-phenol (each isomer), dihexyl-fluorenyl-phenol (each isomer), dihexyl-dodecyl-phenol (each isomer), dihexyl _ Phenyl-phenol (each isomer), dihexyl-phenoxyphenol (each isomer), dihexyl-isopropylidene-p-phenol (each isomer), diheptyl-fluorenyl-phenol (each isomer), diheptyl-ethyl-phenol (each isomer), diheptyl-propylphenol (each isomer), diheptyl-butyl-phenol (each isomer) , diheptyl-pentylphenol (each isomer), 131506. Doc -88- 200948759 Diterpene 庚 Heptyl·Hexyl-Benzene (each isomer), Diheptyl-octyl-Benzene (each isomer), Diheptyl-decyl-phenol (isomeric , diheptyldecylphenol (each isomer), diheptyl-dodecyl-phenol (each isomer), diheptylphenyl-phenol (each isomer), diheptan -Phenoxyphenol (each isomer), diheptyl-cumylphenol (each isomer), = octyl-methyl-phenol (each isomer), dioctyl-ethyl - Benzine (each isomer), dioctyl-propyl-benzene (each isomer), dioctyl-butyl-phenol (each isomer), dioctylpentyl-phenol (each Isomers), dioctyl-hexyl-phenol (each isomer), dioctyl-heptyl-phenol (each isomer), dioctyl-fluorenyl-phenol (each isomer), two Octyl-fluorenyl-phenol (each isomer), dioctyl-dodecylphenol (each isomer), dioctyl-phenyl-phenol (each isomer), dioctyl-benzene Oxyphenol (each isomer), dioctyl-isopropylphenyl·phenol (each isomer), dimercapto-methyl-phenol (each Structure), dimercapto-ethyl-p-phenol (each isomer), dimercapto-propyl-phenol (each isomer), dimercapto-butyl-phenol (each isomer), Dimercapto-pentyl-phenol (each isomer), dimercapto-hexylphenol (each isomer), dimercapto-heptyl-phenol (each isomer), dimercapto-octylphenol (each isomer), dimercapto-fluorenyl-phenol (each isomer), didecyl-undecyl-phenol (each isomer), dimercapto-phenyl-phenol (variety) Structure), fluorenyl-phenoxyphenol (each isomer), dimercapto-isopropylidene-phenol (each isomer), dimercapto-methyl-phenol (each isomer) , dimercapto-ethyl-phenol (each isomer), dimercapto-propyl-benzoin (each isomer), dimercapto-butyl-benzine (each isomer), diterpenes Benzyl-pentyl-benzine (iso-isomer), dimercapto-hexyl-benzine (each isomer), dimercapto-heptyl-benzene (iso-isomer), dimercapto-octyl Phenol (each isomer), dimercapto-indenyl-phenol (isomeric J 3 ) 506. Doc-89- 200948759), Dimercapto-dodecyl-phenol (each isomer), Dimercaptophenylphenol (each isomer), Dimercapto-phenoxyphenol (isomeric , dimercapto-isopropylidene-phenol (each isomer), di(dodecyl)-methyl-phenol (each isomer), di(dodecyl)-ethyl Phenol (each isomer), di(dodecylpropyl-phenol (each isomer), di(dodecyl)-butylphenol (each isomer), di(dodecyl) _Pentyl-phenol (each isomer), di(dodecyl) hexyl-phenol (each isomer), di(dodecyl)-heptylphenol (each isomer), two ( Dodecyl)-octyl-phenol (each isomer), di(dodecyl)-decyl-phenol (each isomer), di(dodecyl)-nonylphenol (variety) Structure), one (dodecyl)-tidedocyl-benzene age (each isomer), bis(dodecyl)-phenyl-phenol (each isomer), di(dodecane) Phenoxyphenol (each isomer), di(dodecyl)-isopropylphenyl-phenol (each Structure), diphenyl-mercapto-phenol (each isomer), diphenylethyl-phenol (each isomer), diphenyl-propyl-phenol (each isomer), two Phenyl-butyl-p-phenol (each isomer), diphenyl-pentyl-phenol (each isomer), diphenyl-hexyl-phenol (each isomer), diphenyl- Heptyl-phenol (each isomer), diphenyl-octyl-phenol (each isomer), diphenyl-mercapto-phenol (each isomer), diphenyl-fluorenyl-phenol ( Each isomer), diphenyl-dodecyl-phenol (each isomer), diphenyl-phenoxyphenol (each isomer), diphenyl-cumylphenyl-phenol (each Isomers), diphenoxymethyl-phenol (each isomer), diphenoxyethyl-phenol (each isomer), diphenoxypropyl-phenol (each isomer), Diphenoxybutyl-phenol (each isomer), diphenoxypentyl-phenol (each isomer), diphenoxyhexyl-phenol (each isomer), diphenoxyheptyl - phenol (each isomer), diphenoxyoctyl-phenol (each isomer), diphenoxyanthracene _ Benzene 131,506. Doc -90- 200948759 Phenol (each isomer), diphenyloxyindenyl-phenol (each isomer), diphenoxydodecyl-phenol (each isomer), diphenoxy -Phenol (each isomer), diphenoxyisopropyl phenyl-phenol (each isomer), diisopropylphenyl 'methyl · phenol (each isomer), dicumyl Ethyl-phenol (each isomer), dicumyl-propyl-phenol (each isomer), dicumyl-butyl-phenol (each isomer), dicumyl -pentyl-phenol (each isomer), dicumyl-hexyl-phenol (each isomer), diisopropylphenyl-heptyl-phenol (each isomer), diisopropylphenyl -octyl-phenol (each isomer), diisopropylphenyl-fluorene-based phenol (each isomer), diisopropylphenyl-fluorenyl-phenol (each isomer), diisopropyl Phenyl-dodecyl-phenol (each isomer), diisopropylphenyl-phenyl-phenol (each isomer), diisopropylphenyl-phenoxyphenol (each isomer), Methyl-ethyl-propyl-phenol (each isomer), methyl-ethyl-butylphenol (isomeric , methyl-ethyl-pentyl phenol (each isomer), methyl ethyl-hexyl-phenol (each isomer), methyl-ethyl-heptyl-phenol (isomeric) , methyl-ethyl-octyl-p-phenol (each isomer), mercapto-ethyl-mercapto-phenol (each isomer), methyl ethyl-mercapto-phenol ( Each isomer), methyl ethyl-dodecyl-phenol (each isomer), mercapto-ethyl-phenyl-phenol (each isomer), mercapto-ethyl-phenoxy Phenol (each isomer), mercapto-ethyl-cumenyl-phenol (each isomer), mercapto-propyl-methyl-propyl-butyl-p-phenol (isomeric , mercapto-propyl-pentyl-phenol (each isomer), methyl propyl-hexyl-phenol (each isomer), mercapto-propyl-heptyl-phenol (variety) Structure), methyl-propyl-octyl-phenol (each isomer), mercapto-propyl-fluorenyl-phenol (each isomer), mercapto-propyl-mercapto-phenol ( Each isomer), mercapto-propyl-dodecyl-phenol (each isomer), methyl-propyl-phenyl-p-phenol (131506. Doc -91 · 200948759 Isomers), methyl-propyl-phenoxyphenol (each isomer), methyl-propyl-isopropyl-benzyl-benzene (each isomer), methyl -butyl-mercapto-phenazine (each isomer), mercapto-butyl-hexyl-phenol (each isomer), methyl-butyl-heptyl-phenol (each isomer), A Benzyl-octyl-phenol (each isomer), methyl butyl-mercapto-iso-(iso isomer), mercapto-butyl-fluorenyl-benzene (iso-isomers) ), mercapto-butyl-dodecyl-phenol (each isomer), mercapto-butyl-phenyl-phenol (each isomer), methyl-butyl-phenoxyphenol (each Isomers), methyl-butyl-isopropylphenyl-phenol (each isomer), methyl-pentyl-hexyl-phenol (each isomer), mercapto-pentylheptyl-phenol (each isomer), fluorenyl-pentyl-octyl-benzine (each isomer), fluorenyl-pentyl-fluorenyl-benzidine (each isomer), methyl-pentyl-oxime -Phenol (each isomer), methyl-pentyl-dodecyl-phenol (each isomer), mercapto-pentyl-phenyl-phenol (each isomer), methyl-pentyl -Phenoxyphenol (each isomer), methyl-pentyl-cumylphenol (each isomer), mercapto-hexyl-heptyl-phenol (each isomer), methyl _Hexyl-octyl-p-phenol (each isomer), mercapto-hexyl-fluorenyl-phenol (isomeric oxime), methyl-hexyl decyl-phenol (each isomer), methyl -hexyldodecyl-phenol (each isomer), methyl-hexyl-phenyl-phenol (each isomer), methyl-hexyl-phenoxyphenol (each isomer), methyl- Hexylisopropyl-p-phenol (each isomer), ethyl-propyl-butyl-phenol (each isomer), ethyl-propyl-pentyl-phenol (each isomer), B - propyl-hexyl- phenol (each isomer), ethyl-propyl-heptyl-phenol (each isomer), ethyl propyl-octyl _ phenol (isomeric), Ethyl propyl-fluorenyl-phenol (each isomer), ethyl-propyl-indenyl-phenol (each isomer), ethyl-propyl-dodecylphenol (isoisomer) ), ethyl-propyl-phenyl group phenol (each isomer), ethyl propyl group stupid 131506. Doc •92- 200948759 oxybenz (each isomer), ethyl-propyl-isopropylphenyl-phenol (each isomer), ethyl-butyl-phenol (each isomer), B Base-butyl-pentyl-phenol (each isomer), ethyl butyl-hexyl-phenol (each isomer), ethyl-butyl-heptyl-benzone (isomers), Ethyl-butyl-octyl-phenol (each isomer), ethyl butyl-mercapto-phenol (each isomer), ethyl-butyl-fluorenyl-phenol (each isomer) , ethyl-butyl-dodecyl-phenol (each isomer), ethyl-butyl-phenyl-phenol (each isomer), ethyl-butyl-phenoxyphenol (variety) Structure), ethyl·butyl-cumyl-phenol (each isomer), ethyl-mercapto-hexyl-benzone (each isomer), ethyl-pentyl-heptyl-phenol (each isomer), ethyl-pentyl-octyl-phenol (each isomer), ethyl-pentyl-mercapto-phenol (each isomer), ethyl-pentyl-fluorenyl Phenol (each isomer), ethyl-pentyl-dodedocthyl-phenol (each isomer), ethyl-pentyl-phenyl-phenol (each isomer), B Base-pentyl-phenoxyphenol (each isomer), ethyl-pentyl-cumenyl-phenol (each isomer), ethylhexyl-heptyl-phenol (each isomer) , ethyl-hexyl-octyl-phenol (each isomer), ethyl-hexyl-fluorenyl _ Φ phenol (each isomer), ethyl-hexyl-decyl-phenol (each isomer), Ethyl-hexyl-dodecyl-phenol (each isomer), ethyl-hexyl-phenyl-phenol (each isomer), ethyl-hexyl-phenoxyphenol (each isomer), Ethyl-hexyl-cumenyl phenol (each isomer), ethyl-heptyl-octyl-phenol (each isomer), ethyl-heptyl-decyl-phenol (isomeric) , ethyl-heptyl-fluorenyl-phenol (each isomer), ethyl-heptyl-dodecyl-phenol (each isomer), ethyl-heptyl-phenyl-phenol (each isomer), ethylheptyl-phenoxyphenol (each isomer), ethyl-heptyl-isopropylphenyl-phenol (each isomer), ethyl-octyl-phenol (each isomer), ethyl-octyl-fluorenyl-phenol (each isomer), 131506. Doc -93- 200948759 ❹ 乙基 Ethyl-octyl-fluorenyl-benzoic acid (each isomer), ethyl. Octyl-12-decyl-benzene (each isomer), ethyloctyl-phenyl (individual isomer), ethyl-octyl-phenoxy (tetra) (isomeric), B base. Octyl cumene. Benzene (each isomer), ethyl-mercaptodecyl-phenol (each isomer), ethyl-mercapto-dodecyl-phenol (each isomer), ethyl-mercapto group Phenyl-phenol (each isomer), ethyl-mercapto-phenoxyphenol (each isomer), ethyl decyl cumyl phenol (each isomer), ethyl fluorenyl · Dodecyl-phenol (isomeric =), ethyl-mercapto-phenyl-phenol (each isomer), ethyl-fluorenyl-phenoxyphenol (each isomer), ethyl · mercapto _ cumyl phenol (each isomer), ethyl-dodecyl-phenyl-phenol (each isomer), ethyl dodecyl phenoxy phenol (different Structure), ethyl-dodecyl-cumylphenol-phenol (each isomer), ethyl-phenyl-phenoxyphenol (each isomer), ethyl-phenyl cumene -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), propylbutyloctyl-phenol (each isomer), -butyl-mercapto-phenol (each isomer), propyl-butyl-mercapto-phenol (each isomer), propyl-butyl-dodecyl-phenol (each isomer) ), propyl-butyl-phenyl-phenol (each isomer), propylbutyl-phenoxyphenol (each isomer), propyl-butyl-isopropylphenyl-phenol (variety) Structure), propyl-pentyl-polyphenol (each isomer), propyl-pentyl-hexyl-phenol (each isomer), propyl-pentyl-heptyl-phenol (each isomer) , propyl-pentyl-octyl-phenol (each isomer), propyl-pentyl-mercapto-phenol (each isomer)' propyl-pentyl-indolyl-phenol (isomeric , propyl-pentyl-dodecyl-benzene (each isomer), propyl-pentyl-phenyl-phenol (each isomer), C 131506. Doc -94- 200948759 〇❹-pentyl-phenoxyphenol (each isomer), propyl-pentyl-cumyl-benzophenone (each isomer), propyl-hexyl-benzoate (each isomer), propyl-hexylheptyl phenol (each isomer), propyl-hexyl-octyl phenol (each isomer), propyl-hexyl-decyl-phenol (each Isomers), propyl-hexyl-fluorenyl-phenol (each isomer), propyl-hexyl-dodecyl-phenol (each isomer), propyl-hexyl-phenyl-phenol (each Isomers), propyl-hexyl-phenoxyphenol (each isomer), propyl-hexyl-cumyl-phenol (each isomer), propyl-heptyl-octyl-phenol ( Each isomer), propylheptyl-decyl-phenol (each isomer), propyl-heptyl-fluorenyl-phenol (each isomer), propyl-heptyl-dodecyl - phenol (each isomer), propyl-heptyl-phenyl-phenol (each isomer), propylheptyl-phenoxyphenol (each isomer), propyl-heptyl-isopropyl Phenyl phenol (each isomer), propyl-octyl-fluorenyl phenol (each isomer), propyl octyl fluorenyl - phenol (each isomer), propyl-octyl-dodecyl-phenol (each isomer), propyl-octyl-phenyl-phenol (each isomer), propyl-octyl Phenoxyphenol (each isomer), propyl-octyl-isopropylphenyl·phenol (each isomer), propyl-indenyl-fluorenyl-phenol (each isomer), propyl- Mercapto-dodecylphenol (each isomer), propyl-mercapto-phenyl-phenol (each isomer), propylsulfonyl-phenoxyphenol (each isomer), propyl _ fluorenyl cumene-phenol (each isomer), propyl decyl-dodecyl phenol (each isomer), propyl-mercapto-phenyl-phenol (isomeric , propyl-fluorenyl-phenoxyphenol (each isomer), propyl-mercapto-isopropylphenyl-phenol (each isomer), propyl-dodecyl-phenyl- Benzene (each isomer), @基-12-院-phenoxyphene (each isomer), propyl-dodecyl-cumylphenol-phenol (each isomer Base benzophenone (each isomer), ethyl benzene age (each isomer), propyl-benzene hope (each 131506. Doc •95- 200948759 isomers), butyl-phenol (each isomer), pentyl-phenol (each isomer), hexyl-phenol (each isomer), heptyl-phenol (isomeric) , octylphenol (each isomer), mercapto-phenol (each isomer), nonylphenol (each isomer), dodecyl-phenol (each isomer), phenyl- Phenol (each isomer), phenoxyphenol (each isomer), cumene-phenol (each isomer) 'propyl phenyl-phenoxyphenol (each isomer), C Base-phenyl-cumylphenol (each isomer), propyl-phenoxy-cumenyl-phenol (each isomer), propyl-butyl-pentyl-phenol (each Isomers), propyl-butyl-hexyl-phenol (each isomer), propyl-butyl-heptyl-phenol (each isomer), propyl-butyl-octyl-phenol (each Isomers), propyl-butyl-fluorenyl-phenol (each isomer), propyl-butyl-mercapto-phenol (each isomer), propyl-butyl-dodecyl_ Phenol (each isomer), propyl-butyl-phenyl-phenol (each isomer), propyl·butyl·benzene Phenol (each isomer), propyl-butyl-isopropylphenyl-phenol (each isomer), propyl-pentyl-phenol (each isomer), propyl-pentyl-hexyl_ Phenol (each isomer), propyl pentanylheptyl-phenol (each isomer), propyl-pentyl-pyryllyl-octyl-phenol (each isomer), propyl-pentyl-oxime -Phenol (each isomer), propyl··pentyl-decyl-phenol (each isomer), propyl-pentyl-dodecyl-benzene (each isomer), propyl -pentyl-phenyl-phenol (each isomer), propyl-pentyl-phenoxyphenol (each isomer), propyl-pentyl-cumyl-phenol (each isomer) , propyl-hexyl-heptyl-phenol (each isomer), propyl-hexyl-octyl-benzone (each isomer), propyl-hexyldecyl-phenol (each isomer), C -hexyl-fluorenyl-phenol (each isomer), propyl-hexyl-dodecyl-phenol (each isomer), propyl-hexyl-phenyl-phenol (each isomer), C Hexyl-phenoxyphenol (each isomer), propyl-hexyl cumene phenyl benzene 96- 200948759 phenol (variety , propyl-heptyl-octyl-phenol (each isomer), propyl-heptyl-fluorenyl-phenol (each isomer), propyl-heptyl-decyl-phenol (variety) Structure), propyl-heptyl-dodecyl-phenol (each isomer), propyl-heptyl-p-styl-phenol (each isomer), propyl-heptyl-phenoxyphenol (each isomer), propyl-heptyl-isopropylphenyl-phenol (each isomer), propyl-octyl-fluorenyl-phenol (each isomer), propyl-octyl-oxime -Phenol (each isomer), propyl-octyl-dodecyl-phenol (each isomer), propyl-octyl-phenyl-benzone (each isomer), propyl- Octyl-phenoxyphenol (each isomer), propyl-octylisoindole, propylphenyl-benzene (iso-isomer), propyl-mercapto-mercapto-benzene-based , propyl-decyl-dodecyl-phenol (each isomer), propyl-mercapto-phenyl-phenol (each isomer), propyl-mercapto-phenoxyphenol ( Each isomer), propyl-mercapto-cumyl-phenol (each isomer), propyl-indenyl-t-cylylene-phenol (each isomer), propyl-hydrazine -Phenyl-phenol (each isomer), propyl-mercapto-phenoxybenz (each isomer), propyl-mercapto-isopropylphenyl-benzene (each isomer), Propyl-dodecyl-phenyl-benzene (each isomer), propionyl-dodecyl-phenoxybenzene (each isomer), cumene-benzene ( Each isomer), propyl-phenyl-phenoxyphenol (each isomer), propyl-phenyl-isopropylphenyl-phenol (each isomer), butyl-pentyl-hexyl Phenol (each isomer), butyl-pentyl-heptyl-phenol (each isomer), butyl-pentyl-octyl-phenol (each isomer), butyl-pentyl-fluorenyl - phenol (each isomer), butyl-pentyl-decyl-phenol (each isomer), butyl-pentyl-dodecanyl-phenol (each isomer), butyl-pentyl -Phenyl-phenol (each isomer), butyl-pentyl-phenoxyphenol (each isomer), butyl-pentyl-cumyl-phenol (each isomer), butyl -hexyl-heptyl-phenol (each isomer) 'butyl-hexyl-octyl-131506. Doc-97- 200948759 Phenol (each isomer), butyl-hexyl-decyl-phenol (each isomer), butyl-hexyl-fluorenyl-phenol (each isomer), butyl-hexyl_ Dodecyl-phenol (each isomer), butyl-hexyl-phenyl-phenol (each isomer), butyl-hexylphenoxyphenol (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-tetradecyl-benazine (each isomer), butyl-heptyl-phenyl-benzene (iso-isomers) ), butyl-heptyl-phenoxyphenol (each isomer), butyl-heptyl_ ® cumyl-phenol (each isomer), butyl-octyl-decyl-phenol ( Each isomer), butyl-octyl-fluorenyl-phenol (each isomer), butyl-octyl-dodecyl-benzine (each isomer), butyl-octylbenzene -Benzene (each isomer), butyl-octyl-p-oxyphenol (each isomer), butyl-octyl-cumenyl-phenol (each isomer), butyl-mercapto-fluorenyl-phenol (each isomer), butyl-fluorenyl-dodecyl-benzene (iso-isomer), butyl-fluorenyl- Stupid-benzoin (each isomer), butyl-mercapto-phenoxybenz (each isomer), butyl-fluorenyl-isopropyl-p-phenylene (iso-isomer), Butyl-fluorenyl-tetradecyl-benzone (different oxime), butyl-mercapto-phenyl-phenol (each isomer), butyl-mercapto-phenoxybenzene ( Each isomer), butyl-mercapto-isopropylphenyl-benzene (each isomer), butyl-dodecyl-phenol (each isomer), butyl-dodecyl group Phenyl-benzoin (each isomer), butyl-dodecyl-phenoxybenz (each isomer), butyl-dodecyl-isopropylidene-benzene (variety) Structure), butyl-styl-phenol (each isomer), butyl-phenyl-phenoxyphenol (each isomer), butyl-phenyl-cumyl-phenol (variety) Structure), amyl-hexylheptyl-phenanthrene (each isomer), mercapto-hexyl-octyl-benzene (each isomer), pentyl-hexyl 131506. Doc -98- 200948759 base-fluorenyl-benzine (each isomer), amyl-hexyl-fluorenyl-benzoic acid (each isomer), pentyl-hexyl-dodecyl-phenol (variety) Structure), pentyl-hexyl-based-isolated (isomeric), mercapto-hexyl-phenoxybenz (each isomer), amyl-hexyl-isopropylphenyl-benzene ( Each isomer), amyl-heptyl-octyl-phenol (each isomer), pentyl-heptyl-fluorenyl-phenol (each isomer), amylheptyl-decyl-phenol ( Each isomer), pentyl-heptyl-dodecyl-benzene (each isomer), pentyl-heptyl-phenyl-phenol (each isomer), pentyl-heptyl-benzene Oxygen phenol (each isomer), pentyl-heptyl-isopropylphenyl-phenol (isomeric product), amyl-octyl-fluorenyl-phenol (each isomer), pentyl - 辛基_癸基_ idiot (each isomer), pentyl-octyl-tetradecyl-benazine (each isomer), pentyl-octyl-phenyl-phenol (isomeric , pentyl-octyl-phenoxyphenol (each isomer), amyl-octyl·cumyl-phenol (each isomer), amyl sulphate -Phenol (each isomer), pentyl-fluorenyl-dodecyl benzene (each isomer), pentyl-fluorenyl-phenyl-phenol (each isomer), pentyl _ Mercaptobenzene emulsions are basically (each isomer), amyl-decyl-cumyl-benzophenone (isomeric), amyl-decyl-dodecyl-phenol (isomeric) , pentyl-fluorenyl-phenyl-phenyl-(individually), pentyl-indolyl-phenoxybenzene (each isomer), pentyl-fluorenyl-isopropyl- Phenol (each isomer), amyl-fluorenyl-dodecyl-phenol (each isomer), pentyl-fluorenyl-phenyl-phenol (each isomer), pentyl-fluorenyl- This milk is basically as appropriate (each isomer), amyl sulfhydryl cumene phenol (each isomer), pentyl-dodecyl-phenyl phenol (each isomer), pent -dodecyl-phenoxyphenol (each isomer), amyl-dodecyl-isopropylidene-benzene (each isomer), pentyl-phenyl-phenoxyphenol (each isomer), pentyl-phenyl-isopropylphenyl-stupid (each isomer), hexyl-heptyl-octane 131506. Doc 99- 200948759 Ο --phenol (each isomer), hexyl-heptyl-decyl-phenol (each isomer), hexyl-heptyl-fluorenyl-benzoic acid (isomer), hexyl -heptyl-dodecyl-benzene (each isomer), hexyl-heptyl-phenyl-phenol (each isomer), hexyl-heptyl-phenoxyphenol (each isomer), Hexyl-heptyl-cumenyl phenol (each isomer), hexyl-octyl-fluorenyl-phenol (each isomer), hexyl-octyl-mercapto-phenyl- (pan) , hexyl-octyl-tetradecyl-phenol (each isomer), hexyl-octyl phenyl phenol (each isomer), hexyl-octyl-phenoxybenzene (each isomer) ), hexyl-octyl-cumyl phenyl-phenol (each isomer), hexyl-fluorenyl-fluorenyl----(iso-isomer), hexyl-fluorenyl-t-cylylene-phenol Each isomer), hexyl-fluorenyl phenyl-phenol (each isomer), hexyldecyl-phenoxyhexyl fluorenyl dodecyl-phenol (each isomer), hexyl-fluorene -Phenyl-phenol (each isomer), hexyl-fluorenyl-phenoxyphenol (each isomer) , hexyl-decyl-isopropylidene-phenol (each isomer), hexyldodecyl-phenyl-phenol (each isomer), hexyl-dodecyl-phenoxyphenol (variety) Structure), hexyl-dodecyl-cumylphenyl-phenol (each isomer) 'hexyl-phenylphenoxyphenol (each isomer), hexylphenyl cumylphenol (each Isomers), heptyl-octyl-fluorenyl-phenol (each isomer), heptyl-octyl-fluorenyl-phenol (each isomer), heptyl-octyl-dodecyl group Phenol (each isomer), heptyl-octyl-phenyl-phenol (each isomer), heptyl-octyl-phenoxy phenol (each isomer), heptyl-octyl-iso Propyl phenyl-phenol (each isomer), heptyl-fluorenyl decyl-phenol (each isomer), heptyl-fluorenyl-dodecyl group idiot (each isomer), heptyl · mercapto-phenyl-benzoquinone (each isomer), heptyl-fluorenyl-phenoxybenzene (each isomer), heptyl-壬mphenylbenzene w isomer), recorded - 癸基·十二统基_Benzene (each isomer), Geng I315〇6. D〇c •100· 200948759 thiol-phenyl-phenol (each isomer), heptyl-fluorenyl-phenoxyphenol (each isomer), heptyl-decyl-isopropyl -phenol (each isomer), heptyl-dodecyl-phenyl-phenol (each isomer), heptyl-dodecyl-phenoxyphenol (each isomer), heptyl- Dodecyl-cumylphenyl-phenol (each isomer), heptyl-phenyl-phenoxyphenol (each isomer), heptyl-phenyl cumylphenol (each isomer) ), octyl-fluorenyl-mercapto-phenol (iso-isomer), octyl

Mercapto-dodecyl-phenol (each isomer), octyl-decyl-phenyl-phenol (each isomer), octyl-fluorenylphenoxyphenol (each isomer), Octyl-decyl-cumenyl-phenol (each isomer), octyl-decyl-dodecyl-phenol (each isomer), octyl-decyl-phenyl-phenol ( Each isomer), octyldecyl-phenoxyphenol (each isomer), octyl-decyl-isopropylphenyl-phenol (each isomer), octyl-dodecyl-stupid -Phenol (each isomer), octyl-dodecyl-phenoxyphenol (each isomer), octyl-dodecyl-cumylphenyl-phenol (each isomer), Octyl-dodecyl-styl-phenol (each isomer), octyl-dodecyl-phenoxyphenol (each isomer), octyl-dodecyl-isopropyl - phenol (each isomer), octyl phenyl-phenoxy phenol (each isomer), octyl phenyl-isopropylphenyl-phenol (each isomer), fluorenyl-fluorenyl Dodecyl-benzone (each (tetra)), fluorenyl-fluorenyl-phenyl-benzene (each isomer), fluorenyl-fluorenyl-phenoxybenzene age (each Structure), mercaptopurinyl 6-phenylphenol (each isomer), mercapto-dodecyl-phenyl-p-phenol (each isomer), mercapto·ten n-phenoxybenzene (each isomer), decyl-dodecyl-pyridylbenzene (each isomer), benzyl phenyloxyphene (each isomer), thiol-ben -Phenylphenyl- phenol (each isomer), decyldodecyl phenyl-benzene (each isomer), fluorenyl-dodecyl phenoxybenzene (131506 each) .doc • 101 · 200948759 Isomers), mercapto-dodecyl-cumyl-phenol (each isomer), mercapto-phenyl-phenoxyphenol (isomers), hydrazine Base-stupyl-cumylphenol (each isomer), dodecyl-phenyl-phenoxyphenol (each isomer), dodecyl-phenyl-isopropylphenyl-phenol (all isomers), triphenyl-substituted benzenes such as phenyl-phenoxyisopropyl-p-benzophenone (each isomer). Among these organic acids, it is preferable to separate from the isocyanate formed in the thermal decomposition reaction in consideration of residual in the thermal decomposition reactor, and it is preferred to select an organic group having a boiling point difference from the standard boiling point of the isocyanate to be at least acid. 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; and introducing a cleaning solvent to the bottom of the thermal decomposition reactor may be used. Various methods such as a method in which the cleaning solvent is boiled in the thermal decomposition reactor to clean the inside. The shai 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., preferably, the operation time is every 2 hours to 2 hours. It is preferable that the operation time is performed every one day to one year, and it is more preferable that the operation time is performed once every J months to one year. The thermal decomposition reactor may be provided with a piping for introducing a cleaning solvent in the thermal decomposition reactor. Further, when the thermal decomposition reaction of the aryl carbamate is carried out for the purpose of the β-washing of the thermal decomposition reactor, the above-mentioned cleaning mixture can be coexisted under the conditions of the thermal decomposition reaction. It is different from the inert solvent of the prior art (for example, see U.S. Patent No. 4,081,472). For example, according to this patent document, an inert solvent refers to a compound which does not react with a cyanate ester which is formed by thermal decomposition of aminocarboxylic acid, and is, for example, in the literature (Journal of the American) Chemical Society &gt; Vol. 64, p. 2229, 1942, describes the reaction of an aromatic hydroxy compound with phenyl isocyanate to form a urethane, and the aromatic trans group compound can be reacted with an isocyanate. The aromatic hydroxy compound can be transported to the thermal decomposition by a reaction mixture obtained by reacting a carbonate with an amine compound or by separating a residue of the base compound and/or a carbonated acid and/or a reaction solvent from the reaction mixture. In the reactor, it may be mixed into the reaction mixture or the residual product to be supplied to the thermal decomposition reactor, or may be separated from the pipeline for supplying the reaction mixture, and a tube for supplying the aromatic mercapto compound may be separately provided. Supply by the road. 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. Further, according to the production method of the present embodiment, the isocyanate can be produced at a high yield without using highly toxic phosgene. Therefore, the present invention is extremely important in the industry. [Examples] Hereinafter, the present invention will be specifically described based on examples, but The scope of the invention is not limited to the embodiments. &lt;Analytical method&gt; 1) NMR analysis method device: Jnm_a4〇〇FT-NMR system (1) manufactured by Japan Electronics Co., Ltd. and preparation of 13C-NMR analysis sample 131506.doc Ί03- 200948759 Weighing 0.3 g sample solution, to solution A. Add about 0.7 g of deuterated gas to the mixture (American 'Aldrich Co., Ltd., 00 co/, Ώ Λ, 99) and 0.05 g as the internal standard Methyl tin (Japan, and #妯蕴τι \ and Wako Pure Chemical Industries, Inc., and light grade), uniformly mixed 'The obtained solution was analyzed as a sample by NMR. (2) Quantitative analysis method A quantitative analysis of the analysis sample solution is carried out based on a calibration curve prepared by performing analysis on each standard substance.

2) Liquid Chromatography Analysis Method = Placement: LC-10AT system column manufactured by Shimadzu Corporation, Japan: Sakamoto, Siliea 6〇 column manufactured by T〇soh Co., Ltd. with 艮 linkage developing solvent: hexane/tetrahydrofuran = 8 〇/2〇 (volume ratio) mixture solvent flow rate: 2 mL / min column temperature: 35. (: Detector: RI (refractive index meter) U) A sample of a sample of about 〇·1 g was analyzed by liquid chromatography, and about i-tetrahydrofuran (Sakamoto, manufactured by Wako Pure Chemical Industries, Ltd., dehydrated) was added thereto. And about 0.02 g of bisphenol A (manufactured by Japan's Wako Pure Chemical Industries, Ltd., first grade) as an internal standard substance, and uniformly mixed 'the obtained solution as a sample for liquid chromatography* analysis. (2) Quantitative analysis method A quantitative analysis of the analysis sample solution is carried out based on a calibration curve prepared by performing analysis on each standard substance. 3) Gas Chromatography Analysis Method 131506.doc 200948759 Device: GC-2010 official column manufactured by Shimadzu Corporation, Japan. DB-i manufactured by Agilent Technologies, USA

The length is 30 m, the inner diameter is 0.250 mm, and the film thickness is υο μιη. Column temperature: after 5 minutes at 50 ° C, the temperature is raised to 200 ° C at a heating rate of 丨〇 ° c / min.

After holding at 200 ° C for 5 minutes, the temperature was raised to 300 ° C at a temperature increase rate. Detector: FID (1) Gas chromatographic analysis of the sample Weighed about 0.05 g of the sample, and added thereto. 1 g of acetone (manufactured by Wako Pure Chemical Industries, Ltd., 'dehydration) and about 0.02 g of toluene as an internal standard substance (manufactured by Wako Pure Chemical Industries, Ltd., dehydrated), uniformly mixed 'the solution obtained as liquid chromatography Analytical samples. (2) Quantitative analysis method Based on the calibration curve prepared by analyzing each standard substance, the quantitative analysis of the sample solution is performed. 4) Inductively coupled plasma mass spectrometry method: Made in Japan, Seiko Electronics Co., Ltd., SPQ_8〇〇〇 (0 inductively coupled plasma mass analysis sample is diluted with dilute sulfuric acid. 15 g sample is ashed, dissolved in (2) Quantitative analysis The quantitative analysis of the sample solution is carried out based on the calibration curve prepared by analyzing each standard substance. [Reference Example 1] Bis(3-methylbutyl) carbonate Manufactured ^315〇6.(j〇c 200948759 .Step (ii): Manufacture of dialkyltin catalyst to a volume of 5000 mL in a flask, 625 g (2 7 m〇1) of di-n-butyl Base tin oxide (manufactured by Sankyo Organic Synthesis Co., Ltd.) and 2〇2〇g (22·7 mol) 3-methyl-indole butanol (manufactured by Wako Pure Chemical Industries, Ltd.). On the evaporator (manufactured by Japan, Shibata Co., Ltd., r_144), the evaporator is connected to an oil bath (made by Japan, Masuda Chemical Industry Co., Ltd., OBH_24) and a vacuum pump (made by Japan, ulvac, Japan). G-5〇A) and vacuum controller (made in Japan, manufactured by Okano Manufacturing Co., Ltd. 'VC-10S). Steaming The vent valve outlet of the generator is connected with the nitrogen gas pipeline flowing under normal pressure. The vent valve of the evaporator is closed, and after decompression in the system, the vent valve is slowly opened to allow nitrogen to flow into the system and return to normal pressure. The oil bath temperature was set to about 145 〇c, and the flask was immersed in the oil bath to start the rotation of the evaporator. After heating at atmospheric pressure for about 40 minutes in the state of the vent valve of the open evaporator, the inclusion was started. Distillation of 3_methyl_丨-butanol in water. After maintaining this state for 7 hours, the vent valve is closed, and the φ in the system is slowly decompressed, and the excess pressure is in the state where the pressure in the system is 74 to 35 kPa. Distillation of 3-methyl-1-butanol was carried out. After the fraction disappeared, the flask was taken out from the oil bath. After cooling the flask to near room temperature (25 〇c), the flask was taken out from the oil bath. The vent valve was slowly opened to return the pressure in the system to atmospheric pressure. 886 g of the reaction liquid was obtained in the flask. It was confirmed by the analysis of ii9Sn, H, 13C-NMR that the yield was 99 with respect to di-n-butyltin oxide. % obtained 1,1,3,3-tetra-n-butylmethylbutoxy )__Snoxane. Repeat the same operation 12 times to obtain a total of 1,635,§1,1,3,3-tetra-n-butyl-1,3-bis(3-methylbutoxy)_ Dioxetane. 131506.doc -106- 200948759. Step (1-2): Production of bis(3-hydrylbutyl)carbonate in a continuous manufacturing apparatus as shown in Fig. 1 to produce carbonic acid double (3) _Methylbutyl) ester. From line 4, to 4388 g / hr, the above-made; mountain 3,3_tetra-butyl 1,3-bis(3-methylbutyl lactyl) tin Oxygen was supplied to a column reactor 1〇2 with a filling of Metal Gauze CY (Switzerland, manufactured by Sulzer Chemtech Ltd.) of 151 mm and an effective length of 5040 mm, from line 2 to 14953 g /hr is supplied to 3-methyl-1·butanol purified in the continuous multi-stage distillation column 1〇1. The reactor 102 was conditioned using a heater and reboiler 112 to bring the liquid temperature to 16 Torr. 〇, use a pressure regulator to adjust to a pressure of approximately 120 kPa_G. The residence time in the reactor was about 17 minutes. From the upper part of the reactor, 3-methyl-1-butanol containing water was supplied via line 6 at 15〇37 g/hr, and the methyl-butanol was transferred to the filled metal Gauze CY via the pipeline. Further, in the continuous multi-stage distillation column 101 including the reboiler 111 and the condenser 121, distillation purification is performed. In the upper portion of the distillation column 101, a fraction containing a high concentration of water is condensed by a helium condenser 121 and recovered from the line 3. The purified 3-methyl-hydrazine-butanol is sent to the column reactor 102 via line 2 located below the continuous multi-stage distillation column 101. From the lower part of the column reactor 1〇2, it was obtained to contain n-butyl-bis(3-methylbutoxy)tin and ruthenium, 1,3,3_tetra-n-butyl_ι, 3_double (3) -Methylbutoxy)distannoxane alkyl tin alkoxide catalyst composition, supplied to thin film distillation apparatus 1〇3 via line 5 (manufactured by K〇be丨c〇ec〇_solutions, Japan) ). The 3-methyl-butanol was distilled off in a thin distillation apparatus 1〇3, and returned to the column reactor 1〇2 via the condenser 123, the line 8 and the line 4. The alkyl tin 131506.doc -107- 200948759 alkoxide catalyst composition is transferred from the lower portion of the thin distillation apparatus 1〇3 via line 7 to di-n-butyl-bis(3-methylbutoxy). The flow rate of tin and M,3,3-tetra-n-butyl qj.bis(3-methylbutoxy)-distannoxane was adjusted to about 5130 g/hr and supplied to the high pressure Cang 104. Carbon dioxide was supplied from the line 9 to the autoclave 1〇4 at 973 g/hr, and the internal pressure of the high pressure dad 1〇4 was maintained at 4 MPa-G. The temperature in the autoclave 104 was set to 12 Torr. (:, the residence time was adjusted to about 4 hours, and the reaction of carbon dioxide with the alkyl tin alkoxide catalyst composition was carried out to obtain a reaction liquid containing bis(3-methylbutyl) carbonate. The valve transports the reaction liquid to the carbon removal tank® 1〇5, removes residual carbon dioxide, and recovers carbon dioxide from the line 11. Thereafter, the reaction liquid is transported via the line 12 to about 142 C, approximately 0.5 kPa thin film distillation apparatus 1〇6 (manufactured by Kobelco eco-solutions, Japan), ΐ, ι, 3,3-tetra-n-butyl-indole, 3·bis(3-mercaptobutoxy) - the flow rate of distannic oxygen is adjusted to about 4388 g / hr to obtain a fraction containing bis(3-methylbutyl) carbonate, and on the other hand, 1,1,3,3-tetrabutyl _ The flow rate of the i,3-bis(3-methylbutoxy)-dixetane was adjusted to about 4388 g/hr, and the evaporation residue was circulated to the column reactor 102 via line 13 and line 4. A fraction comprising bis(3-mercaptobutyl)carbonate is supplied via a condenser 126 and a transfer line 14 to the filled metal Gauze CY at 959 g/hr. In the continuous multi-stage steaming tower 107 of the reboiler 117 and the condenser 127, after steaming purification, 99 wt% of bis(3-methylbutyl) carbonate was obtained from the recovery line 15 at 944 g/hr. The alkyltin alkoxide catalyst composition of the transport line 13 was analyzed by ll9Sn, 丨H, 13C-NMR, and the result contained 1,1,3,3-tetra-n-butyl-1,3-double (3-methylbutoxy) distannoxane, containing no di-n-butyl-bis(3-methylbutyloxy) tin. Performed 131506.doc •108· 200948759 After about 240 hours of continuous operation as described above, The alkylstan alkoxide catalyst composition is discharged from the discharge line 16 at 18*, and on the other hand, from the tube (4), 1133 tetra-n-butyl 13 dimethylbutoxide produced in the above method is supplied in g/hr. Base) a stannoxane. The obtained bis(3-methylbutyl) carbonate contained 23 ppm of iron as a metal atom. [Reference Example 2] Production of dibutyl carbonate. Step (IM): Production of dialkyltin catalyst To a flask having a volume of 3000 mL, 692 g (2.78 mol) of di-n-butyltin oxide and 2001 were added. g (27 mol) ι-butanol (manufactured by Wako Pure Chemical Industries, Ltd.). A flask in which the mixture was added in the form of a white slurry was attached to an evaporator having an oil bath with a temperature regulator attached thereto. Vacuum pump and vacuum controller. The vent valve outlet of the evaporator is connected to a nitrogen gas line flowing under normal pressure. Close the vent valve of the evaporator, and after decompressing the system, slowly open the vent valve to allow nitrogen to flow into the system and return to normal pressure. Set the oil bath temperature to 126. (:, the flask is immersed in the oil bath φ 'to start the rotation of the evaporator. Rotating and stirring under normal pressure in a state of opening the vent valve of the evaporator and heating for about 3 minutes, the mixture boils and starts Distillation of low Buddha component. After maintaining this state for 8 hours, the vent valve was closed, the system was slowly decompressed, and the residual low boiling component was distilled under the pressure of 76 to 54 kpa in the system. After disappearing, the burned plate was taken out from the oil bath. The reaction liquid became a transparent liquid. Thereafter, the flask was taken out from the oil bath, and the vent valve was slowly opened to restore the pressure in the system to normal pressure. 847 g of the reaction liquid was obtained in the flask. According to the analysis results of &quot;9Sn, 4, 13C-NMR, it was confirmed that di-n-butyltin oxide was used as the base 131506.doc •109·200948759, and the product was obtained in a yield of 99%. - n-Butyl 13-di(n-butoxy)-distannoxane was repeated 12 times in the same manner to obtain a total of 1 118 〇g of 1,1,3,3-tetra-n-butyl-i , 3 · bis (n-butoxy) _ disodium oxide. 'Step (II-2): the manufacture of dibutyl carbonate In the continuous manufacturing apparatus shown in Fig. 1, a carbonate is produced. 1133_tetra-n-butyl-1,3-di which is produced in the step (π-1) by the supply line 4' at 42 〇 lg / hr (n-butoxy)-distannoxane supplied to the filler

Mellapak 750Y (Switzerland, manufactured by Sulzer Chemtech Ltd.) in a column reactor with an inner diameter of 151 mm and an effective length of 5040 mm, from line 2, with a continuous multistage distillation column of 24517 g/hr. 1 Purified butanol is supplied to the column reactor 1〇2. The reactor was adjusted by the heater and the turret 2 to bring the liquid temperature to 16 (rc, adjusted by a pressure regulating valve to bring the pressure to about 12 kPa kPa - G. The residence time in the reactor was about 10 minutes. From the upper part of the reactor, 1-butanol containing water was supplied via line 6 at 24715 g/hr, and butbutanol was fed via a supply line 1 at 824^^ to a filled metallurgy CY (Sulzer, Switzerland) Distillation purification is carried out in a continuous distillation column 10 1 having a reboiler 111 and a condenser 121, and a fraction containing a high concentration of water is used in a condenser above the continuous multi-stage distillation column 101. After being condensed, 121 is recovered by the transport line 3. The purified i-butanol is transported through a line 2 below the continuous multi-stage distillation column. From the lower part of the column reactor 1〇2, the second positive is obtained. Butyltin di-n-butoxide and 1,1,3,3-n-butyl-1,3-bis(n-butoxy)-ditin oxide calcined tin-sinter oxide catalyst composition via a pipeline 5 supplied to the thin film distillation unit 1〇3 (Japan, 131506.doc •110· 200948759 -. Co., Ltd.) in a distillation apparatus ⑻ in thin Ge, Gu to 1-butanol, via condenser 123, line 8 and transported back to the transport pipe 4

Returning to the column reactor 102. The alkyl tin alkoxide catalyst composition is transported from the lower portion of the thin film evaporation unit 1〇3 via line 7 to di-n-butyltin di-n-butyl oxide and UW-n-butyl 1,3-bis(n-butoxy) The flow rate of the active ingredient of the stannoxane was adjusted to about 4812 g/hr, and was supplied to the high-duty father. The carbon dioxide was supplied to the autoclave at 973 g/hr via the line 9, and the internal pressure of the high waste dad was maintained at 4 MPa_G. The temperature in the autoclave was set to 12 〇 ° C. The residence time was adjusted to about 4 hours, and the reaction of carbon dioxide with the yard-based stannous oxide catalyst composition was carried out to obtain a reaction solution containing dibutyl carbonate. And the regulating valve transports the reaction liquid to the carbon removal tank 1〇5 to remove residual carbon dioxide, and recovers the carbon dioxide from the pipeline. Thereafter, the reaction liquid is transported through the pipeline 12 to be set to about 14 〇. &lt;t, a thin film evaporation apparatus of about 1.4 kPa 1〇6 (manufactured by K〇beic〇ec〇s〇luti〇ns, Japan), 1,1,3,3_tetra-n-butyl_13_ The flow rate of di(n-butoxy)distannoxane is adjusted to about 4201 g/hr for supply, and the obtained carbonic acid is obtained. The ester fraction, on the other hand, the flow rate of 113,3_tetra-n-butyl- 13 bis(n-butoxy)-distannoxane is adjusted to about 42 〇丨g/hr, and the evaporation residue is passed through the line 13 and Line 4 is recycled to the column reactor 1〇2. The portion containing the dibutyl carbonate is supplied via condenser 126 and line 14 at 830 g/hr to the filled Metal Gauze CY (Sulzer, Switzerland) In a distillation column 107 equipped with a reboiler 117 and a condenser 127, after purification by distillation, 99 wt% of dibutyl carbonate was obtained from the line 15 at 814 g/hr. Using 119Sn, 丨3C-NMR analysis of the alkyl tin alkoxide 131506.doc 200948759 catalyst composition of line 13 resulted in 113 3_tetra-n-butyl-indole, 3-di(n-butoxy)-di-tin Oxygenane, which does not contain di-n-butyltin di-n-butyl oxide. After the above continuous operation for about 600 hours, the discharge line 16 is supplied to the courtyard tin oxide oxide catalyst composition at 16 g/hr, on the other hand, Line 17 was supplied at 16 g/hr of tetra-n-butyl-indole, 3-di(n-butoxy)-distannoxane produced in the step (Π-1). Dibutyl acrylate contains 0.3 ppm of iron as a metal atom. [Reference Example 3] Production of bis(2-ethylbutyl) carbonate • Step (III-1): Production of dialkyl tin catalyst to volume A 5000 mL eggplant flask was charged with 893 g (2.48 mol) of di-n-octyltin oxide (Sakamoto, manufactured by Sankyo Organic Synthesis Co., Ltd.) and 24 g of 3 g (23.6 mol) of 2-ethyl-1-butanol. The flask was mounted on an evaporator to which an oil bath, a vacuum pump and a vacuum controller with a temperature regulator were attached. The vent valve outlet of the evaporator is connected to a nitrogen gas line flowing under normal pressure. Close the vent valve of the evaporator, and after decompressing the system, slowly open the vent valve to allow nitrogen to flow into the system and return to normal pressure. The oil bath temperature δ was again reduced to about 165 ° C, and the flask was immersed in the oil bath to start the rotation of the evaporator. After heating under atmospheric pressure of nitrogen for about 40 minutes in the state of a venting valve of an open evaporator, a steaming station containing 2-ethyl-1-butanol of water was started. After maintaining this state for 7 hours, the vent valve was closed, and the excess 2 - ethyl-1-butanol was distilled while the system was subjected to slow dust reduction in a system pressure of 74 to 25 kPa. After the low boiling component disappeared, the flask was taken out of the oil bath. After cooling the flask to room temperature (25., near the crucible, the flask was taken out of the oil bath, and the vent valve was slowly opened to restore the pressure in the system to a large 131506.doc • 112·200948759 atmosphere. Obtained in the flask. 1125 g of the reaction liquid. According to the analysis results of 1 &gt;9Sn, ι, and 13C-NMR, it was confirmed that 1,1,3,3-tetra-octyl·L3 was obtained in a yield of 99% with respect to di-n-butyltin oxide. - bis(2_ethylbutoxy)-ditin oxide. Repeat the same operation 12 times to obtain a total of 13510 g of 1,1,3,3-tetra-n-octyl-1,3-d (2 -ethylbutoxy)-ditin oxide. Step (III-2): Production of carbonate and recovery of inactivated body composition of dialkyltin catalyst in a continuous manufacturing apparatus as shown in FIG. In the manufacture of carbonates, the 1,1,3,3-tetra-n-octyl-deutero(2-ethylbutoxy)-di which was produced as described above from 60 4 g/hr. The stannoxane is supplied to a column reactor 102 filled with a filler Metal ze CY having an inner diameter of 151 mm and an effective length of 5040 mm. 'Supply from line 2 at 12260 g/hr to be purified by continuous multistage distillation column 101 2-ethyl-1-butanol. The heat exchanger and reboiler 112 adjust the reactor 102 to bring the liquid temperature to 1600. (:, adjust with a pressure regulating valve to bring the pressure to about 12 kPa kPa - G. The hysteresis φ retention time in the reactor It is about 17 minutes. From the upper part of the reactor, 2-ethyl_ι-butanol containing water is fed via line 6 at 12344 g/hr, and 2_ethyl-1-butane is passed through line 1 at 958 §/1111. The alcohol is sent to a continuous multi-stage distillation column 1〇1 filled with a filler Metal Gauze CY and equipped with a reboiler 111 and a condenser 121, and is subjected to distillation purification. In the upper part of the continuous multi-stage distillation column 101, high-concentration water is contained. The fraction is condensed by the condenser 121 and recovered by the recovery line 3. The purified 2·ethyl-1-butanol is sent to the column type reaction via the line 2 located below the continuous multi-stage distillation column 101. 102. From the lower part of the column reactor 1〇2, it is obtained by containing di-n-octyl-bis(2-ethylbutoxy)tin and ruthenium, osmium, ^% four-131506.doc • 113· 200948759 An alkyl stannate catalyst composition of n-octyl-1,3.bis(2-ethylbutoxy)distannoxane via a pipeline 5 is supplied to the thin film distillation apparatus 1〇3. 2-Ethyl-1-butanol is distilled off in the thin film distillation apparatus 103, and returned to the column reactor 1〇2 via the condenser 123, the line 8 and the line 4. Transferring the alkyltin alkoxide catalyst composition from the lower portion of the thin film distillation apparatus 1〇3 via the line 7, and di-n-octyl-bis(2-ethylbutyloxy) tin and ruthenium, The flow rate of % tetra-n-octylethylbutoxy)distannoxane was adjusted to about 6945 g/hr and supplied to the high pressure Cang 104. The carbon dioxide was supplied from the line 9 to the autoclave at 973 g/hr, and the internal pressure of the autoclave was maintained at 4 MPa-G. The temperature in the autoclave was set to 120 C, and the residence time was adjusted to about 4 hours, and the reaction of carbon dioxide with the alkyl tin alkoxide catalyst composition was carried out to obtain a reaction containing bis(2-ethylbutyl carbonate). liquid. The reaction liquid is transported to the carbon removal tank 105 via a line 1 and a regulating valve to remove residual carbon dioxide, and carbon dioxide is recovered from the line. Thereafter, the reaction liquid was transported through the line 12 to be set to about 142. (:, in a thin film distillation apparatus ι〇6 of about 0.5 kPa, the flow rate of φ M,3,3-tetra-n-octyl],3-bis(2-ethylbutoxy)distannoxane was adjusted to Approximately 6074 g/hr was supplied to obtain a column containing bis(2-ethylbutyl) carbonate, and on the other hand '1,1,3,3-tetra-n-octyl_ι,3-double The flow rate of (2-ethylbutoxy)-xanoxide was adjusted to about 6 〇 74 g/hr, and the evaporation residue was circulated through line 13 and line 4 to the column reactor 1 〇 2. The fraction of 2-ethylbutyl) ester was supplied to the distillation column 107 filled with the filler Metal Gauze CY and equipped with the reboiler 117 and the condenser 127 at 959 g/hr through the condenser 126 and the line 丨4. After distillation purification, 99 wt% of bis(2-ethylbutyl) 131506.doc • 114· 200948759 was obtained from the recovery line 15 at 1 075 g/hr. U, nC.R was used for the pipe i3. Analysis of the surface-based tin oxide oxide catalyst composition, the result contains u,3,3_tetra-n-octyl], 3 bis(2-ethylbutoxy)distannoxane, does not contain di-n-octane Base-diethylbutyloxy) tin. After the continuous operation for about 22 hours, the alkyl tin alkoxide catalyst composition was supplied from the discharge line b at 18 g/hr, and on the other hand, the supply line 17 was supplied at 18 g/hr. u,3,3_w • n-octyl-1,3-bis(2-ethylbutoxy)dithion oxide, which is discharged from the discharge line 16 by i'1,3,3-®· An in vivo living composition of octyl-1,3.bis(2-ethyl-oxy) bisoxane. The obtained bis(2-ethylbutyl carbonate) contained 4.8 ppm of iron as a metal atom. [Reference Example 4] Production of diheptyl carbonate. Step (IV-1): Production of dialkyltin catalyst 692 g (2 78 m〇i) of di-n-butyl is added to an eggplant type flask having a volume of 3000 mL. Base tin and 3137 g (27 mol) 1-heptanol (manufactured by Wako Pure Chemical Industries, Ltd., Japan). A flask to which the mixture was added in the form of a white slurry was attached to an @ evaporator equipped with an oil bath equipped with a temperature regulator, a vacuum pump and a vacuum controller. The vent valve outlet of the evaporator is connected to a nitrogen gas line flowing under normal pressure. Close the evaporator vent valve and depressurize the system. Slowly open the vent valve to allow nitrogen to flow into the system, making the system 39 kPa. The oil bath temperature was set to 15 〇»c, and the flask was immersed in the oil bath to start the rotation of the evaporator. After rotating and stirring at normal pressure for about 3 minutes in the state of the vent valve of the open evaporator, the mixture boiled and distillation of the low boiling component was started. 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-fond component was vaporized in the system under the pressure of 39 to 10 kPa 131506.doc -115-200948759. After the low lag component disappeared, the flask was taken out of the oil bath towel. The reaction solution became transparent (4). Thereafter, the flask was taken out of the oil bath, and the vent valve was slowly opened to restore the pressure in the system to normal. 952 g of the reaction liquid was obtained in the flask. According to the analysis results of H9Sn, 咕, i3c_NMR, it was confirmed that the product u, 3,3 tetra-n-butyl+3-diheptyloxy-ditin oxide was obtained in a yield of 99% based on di-n-butyltin oxide. alkyl. The same operation was repeated 12 times to obtain a total of 1,1,3,3-tetra-n-butyl-indole, % bis-heptyloxy-distannoxane. • Step (IV-2): Production of diheptyl carbonate The carbonate was produced in a continuous production apparatus t as shown in FIG. From line 4, the step (ν·ι) manufactured u, 3, 3 tetra-n-butyl 丨, 3 bis-n-heptyloxy-distannoxane was supplied to the filled filled material MeUapak at 4757 g/hr. 75〇γ (Switzerland, manufactured by Sulzer Chemtech Ltd.) in a column reactor with an inner diameter of i5i and an effective length of 5040 mm. From line 2, g/hr will be used as a continuous multi-stage distillation column.丨〇丨 Purified 丨_butanol is supplied to the column reactor 1〇2. The reactor was adjusted by a heater and reboiler 112 to bring the liquid temperature to 170 t, and was adjusted by a pressure regulating valve to bring the pressure to about 120 kPa-G. The residence time in the reactor is about 1 〇 minutes. The upper part of the reactor was passed via line 6 at 14051 g/hr of helium-heptanol containing water, and via line 1 to 1-heptanol at 1086 g/hr to a filled metallurgy CY (Switzerland ' Sulzer It is produced by Chemtech Ltd., and is equipped with a continuous multi-stage distillation column 1 of a reboiler 111 and a condenser 121, and is subjected to distillation purification. In the upper portion of the distillation column 101, a portion containing a high concentration of water is condensed in the condenser 121 and recovered from the line 3. The purified heptanol was delivered via a transfer line 2 below the tower HH of Steamer 131506.doc -116- 200948759. An alkylstannane containing di-n-butyltin di-n-heptane oxide and butyl-1,3-1,3-n-heptyloxy-distannoxane is obtained from the lower portion of the column reactor 1〇2.

The oxide catalyst composition ' is supplied via a line 5 to a thin film distillation apparatus 103 (manufactured by Kobelco eco_s〇lmi〇ns Co., Ltd., Japan). The p-heptanol was distilled off in the thin film distillation apparatus 1〇3, and returned to the column reactor 102 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 film evaporation chamber 103 via line 7 to di-n-butyltin di-n-heptane oxide and 1'1,3,3·tetra-n-butyl-n-glycol The flow rate of the active ingredient of oxy-distannoxane was adjusted to about 5764 g/hr and supplied to the autoclave 1〇4. 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 of the high pressure dad is set to 12 〇 ° C, the residence time is adjusted to about 4 hours, and the reaction of carbon dioxide with the alkyl tin alkoxide catalyst composition is carried out to obtain a reaction liquid containing diheptyl carbonate. The reaction vessel is transported to the carbon tank ι〇5 to remove residual carbon dioxide, and the carbon dioxide is recovered from the pipeline. Thereafter, the reaction liquid was transported through a line 12 to a thin film distillation apparatus 106 (manufactured by Kobeleo ec〇_s〇luti〇ns Co., Ltd., which is 14 (rc, about 1.4 kPa), and 1, 1, 3, The flow rate of 3-tetra-n-butyl-l,3-di-n-heptyloxy-distannoxane was adjusted to about 4757 g/hr and supplied to obtain a fraction containing dibutyl carbonate. On the other hand, '1' 1,3,3-tetra-n-butyl_ι,3-di-n-heptyloxy·one tin-oxygen gas flow rate adjusted to about 5 764 g / hr 'to make evaporation residue through the pipeline; [3 and pipeline 4 It is recycled to the column reactor 1〇2. The deionate containing dibutyl carbonate is supplied via a condenser 126 and a line 14 at 1223 g/hr to a metal Gauze CY filled with a filling 131506.doc-117-200948759 ( In the distillation column i〇7 of the reboiler 117 and the condenser 127, which was equipped with a reboiler 117 and a condenser 127 in Switzerland, after steam purification, 1208 g/hr of 99 wt% of diheptahydrate was obtained from the line 15. The alkyltin alkoxide catalyst composition of the pipeline 13 was analyzed by 119Sn, iH, nC_NMR, and the result contained ^^, Hongsi-n-butyl-^-di-n-heptyloxydistannoxane, no Containing di-n-butyl Base tin di-n-heptane oxide. After the above continuous operation for about 600 hours, the burnt-base tin oxide catalyst composition is discharged from the discharge line 丨6 at 22 g/hr, and on the other hand, the feed line 17 iM, 3,3_tetra-n-butyl], 3_di-n-heptyloxy-distannoxane was produced in step dv-i) at 22 g/hr. The obtained diheptyl carbonate contains 26 paws as iron of a metal atom. [Reference Example 5] Production of bis(2-ethylhexyl) carbonate; Step (V-1): Production of dialkyltin catalyst 692 g (2 78 m) was added to an eggplant type flask having a volume of 3000 mL. 〇1) Di-n-butyltin oxide and 3516 g (27 mol) of 2-ethyl-1-hexanol (manufactured by Nippon & Co., Ltd.). A flask in which the mixture was added in the form of a white slurry was attached to an evaporator to which was connected a plug with a temperature regulator, a vacuum pump, and a vacuum controller. The vent valve outlet of the evaporator is connected to a nitrogen gas line flowing under normal pressure. Close the venting valve of the evaporator, and after decompressing the system, slowly open the venting valve to allow nitrogen to flow into the system, so that the system is about 26 kPa. The oil bath temperature was set to i 5 〇. Thereafter, the flask was immersed in the oil bath to start the rotation of the evaporator. After the mixture was rotated and stirred under normal pressure for about 3 minutes in the state of the open air valve of the evaporator, the mixture boiled and distillation of the low boiling component was started. After maintaining this state for 8 hours, 13l506.doc -118- 200948759 closed the vent valve, slowly depressurizing the system, and distilling the residual low boiling component under the pressure of 26 to 10 kPa in the system. After the low boiling component disappeared, the flask was taken out of the oil bath. The reaction solution became a transparent liquid. Thereafter, the flask was taken out of the oil bath, and the vent valve was slowly opened to restore the pressure in the system to normal pressure. 99 〇 g of the reaction solution was obtained in the flask. According to the analysis results of 119Sn, H, and C-NMR, it was confirmed that the product 113,3 tetra-n-butyl-1,3-bis(2-) was obtained in a yield of 99% based on di-n-butyltin oxide. Ethylhexyloxy)-distannoxane. Repeat the same operation 12 times to obtain a total of 1 1880 g of 1,1,3,3-tetra-n-butyl_ι, 3_bis (2-ethylhexyl) Oxy)-distannoxane. Step (V-2): bis(2-ethylhexyl) carbonate is produced in a continuous manufacturing apparatus as shown in Fig. 1 to produce a carbonate. The tetra-n-butyl-1,3-bis(2-ethylhexyloxy)-di-n-oxide plant manufactured in step OM) at 4943 g/hr, and from line 2 at ι 5565 g/hr Continuous multi-stage distillation column 1〇1 purified 2-ethyl-1·hexanol, supplied to a filled Mellapak 750Y (Switzerland, manufactured by Sulzer Chemtech Ltd.) with an inner diameter of 151 mm and an effective length of 5 In the column reactor 102 of the crucible, the reactor is adjusted by the heater and the reboiler 112 to bring the liquid temperature to 17 Torr, and the pressure regulating valve is used to adjust the pressure to about 12 Torr. kPa-G. The residence time in the reactor is about 1 Minutes. From the upper part of the reactor, 2_ethyl-1-hexanol containing water was fed via line 6 at 15737 g/hr, and 2-ethyl·ι-hexanol was conveyed via line 1 at 1217 g/hr. Filled with filler Metal Gauze CY (Switzerland, Sulzer Chemtech)

Ltd., manufactured by the company, and equipped with continuous multi-stage steaming of reboiler crucible and condenser i21. 131506.doc • 119- 200948759 Distillate 101 is subjected to distillation purification. On the upper portion of the distillation column 1〇1, a fraction containing a high concentration of water is condensed in the condenser 121 and recovered from the line 3. Purified 2-ethylhexanol is delivered via line 2 located below the distillation column 101. Obtained from the lower part of the column reactor 102 containing bis-n-butyltin-bis(2-ethylhexoxide) and ^Hong IV. n-butyl _13 bis(2-ethylhexyloxy)_ oxime oxygen entertainment The xanthene-based oxide catalyst composition is supplied to a thin film distillation apparatus 103 (manufactured by K〇belc〇ec〇s〇luti〇ns Co., Ltd.) via a line 5. In the thin film distillation apparatus 103, 2-ethyl-1-hexanol was distilled off, and returned to the column reactor 1〇2 via the cold 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 distillation apparatus 103 via line 7 to di-n-butyltin-bis(2-hexylhexoxide) and 1,1,3,3 tetra-n-butyl The flow rate of the active ingredient of the base-1,3-bis(2-ethylhexyloxy)-distannoxane was adjusted to about 6083 g/hr, and it was supplied to the autoclave 1 〇4. Carbon dioxide was supplied to the autoclave via line 9 at 973 g/hr, and the internal pressure of the autoclave was maintained at 4 MPa-G. The temperature of the autoclave was set to 12 (rc, the residence time was adjusted to ◎ about 4 hours to carry out the reaction of carbon dioxide with the alkyl tin alkoxide catalyst composition) to obtain a reaction liquid containing bis(2-ethylhexyl) carbonate. The reaction liquid is transported to the carbon removal tank 1〇5 via the line 10 and the regulating valve to remove residual carbon dioxide. The carbon dioxide is recovered from the line 。. Thereafter, the reaction liquid is sent to the pipeline 12 through the line 12 A film purifying device 1〇6 (made by Kobelco eco-solutions, Japan) of 1401 and 1.4 kPa, 1,1,3,3·tetra-n-butyl-丨'3·double (2_B) The flow rate of hexyloxy)-distannoxane is adjusted to about 4943 g/hr, and is supplied to obtain a fraction containing dibutyl carbonate, and on the other hand, 1,1,3,3-tetra-n-butyl- 1,3-bis(2-ethylhexyloxy 131506.doc -120- 200948759 base)-mono- tin-oxygen gas flow rate is adjusted to about 4943 g/hr, and the evaporation residue is circulated to the tower via the conveying line 13 and the conveying line 4. Type reactor 1〇2. The arsenic containing dibutyl sulphate was supplied via condenser 126 and line 14 at 1354 g/hr to the filled metal. Gauze CY (Switzerland, manufactured by Sulzer Chemtech Ltd.) and a distillation column 1〇7 equipped with a reboiler 117 and a condenser 127, after purification by distillation, obtained 丨339 g/hr of 99 wt% of carbonic acid from the line 15. Bis(2-ethylhexyl) ester. The pyrithion tin alkoxide catalyst composition of line 13 was analyzed using 丨i9Sn, iH, !3c_nmr, and the result contained tetra-n-butyl-1,3-bis ( 2-ethylhexyloxy)-distannoxane, which does not contain di-n-butyltin-bis-(2-ethylhexoxide) ^ After the above continuous operation for about 600 hours, 'from the discharge line 16 to 23 g /hr discharging the alkyltin alkoxide catalyst composition', on the other hand, the 1,1,3,3-tetra-positive produced in the step (V-1) by the feed line 17 at 23 g/hr Butyl-1,3-bis(2-ethylhexyloxy)-distannoxol. The obtained bis(2-ethylhexyl) carbonate contains 30 ppm of iron as a metal atom. [Reference Example 6] Production of diphenyl carbonate The diphenyl carbonate was obtained by using dibutyl carbonate obtained in Reference Example 2. • Step (VI-1): Production of aromatic carbonate [Preparation of catalyst] 79 g of phenol and 32 G—lead oxide on 18 It is heated for 10 hours. The water formed is distilled off together with phenol. About 2.5 g of water is discharged in an hour. Then, the catalyst is prepared from the upper part of the reactor to prepare a catalyst. [Aromatic vinegar Manufacture] Use the device shown in Figure 2. 131506.doc -121- 200948759 Continuous multi-stage steaming tower 202 filled with Dixon packing (6 mm phantom with an inner diameter of about 5 cm and a tower length of 2 m) In the middle stage, the dibutyl carbonate, the phenol obtained in the step (1_2), the phenol, and the catalyst prepared above are continuously fed in a liquid form from the line 21 at a temperature of about 270 g/hr via a preheater 2 〇. The mixed liquid (the weight ratio of dibutyl carbonate to phenol in the mixed liquid was prepared to be about 65/35, and the lead concentration was prepared to be about 1% by weight) was reacted. The heat required for the reaction and distillation is supplied by passing the liquid in the lower portion of the column through the line 23 and the reboiler 204#. The liquid temperature at the bottom of the column of the continuous multi-stage distillation column 202 is 238 &lt;&gt;, the top pressure of the crucible is about 250 kPa, and the reflux ratio is about 2. The gas distilled from the top of the continuous multi-stage steaming tower 202 was discharged from the line 22, and continuously discharged from the line 24 to the storage tank 2〇5 at about 67 g/hr via the condenser 2〇3. From the bottom of the column, it was continuously discharged into the storage tank 2〇6 via the line 23 at about 204 g/hr. The composition of the liquid discharged from the line 24 is about 33% by weight of 丨-butanol, about 65% by weight of phenol, and about 2% by weight of dibutyl carbonate. The liquid composition discharged to the storage tank 206 has a phenol content of about 丨丨% by weight, a dibutyl carbonate of about φ 60% by weight, a butyl phenyl carbonate of about 26% by weight, and a diphenyl carbonate of about 1.6% by weight. The lead concentration is about 1% by weight. Next, use the device shown in Figure 3. To the middle of the continuous multi-stage distillation column 302 filled with Dixon packing (6 ππηφ) having an inner diameter of 5 cm and a column length of 2 m, via a preheater 3〇1, from the line 3 i to about 203 g/ The hr is continuously discharged into the liquid in the storage tank 2〇6 in a liquid form. The heat required for the reaction and distillation is supplied by circulating the liquid in the lower portion of the column through the line 33 and the refill unit 304. The liquid temperature at the bottom of the continuous multi-stage distillation column 3〇2 was 240 ° C, the overhead pressure was about 27 kPa, and the reflux ratio was about 2. 131050.doc -122· 200948759 The gas from the top of the continuous steaming tower 302 is condensed via the line μ in the condenser 303, and continuously discharged from the line 34 to the storage tank 305 at about i65 g/hr. . From the bottom of the column, it is continuously discharged to the composition of the liquid discharged from the line 34 in the storage tank 3〇6 via the line 33 at about 39 g/hr, 丨-butanol is about 5 〇〇 ppm, and phenol is about 13% by weight. 'Dibutyl carbonate is about 85% by weight, and butyl phenyl carbonate is about 2% by weight. The composition of the liquid discharged to the storage tank 306 is about 3% by weight of dibutyl carbonate, about 32% by weight of butyl phenyl carbonate, about 61% by weight of diphenyl carbonate, and about 7 weight by weight. 〇/0. [Recycling and Recycling of Alcohol] The alcohol was recovered and reused using the apparatus shown in Fig. 4 . The continuous multi-stage distillation column 402 filled with a Dixon packing (6 ηηπιφ) having an inner diameter of about 5 and a column length of 2 m is about 7 111 at the lowermost portion of the distance from the line, and is passed through the preheater 401 from the line 41. The liquid which was continuously discharged to the storage tank 205 in the above step was continuously fed at about 201 g/hr for distillation separation. The heat required for the distillation separation is supplied by circulating the liquid in the lower portion of the column via the line 43 and the reboiler 404. The liquid temperature at the bottom of the continuous multi-stage distillation column 402 is 145 ° C. The top pressure is about 13 kPa. The reflux ratio is about 0.3. The gas distilled from the continuous multi-stage distillation column 402 was condensed in the condenser 4〇3 via the line 42 and discharged to the storage tank 405 from the line 44 at about 68 g/hr. From the bottom of the column, it is continuously discharged to the storage tank 406 via the line 43 at about I33 g/hr. Of the composition of the liquid discharged from the line 44, the butanol is about 99% by weight and the phenol is about 100 ppm. The composition of the liquid discharged to the storage tank 4〇6 was about 2% by weight of dibutyl carbonate and about 98% by weight of phenol. 131506.doc -123 - 200948759 [Purification of diaryl carbonate] Purification of diaryl carbonate was carried out using a device as shown in Figs. To the middle of a continuous multi-stage distillation column 502 filled with a Dixon packing (6 ππηφ) having an inner diameter of about 5 cm and a column length of 2 m, from the line 51, via the preheater 501, to about 195 g/ The hr is continuously fed to the liquid in the storage tank 3〇6. The heat required for the distillation separation is supplied by circulating the liquid in the lower portion of the column via the line 53 and the reboiler 504. The liquid temperature at the bottom of the continuous multi-stage distillation column 5〇2 is 210 C, the pressure at the top of the column is about 1.5 kPa, and the reflux ratio is about [. The gas distilled from the top of the continuous multi-stage distillation column 502 is condensed in the condenser 503 via the line 52, and continuously discharged from the line 54. From the bottom of the column, it is discharged to the sump 506 via line 53 at about 14 g/hr. In the composition of the liquid discharged from the line 54, the dibutyl carbonate is about 0.3% by weight, the butyl phenyl carbonate is about 34% by weight, and the diphenyl carbonate is about 66% by weight. The middle portion of the continuous multi-stage distillation column 602 having an inner diameter of about 5 cm and a column length of 2 ❹ m, from the line 61, is continuously fed through the preheater 601 ' at about 181 g/hr. The liquid discharged from the line 54 is discharged. The heat required for the distillation separation is supplied by circulating the liquid Zhao at the lower portion of the column through the line 63 and the refill unit 604. The liquid temperature at the bottom of the continuous multi-stage distillation column 602 was 232 ° C, the top pressure was about 15 kPa, and the reflux ratio was about 2. The gas distilled from the top of the continuous multi-stage distillation column 602 is condensed in the condenser 603 via the line 62, and continuously discharged from the line 64. From the bottom of the column, it is discharged to the sump 606 via line 63 at about 119 g/hr. In the composition of the liquid discharged from the line 64, dibutyl carbonate is about 〇6 weight 131506.doc -124- 200948759% by volume 'about butyl phenyl carbonate is about 99% by weight, and diphenyl carbonate is about 0.4% by weight. . The composition of the liquid discharged to the storage tank 606 was 0.1% by weight of butyl phenyl carbonate and about 99.9% by weight of diphenyl carbonate. The diphenyl carbonate contained 8.2 ppm of iron as a metal component. [Example 1] Step (1-1): Production of N,N'-hexanediyl-bis-aminocarbamic acid bis(3-methylbutyl) ester The reaction was carried out using an apparatus as shown in Fig. 2. In the state where the line 24 is closed, 3333 g (16.5 mol) of bis(3-methylbutyl) carbonate of Reference Example 1 is supplied from the storage tank 2〇1 via the line 21 to an internal volume of 5 L. In the SUS reaction vessel 204 of the board, 383.5 g (3.3 mol) of hexamethylenediamine (manufactured by Aldrich Co., Ltd., USA) was supplied from the storage tank 202 to the reactor 204 via a line 22. The temperature of the liquid in the reactor 204 was adjusted to about 80 ° C. From the storage tank 203 via line 23, 6.4 g of methanol (manufactured by Wako Pure Chemical Industries, Ltd., 28% methanol solution) was supplied to the sus reactor. In 204, the reaction is carried out. The solution after the reaction was analyzed by liquid chromatography, and the product was formed in a yield of 99.7%; ^, hexane-diyl-bis-amino bis(3-methylbutyl) phthalate. The line 24 was opened, and the reaction liquid was supplied to an acidic ion exchange resin (Amberly St-15 (spherical): R〇HM &amp; HAAS), which was adjusted to remove moisture, and was insulated by an external casing to 8 Torr. In the column of &lt;t, neutralization of sodium decoxide was carried out. The solution was transported via line 25 to storage 206. • Step (1·2): Distillation of low boiling components 131506.doc -125- 200948759 The apparatus shown in Figure 3 was used to carry out the alcohol store. The intermediate portion of the continuous multi-stage distillation column 302 having an inner diameter of 5 cm and a column length of 2111 filled with a Dixon packing (6 ππηφ) is recovered to a mixture of the storage tank 2〇6, and -i is supplied from the preheater 301, Continuously fed in liquid form from line 31 at about 280 g/hr. The heat required for the steaming station is supplied by circulating the liquid in the lower portion of the column through the line 3 3 and the reboiler 304. The liquid temperature at the bottom of the continuous multi-stage distillation column 3〇2 is 160 ° C, and the pressure at the top of the column is about 7 kPa. The gas distilled from the top of the continuous multi-stage distillation column 302 is passed through the line 32 to the condenser 3. The crucible 3 was condensed and the autogenous helium line 34 was continuously discharged to the storage tank 305 at about 43 g/hr. From the bottom of the column, it was continuously discharged to the storage tank 3〇6 via line 33 at about 237 g/hr. The carbonate was distilled off using the apparatus shown in FIG. The middle portion of the continuous multi-stage distillation column 4〇2 filled with Dickson packing (6 ηιηιφ) having an inner diameter of 5 cm and a column length of 2〇1 is recovered into a mixture of the storage tank 3〇6, The heat exchanger 40 1, is continuously fed in liquid form from the line 41 at about 23 7 g/hr. The heat required for the distillation is supplied by circulating the liquid in the lower portion of the column through the line 43 and the reboiler 404. The liquid temperature at the bottom of the continuous multi-stage distillation column 4〇2 was 160 C, and the pressure at the top of the column was about 2.6 kPa. The gas distilled from the top of the continuous multi-stage steaming tower 4〇2 was condensed in the condenser 4〇3 via the line 42 and continuously discharged to the storage tank 4〇5 from the line 44 at about 15 〇 g/hr. From the bottom of the column, it was continuously discharged to the storage tank 4〇6 via line 43 at about 87 g/hr. The mixture discharged to the storage tank 406 was subjected to liquid chromatography analysis, and as a result, the mixture contained about 98,2 by weight. /〇之Ν,Νι_hexanediyl_bis-aminocarbamic acid bis(3-methylbutyl) vinegar. Step (1-3): Using N,N'-hexanediyl-bis-aminocarbamic acid bis(3-methylbutyl) 131506.doc • 126- 200948759 The thermal decomposition of the ester to produce isocyanate is shown in Figure 5. The device shown is reacted. ❹ 薄膜 A thin film distillation apparatus 5〇1 (manufactured by Kobelc〇 eco-solutions, Japan) with a heat transfer area of 0.1 m2 was heated to 270 ° C to have an internal pressure of about 13 kPa. The mixture recovered in the storage tank 40 in the step (1-2) was heated to i6〇〇c, and supplied to the upper portion of the thin film evaporator 501 via the line 50 at about 280 g/hr. Further, dibutyltin dilaurate (manufactured by Wako Pure Chemical Industries, Ltd., Japan) was fed from the line 51 at about 25.2 g/hr. From the bottom of the thin film distillation apparatus 5〇1, the liquid phase component is discharged from the line 53 and circulated to the upper portion of the thin film distillation apparatus 501 via the line 54. The gas phase components are discharged from line 52. The gas phase component discharged from the membrane (4) device 5〇1 through the line 52 to the middle portion of the continuous multi-stage steaming material filled with Dixon packing (6 ηίΓηφ) and having an inner diameter of about 5 cm and a length of 2 Μ. Continuous feeding, steam separation of the gas phase components is carried out. The heat required for the vapor separation is supplied by circulating the liquid at the lower portion of the column by the line 56 and the reboiler 504. The temperature of the liquid at the bottom of the continuous multi-stage steaming tower 5〇2 is 150. (: The pressure at the top of the tower is about 5 。. The gas (4) from the top (4) of the continuous multi-stage steaming tower 5G2 is condensed by the line 55 in the cold 5〇3, and the continuous flow of FK from the line 57 is continued. The line 59 of the multi-stage distillation column 502 below the line 52 discharges the liquid phase component. To the continuous multi-stage distillation column 505 filled with Dixon packing (6 m ton having an inner diameter of about 5 Å, m) The length of the liquid phase is 8 η 〆 continuous into the liquid phase discharged from the pipeline 59. The steam phase separation of the gas phase component is set. The heat is transferred by the technique required by the technique The liquid in the lower part is supplied via the line 6. The continuous multi-stage steaming tower 5〇5 is the bottom of the 507 circulation tower. The liquid temperature of the crucible is 150 131506.doc •127- 200948759 °c, the top pressure is about 1&gt;5 The kPa is condensed from the top of the continuous multi-stage distillation column 5〇5 through the line 60 in the condenser 506, and continuously discharged to the storage tank 509 via the line 62. The discharge amount in the steady state is about 丨3〇. g/hr After 40 hours of operation, the liquid phase component is discharged from line 64 at about g/hr to storage tank 510. The liquid system discharged from line 62 contains about 99.8% by weight. A solution of hexamethylene diisocyanate having a yield of 96 7 Torr/〇 with respect to hexamethylenediamine was continuously operated for 10 days. As a result, no deposit was accumulated on the wall surface of the thin film distillation apparatus 5〇1. Example 2]. Step (2-1): 3-((3-methylbutoxy)carbonylamino-indenyl_3,5,5-trimethylcyclohexylaminocarboxylic acid (3-indenyl) Preparation of butyl) ester In addition to 3394 g (16.8 mol) of bis(3-methylbutyl) carbonate of Reference Example 1, 596 g (3.5 mol) of 3-aminomethyl substituted hexamethylenediamine The reaction was carried out in the same manner as in Example 1 except that the reaction was carried out by reacting _3,5,5-trimethylcyclohexylamine (manufactured by Aldrich, USA, 6.8 g of sodium hydride (28% methanol solution). - 1) The same method. The solution after the reaction was analyzed by liquid chromatography, and the result was a yield of 99.5 〇 / 3- to give 3-((3-fluorenylbutoxy) amide-yl group. 3,5,5-Dimethylcyclohexylaminocarbamic acid (3-methylbutyl) ester. The reaction solution is supplied to an acidic ion exchange resin (Amberlyst-15 (spherical)) which is adjusted to remove moisture. ROHM &amp; HAAS company) and protected by external casing Neutralization of sodium sterol is carried out in column 205 of 80 C. The solution is transported via line 25 to storage tank 206. • Step (2-2): Distillation of low boiling components 131506.doc -128- 200948759 The middle portion of the continuous multi-stage distillation column 302 filled with a Dixon packing (6 ηιηιφ) having an inner diameter of 5 cm and a column length of 2 〇] was passed through the apparatus shown in Fig. 3. Heater 3〇1, the heat required for the distillation of the mixture from the line 3 i in a liquid continuous feed to the storage tank 2〇6 is carried out by passing the liquid in the lower part of the column through the line 3 3 and The reboiler 304 is circulated and supplied. The liquid temperature at the bottom of the continuous multi-stage distillation column 3〇2 was 160 ° C, and the pressure at the top of the column was about 70 kPa. The gas distilled from the top of the continuous multi-stage distillation column 3〇2 was condensed in the condenser 3〇3 via the line 32, and was continuously discharged from the tube 34 to the storage tank 305 at about 43 μ. From the bottom of the column, it is continuously discharged to the storage tank 306 via line 33 at about 23 7 g/hr. The carbonate was distilled off using the apparatus shown in Fig. 4. The middle section of the continuous multi-stage distillation column 402 filled with Dickson packing (6 ηηηιφ) having an inner diameter of 5 cm and the length of the column was passed through a preheater 4〇1 'from the line " at about 237 g/hr. The mixture is recovered in a continuous liquid feed to a mixture of tanks 3 and 6. The heat required for the distillation is supplied by circulating the liquid in the lower portion of the column via line 43 and reboiler crucible 404. Continuous multi-stage distillation column 4〇2 The liquid temperature at the bottom of the column is 160 ° C, and the pressure at the top of the column is about 2.6 kPa. The gas distilled from the top of the continuous multi-stage distillation column 4 〇 2 is condensed in the condenser 4 〇 3 via line 42. The line 44 is continuously discharged to the storage tank 4〇5 at about 138 g/hr. From the bottom of the column, it is continuously discharged to the storage tank 4〇6 via the line 43' at about 98 g/hr. The liquid phase of the mixture discharged to the storage tank 406 is carried out. Analysis by analytical analysis revealed that the mixture contained about 99% by weight of 3-((3-methylbutoxy)carbonylamino-methyl-3,5,5-trimethylcyclohexylaminocarboxylic acid (3_). Methyl butyl) ester, step (2-3): using 3_((3_methylbutoxydecylaminomethyl-3,5,5-131506.doc •129- 200948759 trimethylcyclohexyl) Aminocarboxylic acid (3_ The thermal decomposition of butyl butyl ester to produce isofluoric acid vinegar is carried out by using the apparatus shown in Fig. 5. The thin film distillation apparatus 5〇1 having a heat transfer area of 〇·1 m2 is heated to 27 〇β (:, The internal pressure is about 13 kPa. The mixture recovered in the storage tank 406 in the step (2-2) is heated to 17 〇c, and supplied to the upper portion of the thin film evaporator 501 via the line 50 at about 2 〇〇g/hr. Further, dibutyltin dilaurate (manufactured by Wako Pure Chemical Industries, Ltd.) was fed from the line 51 at a rate of about 25 2 /. From the bottom of the thin film distillation apparatus 501, the liquid phase component was discharged from the line 53 so that It is circulated to the upper portion of the thin film distillation apparatus 5〇1 via the line 54. The gas phase component is discharged from the line 52. The inner diameter of the Dixon packing (6 ηπηφ) is about 5 cm and the length of the tower is 2 m. In the middle section of the continuous multi-stage distillation column 5〇2, the gas phase component discharged from the thin film distillation apparatus 501 via the line 52 is continuously fed, and the vapor phase component is subjected to distillation separation. The heat required for the distillation separation is made by the tower. The lower liquid is supplied through the tube 0 path 56 and the reboiler 504. The continuous multi-stage distillation column 5〇2 tower The liquid temperature at the bottom is 150 ° C and the pressure at the top of the column is about 50 kPa. The gas distilled from the top of the continuous multi-stage distillation column 502 is condensed in the condenser via line 55 and continuously discharged from the line 57. The liquid phase component is discharged from the line 59 of the continuous multi-stage distillation column 5〇2 below the line 52. The inner diameter of the filled Dixon packing (6 ηιιηφ) is about 5 cm, and the length is 2 m. In the middle of the continuous multi-stage distillation column 505, the liquid phase component discharged from the line 59 is continuously fed, and the vapor phase component is subjected to distillation separation. The heat required for the distillation separation is supplied by passing the liquid in the lower portion of the column through the line 61 and the reboiler 5 〇 7 by illuminating 131506.doc - 130 - 200948759. The liquid temperature at the bottom of the column of the continuous multi-stage distillation column 505 is 15 ° C, and the pressure at the top of the column is about 1.5 kPa. The gas distilled from the overhead of the continuous multi-stage distillation column 5〇5 is condensed in the condenser 506 via the line 60, and continuously discharged to the storage tank 509 via the line 62. The steady state discharge is about 1〇7 g/hr. After 40 hours of operation, the liquid phase component was discharged from the line 64 to the storage tank 5 10 at about 9 g/hr. The liquid system discharged from line 62 contained about 99.8% by weight of a solution of isophorone diisocyanate. The yield relative to hexamethylenediamine was 96.5%. The continuous operation was carried out for 10 days, and no deposit was accumulated on the wall surface of the film vaporizing apparatus 5〇1. [Example 3] Step (3-1) 'Manufacture of N,N'-(4,4'-methylene-diphenyl)-bis-aminocarbamic acid bis(3-methylbutyl) ester To a reference example The bis(3-mercaptobutyl)carbonate of 1 is added with iron (II) acetonitrile. 'Preparation of bis(3-mercaptobutyl)carbonate containing 7.4% of iron as a metal atom. In addition to 2917 g (l 4.4 mol) of bis(3-mercaptobutyl) vinegar, 753 g (3.8 mol) of 4,4'-methylenediamine (manufactured by Aldrich, USA) in place of hexamethylenediamine, The reaction was carried out in the same manner as in the step (1_1} of Example 1 except that 7.3 g of sodium methoxide (28% decyl alcohol solution) was reacted. The solution after the reaction was analyzed by liquid chromatography, and the yield was 99.丨% produces N,n,_(4,4·-methylene-diphenyl)-bis(3-methylbutyl) dimethyl carbamate. The reaction solution is supplied to contain moisture and is adjusted. An acidic ion exchange resin (Amberlyst-15 (spherical): r〇HNI &amp; manufactured by HAAS) was used in the column 205 which was insulated with an outer sleeve of 80 C to carry out the neutralization of the collagen. 131506.doc 131 - 200948759 This solution is transported via line 25 to storage tank 2〇6. 'Step (3·2): Low-boiling ingredients to use the device shown in Figure 3 to go to the alcohol hall. The middle portion of the continuous multi-stage distillation column 302 having a packing inner diameter of 5 cm and a column length of 2 claws was continuously fed from the line 31 at a flow rate of about 270 g/hr in a liquid form via a preheater 3〇1. The mixture to the storage tank 2〇6. The heat required for the distillation is supplied by circulating the liquid in the lower portion of the column through the line 33 and the reboiler 304. The liquid temperature at the bottom of the continuous multi-stage distillation column 302 is 160 C. The top pressure is about 70 kPa. The gas distilled from the top of the continuous multi-stage steaming tower 3〇2 is condensed in the condenser 3〇3 via line 32, from line 34 at about 48 g/hr. It is continuously discharged to the storage tank 3〇5. From the bottom of the tower, it is discharged to the storage tank 3〇6 through the line 33 at a rate of about 222 g/hr. The carbonate is distilled off using the apparatus shown in Fig. 4. The middle section of the Dixon packing (6 ηιηιφ) having an inner diameter of 5 cm and a column length of 2 m is passed through a preheater 4 〇!, and a liquid of about 237 g/hr from the line 4 i ❿ The continuous feed is recovered to the mixture of storage tanks 3. The heat required for the distillation is supplied by circulating the liquid in the lower portion of the column via line 43 and reboiler 404. The bottom of the continuous multi-stage distillation column 4〇2 The liquid temperature is 160 C 'the top pressure is about 2.6 kPa. The gas distilled from the top of the continuous multi-stage distillation column 4〇2 is passed through the line 42 to the condenser 4 The condensation in 03 was continuously discharged from the line 44 to the storage tank 405 at about 102 g/hr. From the bottom of the column, it was continuously discharged to the storage tank 406 via the line 43 at about 120 g/hr. The liquid phase of the mixture discharged to the storage tank 406 was carried out. Analysis by analytical analysis revealed that the mixture contained about 98.5% by weight of 2Ν,Ν'-(4,4,-methylene-diphenyl)_double I3I506.doc 132- 200948759 bis(3-methylbutyl)carbamate )ester. Acid double l 骤 Ο 3 3). Use of thermal decomposition of Ν 'Ν, · (4'4, _ methylene _ diphenyl) bis bis bis carbamic acid ester to produce isocyanate The reaction was carried out using a device as shown in FIG.

The heat transfer area is (MW 臈 thin steaming (four) m is heated to 27 generations, the internal pressure is about red 3 hearts. The mixture recovered in step (4) to the storage tank 4〇6 is heated to mt' via the pipeline 7〇, About 19 coffee is supplied to the upper portion of the thin film evaporator 7〇1. Further, dibutyltin dilaurate is fed from the tube (4) at about i4 g/hr. From the bottom of the thin tantalum distillation unit 7〇1, the liquid phase is self-contained. The line 73 is discharged and circulated to the upper portion of the thin film distillation unit via the line 74. The gas phase component is discharged from the line 72. The inside is filled with a Dixon packing (the inner diameter of 6 is about 5 cm, and the length of the column is In the middle of the continuous multi-stage distillation column 702 of 2 m, the gas phase component discharged from the thin film distillation apparatus 701 via the line 72 is continuously fed, and the vapor phase component is subjected to distillation separation. The heat required for the distillation separation is made by lowering the lower portion of the column. The liquid is supplied by circulating through the line 76 and the reboiler 704. The temperature of the liquid at the bottom of the column of the continuous multi-stage distillation column 7〇2 is 200 C, and the pressure at the top of the column is 60 kPa. The top of the continuous multi-stage distillation column 702 is made. The distillate gas is condensed in the condenser 7〇3 via the line 75, and continuously discharged from the line 77. 78. The liquid phase component is discharged. The liquid is discharged continuously from the pipe 78 to the middle section of the continuous multi-stage distillation column 705 filled with Dickson packing (6 ηιπιφ) having an inner diameter of about 5 cm and a column length of 2 m. The phase component performs distillation separation of the liquid phase component. The heat required for the distillation separation is supplied by circulating the liquid in the lower portion of the column via the line 81 and the reboiler 707. The liquid at the bottom of the column of the continuous multi-stage distillation column 705 The temperature is 21〇131506.doc •133· 200948759 C, the overhead pressure is about 2.5 kPa. The gas distilled from the top of the continuous multi-stage distillation column 7〇5 is condensed in the condenser 706 via line 80. The liquid phase component is continuously discharged through the line 82. The middle portion of the continuous multi-stage distillation column 708 having an inner diameter of about 5 cm and a column length of 2 m filled with a Dixon packing (6 ππηφ) The liquid phase component discharged from the line 84 is continuously fed to perform distillation separation of the liquid phase component. The heat required for the distillation separation is supplied by circulating the liquid in the lower portion of the column through the line 86 and the reboiler 71. The liquid temperature at the bottom of the continuous multi-stage distillation column 7〇8 is 22〇C, the top of the tower The force is about 55 kPa. The gas distilled from the top of the continuous multi-stage distillation column 7〇8 is condensed in the condenser 709 via line 85, and is continuously continuous at about 1〇5 g/hr via line 87. The liquid discharged from the line 87 contains about 99.9% by weight of 4,4-diphenylmethane diisocyanate. The yield of methylene monoaniline is 95.3% with respect to 44. The continuous operation for 10 days is not found. Attachment was accumulated on the wall surface of the thin film distillation apparatus 701. [Example 4] 步骤. Step (4·1): bis(3-methylbutyl)-4,4,-fluorenylene-dicyclohexylamine The manufacture of the urethane is carried out in addition to 3 〇 64 g (1·5 mol) of bis(3-methylbutyl) carbonate of Reference Example 1, 778 g (3-7 mol) instead of hexanediamine 4, 4,- Yttrium bis(cyclohexylamine) (manufactured by Aldrich, USA), 7.1 g of sodium methoxide (28. The reaction was carried out in the same manner as in the step (1_1) of Example 1. The solution after the reaction was analyzed by liquid chromatography, and a double (3-) was produced in a yield of 99.0%. Methyl butyl)·4,4′·methylene-dicyclohexylamine bismuth citrate. The reaction solution is supplied to an acid ion that is adjusted to contain moisture and is adjusted. 131506.doc -134- 200948759 exchange resin ( Amberlyst-15 (spherical): manufactured by R0HM &amp; HAAS) and neutralized with sodium methoxide using an external casing held at 80 ° C. The solution is transported via line 25 to a storage tank. 2〇6. • Step (4-2): Distillation of the low-boiling component is carried out using the apparatus shown in Figure 3 to remove the alcohol. The inner diameter of the filled Dixon filler (6 ιηπιφ) is 5 cm. The middle section of the continuous multi-stage distillation column 302 having a column length of 2 m was recovered into a mixture of the storage tanks 2 to 6 via a preheater 3 (H, continuously fed from the line 3 i in a liquid form at about 270 g/hr. The heat required for the steaming plant is supplied by circulating the liquid in the lower portion of the column through the line 33 and the reboiler 304. The continuous multi-stage distillation column 3〇2 The liquid temperature at the bottom is 160 C 'the top pressure is about 70 kPa. The gas distilled from the top of the continuous multi-stage distillation column 3〇2 is condensed in the condenser 303 via line 32, from the line 34 45 g/hr was continuously discharged to the storage tank 3〇5. From the bottom of the column, it was continuously discharged to the storage tank 3〇6 via the line 33 at about 225 g/hr. The carbonate was distilled off using the apparatus shown in Fig. 4. The middle section of the continuous multi-stage distillation column 402 filled with Dixon packing (6 ππηφ) having an inner diameter of 5 cm and a column length of 2 m, via the preheater 4〇1, from the line 4 1 to about 225 g /hr is recovered as a mixture of tanks 3〇6 in a continuous liquid feed. The heat required for distillation is supplied to the continuous multi-stage distillation column by circulating the liquid in the lower portion of the column via line 43 and reboiler 404. The liquid temperature at the bottom of the column 2 is 160 ° C and the overhead pressure is about 2.6 kPa. The gas distilled from the top of the continuous multi-stage distillation column 402 is condensed in the condenser 403 via line 42 from the line 44. It was continuously discharged to the storage tank 405 at about 111 g/hr. From the bottom of the column, it was continuously discharged to the storage tank 406 via the line 43 at about 114 g/hr. 131506.doc -135- 200948759 The mixture discharged to the storage tank 406 was subjected to liquid chromatography analysis, and as a result, the mixture contained about 99. wt% of bis (3-methylbutyl M4, methylene-cyclohexylamino formate vinegar. 4_3): The isocyanate is produced by thermal decomposition of ruthenium, osmium, (4,4,_methylene-diphenyl)-bis(3-methylbutyl) biscarbamate, as shown in FIG. The device is reacted. The thin film distillation apparatus 7〇1 having a heat transfer area of 0.1 m2 was heated to 27 Torr to make the internal pressure approximately U core. The mixture recovered in the step (4.2) to the storage tank 4〇6 is heated to &apos; via line 70 and supplied to the upper portion of the thin (four) generator 701 at about 2 〇〇 g/hr. Further, dibutyltin dilaurate was fed from line 71 at about 14 g/hr. From the bottom of the film evaporation chamber 7〇1, the liquid phase component is discharged from the line 73, and is circulated through the line 74 to the upper portion of the film evaporation device 7〇1. The gas phase components are discharged from line 72. The middle portion of the continuous multi-stage steaming tower 702 filled with the Dixon packing (6 ηιιηφ) having an inner diameter of about 5 cm and a tower length of 2 m is continuously fed from the membrane steaming unit 701 through the line 72. The phase component 'distills the vapor phase component. The heat required for the steam separation is supplied by circulating the liquid in the lower portion of the column through the line 76 and the reboiler 704. The liquid temperature at the bottom of the continuous multi-stage distillation column 7〇2 is 20 (TC, the column top pressure is 6 〇kpa. The gas distilled from the top of the continuous multi-stage distillation column 702 is passed through the line) to the condenser 7 Condensation in 〇3, continuous discharge from line 77. Liquid phase component is discharged from line 78. Continuous multi-stage steaming with an inner diameter of about 5 cm and a length of 2 m filled with a Dixon packing (6 ηιηιφ) The middle section of Guta 7〇5 'continuously feeding the liquid phase component discharged from the pipeline redundantly' performs the distillation separation of the liquid phase component. The heat required for the distillation separation is 131506.doc • 136- 200948759 by the lower part of the tower The liquid is supplied by circulating through the line 81 and the reboiler 7 〇 7. The liquid temperature at the bottom of the column of the continuous multi-stage distillation column 705 is 21 〇 C, and the pressure at the top of the column is about 2.5 kPa. The gas distilled from the top of the crucible 5 is condensed in the condenser 7〇6 via the line 8 and continuously discharged through the line 82. The liquid phase component is discharged from the line 84.

The liquid phase component discharged from the line 84 is continuously fed to a middle portion of a continuous multi-stage distillation column 708 filled with a Dixon packing (6 ηπηφ) having an inner diameter of about 5 cm and a column length of 2 m, and the liquid is discharged. Distillation separation of phase components. The heat required for the distillation separation is supplied by circulating the liquid in the lower portion of the column via the line 86 and the re-reservator 71. The liquid temperature at the bottom of the continuous multi-stage distillation column 708 is 22 Torr and the top pressure is about 0.5 kPa. The gas taken from the tower of the continuous multi-stage distillation column 7〇8 was condensed in the condenser 709 via the line 85, and continuously discharged via the line 87 at about 1 〇 5 g/hr. The liquid discharged from the line 87 contains about 99.8% by weight of 4,4··methylene bis(cyclohexyl isocyanate). The yield relative to 4,4,_methylene bis(cyclohexylamine) was 93.2%. The continuous operation was carried out for 1 day. As a result, no deposit was accumulated on the wall surface of the thin film distillation apparatus 701. The continuous operation was carried out for 30 days. As a result, no deposit was accumulated on the wall surface of the film vaporizing apparatus. [Example 5] • Step (5-1): Production of toluene-2,4-diaminodecanoic acid bis(2-ethylbutyl) ester The bis(2-ethylbutyl carbonate) of Reference Example 3 was used. Cool into the flask with the inner volume of l. Install a three-way cock on the eggplant flask, and connect the reflow cooler to the steam column and the liquid receiver filled with the spiral packing Νο·3. The fractionation column and the thermometer were subjected to vacuum-nitrogen replacement in the system, and the purified bis(2-ethylbutyl) carbonate was distilled by 131506.doc -137· 200948759. The distilled purified product was subjected to 1H_NMR measurement, and as a result, it contained about 99.9% by weight of bis(2-ethylbutyl) carbonate. Further, it contains 0.003 ppm of iron as a metal atom. In addition to supplying 3589 g (15_6 mol) instead of the above bis(2-ethylbutyl) carbonate, 464 g (3·8 mol) instead of hexanediamine 2, The same procedure as in the step (1) of Example 1 was carried out, except that 4-toluenediamine (manufactured by Aldrich Co., Ltd.) and 7.3 g of sodium decoxide (28% decyl alcohol solution) were reacted. The solution after the reaction was analyzed by liquid chromatography, and the result was a yield of 98.5% of acetonyl-2,4-dicarbamic acid bis(2-ethylbutyl) vinegar. The reaction liquid was supplied to a column 205 in which an acid ion exchange resin (Amberlyst-15 (spherical): ROHM &amp; HAAS), which was adjusted to remove moisture, and which was kept at 80 ° C by an external sleeve, was used. Neutralization with sodium methoxide. This solution is transported via line 25 to storage tank 206. • Step (5-2): Distillation of low-boiling components The distillation of the alcohol was carried out using the apparatus shown in Fig. 3. The middle portion of the continuous multi-stage distillation column 302 filled with Dixon packing (6 ηιηηφ) having an inner diameter of 5 cm and a column length of 2 m was passed through the preheater 301 from the line 31 at about 300 g/hr. The continuous feed is recovered to the mixture of storage tanks 206. The heat required for the distillation is supplied by circulating the liquid in the lower portion of the column through the line 33 and the reboiler 304. The liquid temperature at the bottom of the continuous multi-stage steaming tower 3 02 is 160 ° C and the top pressure is about 60 kPa. The gas distilled from the top of the continuous multi-stage steaming tower 302 was condensed in the condenser 303 via line 32, and continuously discharged from the line 34 to the storage tank 305 at about 56 g/hr. From the bottom of the column, through line 33, it was continuously discharged to the storage tank 306 at about 244 g/hr. 131506.doc -138- 200948759 The carbonate is distilled off using the apparatus shown in FIG. To the middle section of a continuous multi-stage distillation column 402 filled with a Dixon packing (6 having an inner diameter of 5 cm and a column length of 2 (7), via a preheater 4〇1, from the line "at about 244 g/hr, The liquid continuous feed is recovered to the mixture of the storage tanks 3 to 6. The heat required for steaming is supplied by circulating the liquid in the lower portion of the tower via the line 43 and the refilling unit 4〇4. The continuous multi-stage steaming tower 402 The liquid temperature at the bottom of the column is 1 60 C 'the top pressure is about k7 kpa. The gas distilled from the top of the continuous multi-stage steam column 402 is condensed in the condenser 403 via line 42 from the manifold. The passage 44 is continuously discharged to the storage tank at about 138 g/hr. From the bottom of the column, it is continuously discharged to the storage tank 4〇6 via the line 43 at about 1〇6 g/hr. The liquid phase of the mixture discharged to the storage tank 406 is carried out. Analysis by analytical analysis revealed that the mixture contained about 98.9 wt% of bis(2-ethylbutyl) 2,4-diaminocarbamate. Step (5·3): using toluene-2,4- Thermal decomposition of bis(2-ethylbutyl) acetate to produce isocyanate @ The reaction was carried out using the apparatus shown in Figure 5. Thin film distillation with a heat transfer area of 0.1 m2 5 〇 1 was heated to 27 〇χ:, the internal pressure was about 13 kPa. The mixture recovered in step (5-2) to the storage tank 4〇6 was heated to 170. 〇, via line 5 〇 about 19 〇 g / The hr is supplied to the upper portion of the thin film evaporator 501. Further, dibutyltin dilaurate is fed from the line 51 at about 15 years old. From the bottom of the thin film distillation apparatus 5〇1, the liquid phase component is discharged from the official line 53. This is circulated to the upper portion of the thin distillation apparatus 5〇1 via the line 54. The gas phase component is discharged from the line 52. The inner diameter filled with the Dixon packing (6 ππηφ) is about 5 em, and the length of the column is 2 131506.doc _ 139· 200948759 m continuous multi-stage distillation tower 5 〇 501 501 又 又 4 续 续 续 续 续 续 续 续 续 续 续 续 薄膜 薄膜 薄膜 薄膜 薄膜 薄膜 薄膜 薄膜 薄膜 薄膜 薄膜 薄膜 薄膜 薄膜 薄膜 薄膜 薄膜 薄膜 薄膜 薄膜 薄膜 薄膜 气相 气相^ The heat required to remove the distillation component from the distillation phase is supplied by circulating the liquid in the lower part of the column through the tube and the re-circulating device 5. The bottom of the continuous multi-stage steaming tower (10) The liquid temperature is 160. The overhead pressure is about 5 〇 I to allow the gas distilled from the top of the continuous multi-stage distillation column 502 to pass through the line. ❹

Condensation in 5〇3, continuous discharge from line 57. The liquid phase component is withdrawn from the continuous stage multi-stage steaming column such as line 59 below the line 52. The middle portion of the continuous multi-stage distillation column 5〇5 filled with a Dixon packing (6 having an inner diameter of about 5 cm and a column length of 2 m) is continuously fed from the line 5 to discharge the liquid component of the liquid phase. Distillation separation of the gas phase component is carried out. The heat required for the distillation separation is supplied by circulating the liquid in the lower portion of the column via the line 61 and the reboiler 5 〇 7. The liquid temperature at the bottom of the column of the continuous multi-stage distillation column 505 At 16 ° C, the overhead pressure is about 1,5 kPa. The gas taken from the top of the continuous multi-stage distillation column 5〇5 is condensed in the condenser 506 via line 60, and continuously discharged through line 62. The discharge amount to the storage tank 509 is about 83 g/hr. After 40 hours of operation, the liquid phase component is discharged from the line 64 at about 16 g/hr to the storage tank 510. The liquid system discharged from the line 62 contains about 99.8% by weight of a solution of 2,4-indole diisocyanate. The yield relative to 2,4-nonylphenylenediamine was 94.7%. After 10 days of continuous operation, no accumulation was found on the wall of the thin film distillation apparatus 501. Attachment. [Example 6] .Step (6-1) : N,N'-hexanediyl-bis-aminocarbamic acid bis(2-ethylbutyl) ester 131506.do C -140- 200948759 Manufacture of 3,83 g (3.6 mol) of bis(2-ethylbutyl) carbonate in Reference Example 3 in addition to 3843 g (15.1 mol) instead of bis(2-methylbutyl) carbonate The reaction was carried out in place of the reaction of the diamine-containing hexamethylenediamine with 368 g (3.8 mol) of 2-ethyl-1-butanol and 69 g of sodium methoxide (28% decyl alcohol solution). The same method as in the step (1-1). The solution after the reaction was analyzed by liquid chromatography. The result was N,N,-hexanediyl-bis-aminocarbamic acid bis (2- in a yield of 99.5%). Ethyl butyl acrylate. The reaction solution was supplied to an acidic ion exchange resin (Amberlyst-1 5 (spherical): ROHM &amp; HAAS) containing the moisture removed and adjusted by an external casing to 8 In the column 2〇5 of 〇〇c, sodium sterol is neutralized. The solution is transported to the storage tank 206° via line 25. • Step (6-2): distillation of the low boiling component is used as shown in Fig. 3. The apparatus shown is subjected to distillation of alcohol. The middle section 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 ππηφ) is self-managed via the preheater 301. 31 is continuously fed in a liquid form at about 270 g/hr to a mixture of tanks 2 and 6. The heat required for steaming is supplied by circulating the liquid in the lower portion of the column via line 33 and reboiler 304. The liquid temperature at the bottom of the column of the multi-stage distillation column 3〇2 is 160 C 'the column top pressure is about 60 kPa. The gas distilled from the top of the continuous multi-stage distillation column 302 is passed through the line 32 in the condenser 303. Condensation is continuously discharged from line 34 to storage tank 305 at about 69 g/hr. From the bottom of the column, it was continuously discharged to the storage tank 306 at about 201 g/hr via the line 33'. The carbonate was distilled off using a device as shown in FIG. 131506.doc -141 - 200948759 The middle section of the continuous multi-stage distillation column 402 filled with Dixon packing (6 ιηηιφ) having an inner diameter of 5 cm and a column length of 2 m, via the preheater 401, from the line 41 The mixture was continuously recovered in liquid form at about 201 g/hr to a mixture of tanks 3〇6. The heat required for the steaming is supplied by circulating the liquid in the lower portion of the column through the line 43 and the reboiler 404. The liquid temperature at the bottom of the continuous multi-stage distillation column 4〇2 was 160 ° C, and the pressure at the top of the column was about 77 kPa. The gas from the top of the continuous multi-stage distillation column 4〇2 was condensed in the condenser 403 via line 42, and continuously discharged from the line 44 to the storage tank 405 at about 115 g/hr. From the bottom of the column, it was continuously discharged to the storage tank 4〇6 via the line 43, at about 86 g/hr. The result of liquid chromatography analysis of the mixture discharged to the storage tank 406 was that the mixture contained about 98·3 weight ❶/. N,N,-hexanediyl-bis-amino phthalic acid bis(2-ethylbutyl)g. Step (6-3) The isocyanate was produced by thermal decomposition of N,N'-hexanediyl-bis-aminobisruthenate bis(2-ethylbutyl) ester using a device as shown in Fig. 5.加热 Heat the thin tantalum distillation unit 5〇1 with a heat transfer area of m2 to 27〇 (&gt;c, and let the internal pressure be about 13 kPa. Heat the mixture recovered in step (6_2) to the storage tank to heat. The road 5〇 is supplied to the upper portion of the thin film evaporator 5〇1 at about 27 〇*. Further, dibutyltin dilaurate is fed from the line 51 at about 22 7 g/hr. From the bottom of the film evaporation chamber 5〇1 The liquid phase component is discharged from the line 53 and circulated to the upper portion of the thin steaming chamber device 5〇1 via the pipe. The gas phase component is discharged from the pipe 52. The filling is filled with Dixon packing (6 jobs Φ The middle section of the continuous multi-stage steaming tower 5〇2 with an inner diameter of about 5 cm and a tower length of 2 m, continuous feeding from the thin medium steaming device 131506.doc • 142· 200948759 501 red discharged by the line 52 The gas phase component is subjected to vapor separation of the gas phase component. The heat required for the vaporization separation is supplied by circulating the liquid in the lower portion of the column via the line 56 and the reboiler 504. The liquid temperature at the bottom of the continuous multi-stage distillation column 5〇2 is 16 (TC, the top pressure is about 5 〇kpa. The gas from the tower of the continuous multi-stage steaming tower 502 is condensed via the line 55. Condensed in the vessel 5〇3 and continuously discharged from the line 57. The liquid phase component is discharged from the line 59 of the continuous multistage steaming tower 5〇2 below the line 52. The filling is filled with a Dixon packing (6) Ηπηφ) is a middle portion of a continuous multi-stage distillation column 5〇5 having an inner diameter of about 5 em and a column length of 2 m, continuously feeding a liquid phase component discharged from the line 59, and performing distillation separation of the gas phase component. The heat required for the separation is supplied by circulating the liquid in the lower portion of the column via the line 61 and the reboiler 5 〇 7. The liquid temperature at the bottom of the column of the continuous multi-stage distillation column 505 is 16 〇 ° C, and the pressure at the top of the column is about The gas distilled from the top of the continuous multi-stage distillation column 5〇5 is condensed in the condenser 506 via the line 60, and is continuously discharged to the storage tank 509 via the line 62. The discharge amount in the steady state is about 55 kPae. Ii6g/hr. After 40 hours of operation, the liquid phase component is discharged from the line 64 to the storage tank 510 at about U g/hr. The liquid system contained a solution of about 99.8% by weight of hexamethylene diisocyanate. The yield relative to hexamethylenediamine was 95 5%. The continuous operation of ίο天 was not found on the wall of the thin film distillation apparatus 5〇1. Attachment. [Example 7] . Step (7-1): Production of 3-(phenoxycarbonylamino-methyl)-3,5,5-trimethylcyclohexylaminocarboxylic acid stearyl ester 131506.doc • 143- 200948759 The reaction was carried out using the apparatus shown in Fig. 7. In the state where the line A4 was closed, ^92 g (9.3 mol) of diphenyl carbonate of Reference Example 6 was supplied from the storage tank 721 via the line A1. The internal volume of 5 L of the SUS reaction vessel 724 with a baffle was supplied from the storage tank 722 through the line A2' to 1311 g (14.0 mol) of phenol to the reactor made of SUS. The temperature of the liquid in the reactor 724 was adjusted to about 50 t, and from the storage tank 723 via line A3, 528 g (3.1 mol) of 3-aminomethyl-3,5,5-trimethyl was added at about 250 g/hr. Cyclohexylamine is supplied to the reactor 724. The solution after the reaction was analyzed by liquid chromatography to give 3-(phenoxycarbonylamino-methyl)_3,5,5-trimethylcyclohexylaminocarboxylic acid in a yield of 99_3 ° / hydrazine. Benzene vinegar. The line Α4 is opened, and the reaction liquid is transported to the storage tank 725 via the line Α4. • Step (7-2): Distillation of the low-boiling component The apparatus shown in Fig. 3 is used to carry out the distillation of the phenol. The middle section of the continuous multi-stage distillation column 302 filled with Dixon packing (6 mm or more) having an inner diameter of 5 cm and a column length of 2 m was passed through the preheater 301 from the line 31 at about 300 g/hr. The liquid continuous feed is recovered to a mixture of tanks 2〇6. The heat required for steaming is supplied by circulating the liquid in the lower portion of the column through the line 33 and the refill unit 34. The liquid temperature at the bottom of the continuous multi-stage distillation column 3〇2 was 160 ° C, and the top pressure was about 60 kPa. The gas distilled from the top of the continuous multi-stage distillation column 3〇2 was condensed in the condenser 303 via line 32, and continuously discharged from the line 34 to the storage tank 305 at about 155 g/hr. From the bottom of the column, through line 33, it is continuously discharged to the storage tank 306 at about 145 g/hr. 131506.doc 200948759 The carbonate is distilled off using the apparatus shown in FIG. The middle section of a continuous multi-stage distillation column 402 filled with a Dixon packing (6 mm phantom inner diameter of 5 cm and a column length of 2 m) was passed through the preheater 401 from the line 41 at about 145 g/hr. The liquid continuous feed is recovered to the mixture of the storage tank 306. The heat required for the steaming is supplied by circulating the liquid in the lower portion of the column via the line 43 and the reboiler 4〇4. The continuous multi-stage distillation column 4〇2 The liquid temperature at the bottom of the column is 160 ° C, and the pressure at the top of the column is about 〇, 4 kPa. The gas distilled from the column of the continuous multi-stage distillation column 4 〇 2 is condensed in the condenser 403 via the line 42 The manifold 44 is continuously discharged to the storage tank 405 at about 55 g/hr. The mixture is continuously discharged to the storage tank 406 at a rate of about 90 g/hr from the bottom of the column via a line 43', and the mixture discharged to the storage tank 406 is subjected to liquid chromatography analysis. As a result, the mixture contained about 99.1% by weight of 3-(phenoxycarbonylamino-methyl)- 3,5,5-trimethylcyclohexylaminodecanoic acid phenyl ester. Step (7-3): Utilization 3·(Phenoxycarbonylamino-methyl)·3,5,5-tridecylcyclohexylcarbamic acid phenyl ester was thermally decomposed to produce isocyanate vinegar using a device as shown in FIG.The thin film distillation apparatus 5〇1 having a heat transfer area of 0.1 m2 is heated to 22〇t&gt;c such that the internal σ卩 pressure is about 13 kPa. The mixture recovered in the step (5-2) to the storage tank 406 is heated to 170°. C' is supplied to the upper portion of the thin film evaporator 501 via line 50 at about 3 〇〇g/hr. From the bottom of the thin film distillation apparatus 5〇1, the liquid phase component is discharged from the line 53 to be circulated through the line 54. To the upper part of the thin film distillation apparatus 5〇1, the gas phase component is discharged from the line 52. The continuous multi-stage distillation tower having an inner diameter of about 5 cm and a column length of 2 m filled with a Dixon packing (6 πιηηφ) The middle section of 5〇2 is continuously fed from the thin film distillation apparatus 131506.doc -145· 200948759. The gas phase component discharged through the pipeline 52 is used to carry out the vaporization of the vapor phase component. The liquid in the lower part of the tower is supplied and supplied via the line 56 and the vortex 504. The liquid temperature at the bottom of the tower of the continuous multi-stage steam storage tower 5〇2 is 15 〇. (:, the top pressure Approximately 15 kpa. The gas distilled from the top of the continuous multi-stage distillation column 502 is condensed in the condenser 5〇3 via a line. The line 57 is continuously discharged. The liquid phase component is discharged from the line 59 of the continuous multi-stage steaming tower 5〇2 below the line 52. The inner diameter is filled with a Dixon packing (6 is about 5 cm, The middle section of the continuous multi-stage distillation column 505 having a column length of 2 m continuously feeds the liquid phase component discharged from the line 59 to carry out distillation separation of the gas phase component. The heat required for the distillation separation is made by lowering the lower portion of the column. The liquid is supplied through the line 61 and the reboiler 5〇7. The liquid temperature at the bottom of the continuous multi-stage distillation column 5〇5 is 15 〇 ° C, and the pressure at the top of the column is about 丨.3 kPa. The gas from the top of the continuous multi-stage distillation column 5〇5 was condensed in the condenser 506 via the line 60, and continuously discharged to the storage tank 509 via the line 62 at about 135 g/hr. The liquid system discharged from line 92 contained a solution of about 99.8% by weight of isophoric-diisocyanate. The yield based on 3-aminomethyl-3,5,5-trimethylcyclohexylamine was 95.3%. The continuous operation was carried out for 100 days, and no deposit was accumulated on the wall surface of the thin tandem distillation apparatus 501. [Example 8] • Step (8-1): Production of N,N'-hexanediyl-bis-aminocarbamic acid di(n-heptyl) ester In addition to supplying 3445 g (13.3 mol) instead of carbonic acid double (2- In addition to the reaction of dinonheptyl carbonate, 36 〇g (3 Λ mol) hexamethylenediamine, and 6 〇g methanol steel (28°/. sterol solution) of thiobutyl butyl vinegar, the implementation and implementation were carried out. Step 1 of Example 1 〇131506.doc •146- 200948759 i) The same method. The solution after the reaction was analyzed by liquid chromatography, and as a result, N,N,-hexanediyl-bis-aminocarbamic acid di(n-heptyl) ester was obtained in a yield of 98.9%. The reaction liquid was supplied to an acid ion exchange resin (Amberly St_15 (spherical): R〇HM &amp; Haas &amp; s) which was subjected to removal of moisture and was insulated by an external sleeve to 8 〇&lt;t. Sodium methoxide was neutralized in 〇5. This solution is transported via line 25 to storage tank 2〇6. • Step (8-2): Distillation of low-boiling components. Use the device as shown in Figure 3 to carry out the alcohol hall. The middle section of the continuous multi-stage distillation column 302 filled with Dixon packing (6 πιιηφ) having an inner diameter of 5 cm and a column length of 2 m was passed through the preheater 3〇1 from the line 31 at about 280 g/hr. The mixture was recovered as a mixture of tanks 2〇6 in a continuous liquid feed. The heat required for the distillation is supplied by circulating the liquid in the lower portion of the column through the line 33 and the reboiler 34. The liquid temperature at the bottom of the continuous multi-stage distillation column 3〇2 was 160 ° C, and the top pressure was about 13 kPa. The gas distilled from the top of the continuous multi-stage distillation column 3〇2 was condensed in the condenser 303 via the line 32, and continuously discharged from the line 34 to the storage tank 305 at about 52 g/hr. From the bottom of the column, through line 33, it was continuously discharged to the storage tank 3〇6 at about 228 g/hr. Using the apparatus shown in Figure 4, the carbonate pavilion was removed. The middle section of the continuous multi-stage distillation column 402 filled with Dixon packing (6 ιηιηφ) having an inner diameter of 5 cm and a column length of 2 m was passed through the preheater 4〇1 from the line 41 at about 228 g/hr. The mixture was recovered as a mixture of tanks 3〇6 in a continuous liquid feed. The heat required for the distillation is supplied by circulating the liquid in the lower portion of the column through the line 43 and the reboiler 404. The liquid temperature at the bottom of the continuous multi-stage distillation column 4〇2 is 170 C 'the top pressure is about 〇·13 kPa. The gas distilled from the continuous multi-stage steaming tower 131506.doc • 147- 200948759 2 was condensed in the condenser 4〇3 via the line core, and continuously discharged from the line 44 at about 136 g/hr. Storage tank 4〇5. From the bottom of the column, it is continuously discharged to the storage tank 4〇6 via the pipe 43' at about 92 g/hr. The mixture discharged to the storage tank was subjected to liquid chromatography analysis, and as a result, the mixture contained about 98-6 weight of bis(n-heptyl) hexamethylenedicarbamate. Step (6) Production of Isocyanate by Thermal Decomposition of N,N,-hexanediyl-bis-aminocarbamic acid Di(n-heptyl) Brewing The reaction was carried out using a apparatus as shown in Fig. 5. The thin film distillation crucible having a heat transfer area of 0.1 m2 was placed at 5 〇 1 to 27 〇 (&gt;c, and the internal friction was about 13 kPa. The mixture recovered in the step (4) to the storage tank 4〇6 was heated to 17 :. (: 'Approximately 27 〇g/hr via line 5〇1 is supplied to the thin film evaporator 5 (H above the pipe from the line 51 to about 19 6 coffee feed dibutyl tin dilaurate. From the thin film distillation unit 5〇 At the bottom of 1, the liquid phase component is discharged from the line 53 and "circulated to the upper portion of the film evaporation device 501 via the line. The gas phase component is discharged from the line 52. The filling is filled with a Dixon packing (6 The middle section of the continuous multi-stage distillation column 502 having an inner diameter of about 5 (10) and a column length of 2 m is continuously fed from the vapor phase component discharged from the thin film distillation apparatus 5〇1 via the line 52, and the vapor phase separation of the gas phase component is performed. The heat required for the vaporization separation is supplied by circulating the liquid in the lower portion of the column via the line 56 and the reboiler 504. The temperature of the liquid at the bottom of the column of the continuous multi-stage distillation column 5〇2 is 160. (:, Tower The top pressure is about 5〇kpa, so that the gas from the continuous multi-stage steaming tower 502 (four) ^ gas is condensed through the pipeline condenser 5〇3, self-management The passage 57 is continuously discharged. The liquid phase component is discharged from the line 59 at the position of the line 52 from the low level of the continuous multi-stage steaming tower 5〇2, 506.doc 200948759. The inner diameter is filled with the Dixon packing (6) 5 cm, the length of the tower is 2: the middle section of the continuous multi-stage steaming tower 5G5, continuously feeding the gas phase component discharged from the pipeline %, and performing the steaming separation of the gas phase component. The liquid in the lower portion of the column is supplied by circulating the line 61 and the reboiler. The liquid temperature at the bottom of the column of the continuous multi-stage distillation column 505 is (10) C, and the pressure at the top of the column is about 1.5 kPa. The gas from the tower top of the steaming tower 5〇5 is condensed in the condenser 5〇6 via the line 60, and continuously discharged to the storage tank 5〇9 via the line 62. The discharge amount in the steady state is about 〇7 years old. After 40 hours of operation, the liquid phase component was discharged from the line 64 to the storage tank 510 at about 21 coffee. The liquid system discharged from the line 62 contained a solution of about 99.8% by weight of hexamethylene diisocyanate. The yield of the diamine was 94 9%. The continuous operation was carried out for 10 days, and no accumulation was found on the wall of the thin film distillation apparatus 5〇1. Attachment. [Example 9] Step (9-1) . Production of N,N'-hexanediyl-bis-aminocarbamic acid bis(3-methylbutyl) ester except 2 ό 87 g (l3·3 mol) In addition to the reaction of the bis(3-methylbutyl)S曰 carbonate, 407 g (3.5 mol) hexamethylenediamine, and 6.8 g of sodium methoxide (28% methanol solution) of Reference Example 1, the examples and the examples were carried out. Step G - 丨) The same method. The solution after the reaction was analyzed by liquid chromatography, and as a result, ruthenium, Ν·-hexanediyl-bis-aminocarbamic acid bis(3 methyl butyl) was formed in a yield of 99.5%. Base) ester. The line 24 was opened, and the reaction liquid was supplied to an acid ion exchange tree wax (Amberlyst-15 (spherical): R〇hm &amp; HAAS company) which was subjected to the removal of moisture and adjusted to 131506.doc -149-200948759. And using an external casing to keep 8 〇〇c of the column 2〇5 in the middle of sodium methoxide neutralization. The solution is conveyed via line 25 to a storage tank 206°. Step (9-2): the low boiling component is distilled to the middle of the continuous multi-stage distillation column 302, via the preheater 301, from the line 31 at about 300 g/ The hr is continuously fed to the mixture of the storage tank 2〇6 in a liquid form, and the liquid phase component is continuously discharged from the bottom of the column to the storage tank 3〇6' to the continuous multi-stage distillation column 4 via the line 33 at about 241 g/hr. In the middle section of 〇2, the mixture of the tanks 3〇6 is continuously fed from the line 41 at a flow rate of about 241 g/hr through the preheater 4〇1, and the steps of the embodiment are carried out. (1_2) The same method. The gas distilled from the top of the continuous multi-stage distillation column 402 was condensed in the condenser 403 via the line 42, and continuously discharged from the line 44 to the storage tank 405 at about 123 g/hr. From the bottom of the column, via line 43, it is continuously discharged to the sump 406 at about 118 g/hr.液相 The mixture discharged to the storage tank 4〇6 was subjected to liquid chromatography analysis, and as a result, the mixture contained about 98.5 wt% of bis(3-mercaptobutyl) hexyldiyl-bis-amino phthalate. Step (9-3): Production of isocyanate by thermal decomposition of N,N'-hexanediyl-bis-amino bis(3.methylbutyl) phthalate using a device as shown in FIG. . A thin tantalum distillation apparatus 5〇1 (manufactured by K〇bel (3) eco-solutions, Japan) having a heat transfer area of 〇 was heated to 27 CTC so that the internal pressure was about 13 kPa. The mixture recovered in the step (9-2) to the storage tank 406 is heated to 2〇〇131506.doc -150-200948759 °C, and supplied to the upper portion of the thin film evaporator 501 via the line 50 at about 280 g/hr. The same procedure as in the step (1-3) of Example 1 was carried out except that the line 51 was fed with dibutyltin dilaurate at about 25.3 g/hr. The liquid was continuously discharged to the storage tank 5〇9 via line 62 at about 107 g/hr. After 40 hours of operation, the liquid phase component was discharged from the line 64 to the storage tank 510 at about 82 g/hr. The liquid system discharged from line 62 contained a solution of about 99.8% by weight of hexamethylene diisocyanate. The yield relative to hexamethylenediamine was 79 〇/〇. The continuous operation was carried out for 10 days. The deposit was not found on the wall surface of the thin film distillation apparatus 501. [Example 10] Step (10-1): Production of bis(3-mercaptobutyl)-4,4,-methylene-dicyclohexylamino phthalate except for supply of 3272 g (16.2 mol) Example 1, bis(3-mercaptobutyl)carbonate, 757 g (3.6 mol) 4,4,-decylene bis(cyclohexylamine) in place of hexamethylenediamine, 6.9 g sodium methoxide (28% decyl alcohol solution) In addition to the reaction, the same procedure as in the step (1-1) of Example 1 was carried out. The solution after the reaction was analyzed by liquid chromatography, and bis(3-methylbutyl) 44,-methylene-dicyclohexylamino phthalate was obtained in a yield of 98,9%. The reaction solution was supplied to a column 205 in which an acidic ion exchange resin (Amberlyst_15 (spheroidal ROHM &amp; HAAS)) containing moisture was removed and held in an outer sleeve by (9) C, and sodium methoxide was neutralized. The solution is transported via line 25 to storage tank 206. Step (10-2): Distillation of low boiling components 131506.doc -151- 200948759 Using the apparatus shown in Figure 3, the alcohol is sold. The middle section of a continuous multi-stage distillation column 312 filled with a Dixon packing (6 π ΐΓ πφ) having an inner diameter of 5 cm and a column length of 2 m, via a preheater 3〇1, from the line 31 at about 280 g/ The hr is continuously fed in liquid form to the mixture of the storage tanks 2 to 6. The heat required for the distillation is supplied by circulating the liquid in the lower portion of the column via the line 33 and the reboiler 304. The continuous multi-stage distillation column 3〇2 The liquid temperature at the bottom of the tower is 160 C, and the pressure at the top of the column is about 70 kPa. The gas distilled from the top of the continuous multi-stage distillation column 3〇2 is condensed in the condenser 3〇3 via line 32, and self-management The weir 34, about 44 g/hr, is continuously discharged to the sump 305. It is continuously discharged from the bottom of the tower via the line 33' at about 236 g/hr. Exit to the storage tank 3〇6. Distillation of the carbonate is carried out using a device as shown in Fig. 4. The continuous multi-stage distillation column 402 is filled with a Dixon packing (6 having an inner diameter of 5 em and a column length of 2111). The middle section, through the preheater 4〇1, is continuously fed from the line 41 at about 236 g/hr in liquid form to the mixture of the storage tanks 3〇6. The heat required for the distillation is obtained by passing the liquid in the lower part of the tower. The line 43 and the reboiler 〇 404 are circulated and supplied. The liquid temperature at the bottom of the continuous multi-stage distillation column 4〇2 is 160 C 'the top pressure is about 2.6 kPa. The self-continuous multi-stage steaming tower 4〇2 The overhead gas is condensed in condenser 4〇3 via line 42 and continuously discharged from line 44 to storage tank 4〇5 at about 127 g/hr. From the bottom of the column via line 43' to about 1 〇 9 g/hr was continuously discharged to the storage tank 4〇6. The mixture discharged to the storage tank 406 was subjected to liquid chromatography analysis, and as a result, the mixture contained about 99.0% by weight of bis(3-methylbutyl)4 4, a Base _-cyclohexylamino formate vinegar. Step (10-3): Preparation of bis(3-methylbutyl)-4,4|_methylene-dicyclohexyl 131506.doc 152· 200948759 amide group A The thermal decomposition of the acid ester to produce an isocyanate is carried out by using a device as shown in Fig. 8. The continuous multi-stage distillation column 801 having an inner diameter of about 5 cm and a column length of 2 m filled with a Dixon packing (6 ππηφ) Middle section 'The mixture recovered in step (1〇-2) to storage tank 406 is heated to 170 ° C. 'Feed at about 220 g/hr via line B0, while feeding from line B1 at 15.7 g/hr Dibutyltin dilaurate is subjected to thermal decomposition reaction. The heat required for the thermal decomposition reaction is supplied by circulating the liquid in the lower portion of the column through the line B3 and the reboiler 803. The liquid temperature at the bottom of the column of the continuous multi-stage distillation column 801 was 280 ° C, and the pressure at the top of the column was about 15 kPa. The gas distilled from the top of the continuous multi-stage distillation column 801 is condensed in the condenser 802 via the line B2, and continuously discharged from the line B4. From the bottom of the continuous multi-stage distillation column 801, the liquid phase component is recovered via line B3. The middle portion of the continuous multi-stage steaming tower 8〇4 filled with the Dixon packing (6 ππηφ) having an inner diameter of about 5 cm and a column length of 2 m is continuously fed through the liquid phase component discharged from the pipe B6. 'Distillation separation of the liquid phase components. The heat required for the distillation separation is supplied by circulating the liquid in the lower portion of the column through the line and the reboiler 8〇6. The liquid temperature at the bottom of the continuous multi-stage steaming tower 804 is 220 C, and the top pressure is about 5.2 kPa. The gas distilled from the top of the continuous multi-stage steaming tower 8〇4 was condensed in the condenser 805 via the line B7, and continuously discharged from the line B9. From the bottom of the continuous multi-stage distillation column 804, the liquid phase components are recovered via line B8 and line B11. The liquid phase component discharged from the pipe B8 is continuously fed to the middle portion of the continuous multi-stage distillation column 807 filled with the Dixon packing (6 ηιιηφ) 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. Distillation separation required 131506.doc • 153· 200948759 ... is given by circulating the liquid in the lower part of the tower through the pipeline and the reboiler. The liquid temperature at the bottom of the continuous multi-stage steaming tower 807 is 220 C ′ ^ The top waste force is about 〇.4〇 kPa. The gas distilled from the continuous multi-stage steaming tower is condensed in the condenser 8A through the line B12, and continuously discharged through the line B13. ^ The discharge of the normal state is about (10) coffee. The liquid helium discharged from the line B13 contains a solution of about 99% by weight of 4,4,methylenebis(cyclohexyl isocyanate). The yield of methylene bis(cyclohexylamine) was 82.2% with respect to 4,4. After continuous operation for 10 days, it was found that deposits were accumulated in the inside of the continuous multi-stage distillation column 801. [Example 11] Step (11-1): Production of N,N'-hexanediyl-bis-amino bismuthanoate bis(2-ethylbutyl) ester In addition to supplying 3547 g (15.4 mol) instead of carbonic acid Bis(2-methylbutyl) ester of bis(2-ethylbutyl) carbonate of Reference Example 3, 407 g (3.5 mol) of hexamethylenediamine, 6.8 g of sodium decoxide (28% decyl alcohol solution) The same procedure as in the step (1-1) of Example 1 was carried out, except that the reaction was carried out. The reaction solution was analyzed by liquid chromatography to give yttrium, Ν'-hexanediyl-bis-amino bis(2-ethylbutyl) phthalate at a yield of 99.1 ° / ◦. . The reaction solution was supplied to a column 205 containing an acidic ion exchange resin (Amberlyst-15 (spherical): ROHM &amp; HAAS), which was adjusted to remove moisture, and kept at 80 t by an external sleeve, to carry out sodium methoxide. Neutral. This solution is transported via line 25 to storage tank 206. Step (11-2): Thermal decomposition of N,N'-hexanediyl-bis-carbamic acid bis(2-ethylbutyl) ester to produce isocyanate 131506.doc -154- 200948759 The device shown is reacted. The thin film distillation apparatus 5〇1 having a heat transfer area of 0.1 m2 was heated to 27 (rc, and the internal pressure was about 13 kPa. The mixture recovered in the step to the storage tank 2〇6 was heated to 1 70. (:, via the piping 50 is supplied to the upper portion of the thin film evaporator 501 at about 790 g/hr. Further, dibutyltin dilaurate is fed from the line 51 at about 21 9 §/1^. From the bottom of the thin film distillation apparatus 5〇1, the liquid is supplied. The phase component is discharged from line 53 and circulated to the upper portion of the thin film distillation apparatus 5〇 via line 54. The gas phase component is discharged from line 52.

The middle portion of the continuous multi-stage distillation column 5〇2 filled with a Dixon packing (6 πιηιφ) having an inner diameter of about 5 cm and a column length of 2 m is continuously fed from the thin film distillation apparatus 501 through the line 52. The gas phase component is subjected to distillation separation of the gas phase component. The heat required for the distillation separation is supplied by circulating the liquid in the lower portion of the column through the line 56 and the reboiler 504. The liquid temperature at the bottom of the continuous multi-stage distillation column 5〇2 was 160. (:, the top pressure is about 5 〇 kpa, so that the gas from the tower top of the continuous multi-stage steaming tower 502 is condensed in the condenser 5〇3 via the line 55. The liquid phase component is discharged from the line 59 of the continuous multi-stage steaming tower 5〇2 below the line 52. The filling is filled with a Dixon packing (the inner diameter of 6 is about 5 plus, and the test length is 2 m continuous). The middle section of the multi-stage steaming tower 505 continuously feeds the liquid phase component discharged from the pipeline to carry out the distillation separation of the gas phase component. The heat required for the distillation separation is performed by passing the liquid in the lower portion of the tower through the pipeline 61 and The reboiler 507 is circulated and supplied. The temperature of the liquid at the bottom of the continuous multi-stage steaming tower 5〇5 is (10) C 'the top pressure is about h5 kPa°, so that the technology from the continuous multi-stage steaming tower 505 is The gas is condensed in the condensation (4) 6 via the tube (4) and continuously discharged to the storage tank 509 via the line 131506.doc • 155· 200948759 62. The discharge amount in the steady state is about 112 g/hr. After 40 hours of operation, about 182 from the line 64 The liquid phase component is discharged to the storage tank 510 by g/hr. The liquid system discharged from the line 62 contains about 99.8% by weight of diisocyanate. The solution was 88 2 Torr/〇 with respect to hexamethylenediamine. The continuous operation was carried out for 10 days, and no deposit was found on the wall surface of the thin distillation apparatus 501. [Example 12] ^. Step (12 -1) : Production of 3-((3-methylbutoxy)carbonylaminomethyl_methyl_3,5,5-trimethylcyclohexylaminocarbamic acid (3-methylbutyl) ester 3224 g (l6. 〇mol) of bis(3-mercaptobutyl)carbonate of Reference Example 1, 647 g (3.8 mol) of 3-aminomethyl·3 3 5_trimethyl ring instead of hexamethylenediamine The reaction was carried out in the same manner as in the step (1 - hydrazine) of Example 1 except that hexylamine and 7.3 g of sodium decoxide (28% methanol solution) were reacted. The solution after the reaction was analyzed by liquid chromatography. As a result, 3-((3•indenyl)butoxy)carbonylamino-methyl-3,5,5-trimethylcyclohexylaminodecanoic acid (3-methylbutyl) was produced in a yield of 98 8%. Ester. The reaction solution is supplied to the container for removal of moisture and adjusted.

An acidic ion exchange resin (Amberlyst-15 (spherical): r〇hm &amp; manufactured by HAAS) was used and the inner column was immersed in a column 205 of 80»c to carry out sodium hydride neutralization. This solution is transported via line 25 to storage tank 2〇6. • Step (12-2): Go to the low-boiling ingredients. Use the device shown in Figure 3 to carry out the alcohol. The middle section of the continuous multi-stage distillation column 302 filled with Dixon packing (6 ππηφ) having an inner diameter of 5 cm and a column length of 2 m passes through the preheater 3〇1, from the line 31 131506.doc -156- 200948759 A mixture of tanks 2〇6 was recovered as a continuous feed in liquid form at about 280 g/hr. The heat required for the distillation is supplied by circulating the liquid in the lower portion of the column through the line 33 and the reboiler 304. The liquid temperature at the bottom of the tower of the continuous multi-stage distillation column 3〇2 is 160 ° C, and the pressure at the top of the tower is about 7 〇 kpa. The gas distilled from the top of the continuous multi-stage distillation column 3〇2 was condensed in the condenser 3〇3 via the line 32, and continuously discharged to the storage tank 3〇5 from the line 34 at about 48 g/hr. From the bottom of the column, it was continuously discharged to the storage tank 3〇6 via line 33 at about 232 g/hr. The carbonate was distilled off using a device as shown in FIG. The middle section of the continuous multi-stage distillation column 402 filled with Dixon packing (6 ηηηιφ) having an inner diameter of 5 cm and a column length of 2 m, via the preheater 4〇i, from the line 4j to about 237 g /hr is recovered as a mixture of tanks 3〇6 in a continuous liquid feed. The heat required for the distillation is supplied by circulating the liquid in the lower portion of the column through the line 43 and the reboiler 404. The liquid temperature at the bottom of the continuous multi-stage distillation column 4〇2 was 200 C, and the pressure at the top of the column was about 7.9 kPa. The gas from the top of the continuous multi-stage distillation column 402 was condensed in the condenser 403 via line 42, and continuously discharged from the line 44 to the storage tank 4〇5 at about 123 g/hr. From the bottom of the column, through line 43, it is continuously discharged to the storage tank 406 at about 109 g/hr. The mixture discharged to the storage tank 406 was subjected to liquid chromatography analysis, and as a result, the mixture contained about 84.0% by weight. 3-((3-methylbutoxy)carbonylamino]indolyl-3,5,5-trimethylcyclohexylaminocarbamic acid (3-decylbutyl) ester. Step (12-3) Manufactured by thermal decomposition of 3-((3-methylbutoxy)carbonylamino-methyl-3,5,5-dimethylcyclohexylaminodecanoic acid (3-mercaptobutyl) ester The isocyanate was reacted using a device as shown in Figure 5. 131506.doc -157- 200948759 The film vaporizing device with a heat transfer area of G] m2 was heated to 27 generations, and the P pressure in θ was about 131 Pa. The 2*) recovered to the sump 406 is heated to 170 C' and supplied to the upper portion of the film 501 via the line 50 at about 200 g/hr. Again, about 2 g/h from the line 51. Feeding monobutyltin dilaurate (manufactured by Sakamoto's Wako Pure Chemical Industries, Ltd.). From the bottom of the membrane smelting apparatus 5〇1, the liquid phase component is discharged from the line 53 and passed through the line 54 to the film. The distillation apparatus 5〇1 is above #. The gas phase component is discharged from the line 5 2 .

The middle section of the continuous steaming tower 502 filled with Dixon packing (6) having an inner diameter of about 5 (10) and a length of 2 is continuously fed from the thin film steaming device = 1 &amp; s road 52 The gas phase component that is discharged is supplied with the heat required to separate the vapor phase component from the vaporization column 5 by circulating the column (four) and reboiling (four) four cycles. The liquid temperature of the continuous multi-stage steaming material 5Q2 is 150. (: 'The top pressure is about 5 。. The gas from the tower top of the continuous steaming tower 502 is condensed in the condenser via line 55, and is continuously discharged from the line 57. Since continuous continuous multi-stage The gas phase component is discharged from the line 59 of the steam tower 5〇2 below the line 52. The continuous multi-stage steaming is filled with a Dixon packing (6 having an inner diameter of about 5 cm and a tower length of 2 m). In the middle section of the tower 5G5, the gas phase component discharged from the pipeline 59 is continuously fed to perform distillation separation of the gas phase component. The heat required for the distillation separation is performed by circulating the liquid in the lower portion of the tower via (4) 61 and then (4) 5〇7. However, the liquid temperature at the bottom of the tower of the multi-stage steaming tower 505 is &quot;Ο °c 'the tower (four) force is about 1 &gt; 5 kPa. The gas distilled from the top of the continuous multi-stage steaming tower 5〇5 It is condensed in the condenser 5〇6 via the line 60, and continuously discharged to the storage tank 509 via the pipeline I31506.doc-158-200948759 62. The discharge amount in the steady state is about 90.0 g/hr, and after the operation for 40 hours, the self-pipeline 64. The liquid phase component is discharged to the storage tank 510 at about 44 g/hr. The liquid system discharged from the line 62 contains about 99.8 weights. The solution of diisocyanate was 8 1.5% based on the yield of hexamethylenediamine. The continuous operation was carried out for 10 days, and no deposit was accumulated on the wall surface of the thin film distillation apparatus 501. [Example 13] Step (13-1) : Preparation of N,N'-hexanediyl-bis-aminocarbamic acid bis(2-ethylhexyl) ester except for the supply of 3609 g (12,6 mol) instead of bis(2-methylbutyl) carbonate The reaction was carried out in the same manner as in Example 5 except that bis(2-ethylhexyl) carbonate, 349 g (3.0 mol) of hexamethylenediamine, and 5.8 g of sodium decanoate (28% decyl alcohol solution) were reacted. The same procedure as in the step (1-1). The solution after the reaction was analyzed by liquid chromatography, and the result was N,N,·hexanediyl-bis-aminocarbamic acid bis(2- in a yield of 98.5%). Ethylhexyl) ester. The reaction solution was supplied to an acidic ion exchange resin (AmbeHyst_15 (spherical): ROHM & HAAS), which was adjusted to remove moisture, and was kept at 8 Torr by an external sleeve (&gt;c In the column 205, neutralization of sodium decoxide is carried out. The solution is transported to the storage tank 206 via a pipeline. • Step (13-2): the low boiling component is used as shown in Fig. 3. The device shown is 'worked in the middle of the continuous multi-stage distillation column 302 filled with Dixon packing (6) with an inner diameter of 5 (10) and a length of 2 m 131506.doc -159-200948759. The preheater 301 is continuously fed from the line 31 at a rate of about 300 g/hr in a liquid to the mixture of the storage tank 206. The heat required for steaming is performed by passing the liquid in the lower portion of the column through the line 33 and the reboiler. 304 cycles to supply. The liquid temperature at the bottom of the continuous multi-stage distillation column 3〇2 is 160 C 'top pressure of about 13 kPa. The gas distilled from the top of the continuous multi-stage distillation column 302 was condensed in the condenser 303 via line 32, and continuously discharged from the line 34 to the storage tank 305 at about 58 g/hr. From the bottom of the column, it was continuously discharged to the storage tank 3〇6 via the line 33' at about 242 g/hr. The carbonate was distilled off using a device as shown in FIG. The middle section of the continuous multi-stage distillation column 402 filled with Dixon packing (6 ιηιηφ) having an inner diameter of 5 cm and a column length of 2 m was passed through the preheater 4〇i from the line 4 i at about 219 g/hr. The mixture was recovered as a mixture of tanks 3 and 6 in a continuous liquid feed. The heat required for steaming is supplied by circulating the liquid in the lower portion of the column through the line crucible and the reboiler 404. The liquid temperature at the bottom of the continuous multi-stage distillation column 4〇2 is 210 C ^ ^ top pressure is about 0.13 kPa. The gas distilled from the top of the continuous multi-stage steaming tower 402 was condensed in the condenser 4〇3 via the line 42 and continuously discharged to the storage tank 4〇5 from the line 44 at about 145 g/hr. From the bottom of the column, it was continuously discharged to the storage tank 4〇6 via a line 43' at about 98 g/hr. The mixture discharged to the storage tank 406 was subjected to liquid chromatography analysis, and as a result, the mixture contained about 73.9% by weight of &lt;Ν,Ν,-hexanediyl-bis-aminocarbamic acid bis(2-ethylhexyl) ester. Step (U-3): The isocyanate was produced by thermal decomposition of N,N,-hexanediaminocarbamic acid bis(2.ethylhexyl) ester using a device as shown in FIG. 13I506.doc .160- 200948759 A thin film distillation apparatus 5〇1 having a heat transfer area of 0.1 m2 is heated to 27 〇&lt;t, so that the inner (four) force is about 13 kPa. The mixture recovered in the step (13_2) to the storage tank 4〇6 is heated to 17 (TC, via line 50, to the thin film evaporator 5 at about 27 〇g/hH^ (the upper part of the crucible. Again 'from the line 51 Dibutyltin dilaurate was fed at about 22 g/hr. From the bottom of the thin film distillation apparatus 501, the liquid phase component was discharged from the line 53 and circulated through the line 54 to the upper portion of the thin film distillation apparatus 501. The phase components are discharged from line 52.

The middle section of a continuous multi-stage steaming tower 5.2 filled with Dixon packing (6 mm &lt;)&gt; with an inner diameter of about 5 cm and a tower length of 2 m is continuously fed from the thin film steaming device 01 The gas phase component discharged from the g channel 52 is subjected to distillation separation of the gas phase component. The heat required for the distillation separation is supplied by circulating the liquid in the lower portion of the column through the line 56 and the reboiler 504. The liquid temperature at the bottom of the continuous multi-stage distillation column 5〇2 is 160 ° C, and the pressure at the top of the column is about 5 〇 kpa. The gas distilled from the top of the continuous multi-stage distillation column 502 is condensed in the condenser via a line and continuously discharged from the line 57. The liquid phase component is discharged from the line 59 at a position lower than the line 52 of the continuous multi-stage steaming tower 5 〇 2 °. The middle section of the continuous multi-stage distillation column 505 having an inner diameter of about 5 m filled with a Dixon packing (6 ππηφ) in a 2 direction, and continuously feeding the liquid phase component discharged from the line 59 to carry out the gas. Distillation separation of phase components. The heat required for the distillation separation is supplied by circulating the liquid in the lower portion of the column through the line 61 and the reboiler 5?7. The liquid temperature at the bottom of the column of the continuous multi-stage distillation column 505 is 16 〇 'the top pressure is about μ kPae. The gas distilled from the top of the continuous multi-stage steaming tower 5 〇 5 is passed through the line 60 in the condenser 506. The condensation is continuously discharged to the storage tank 509 via the line 62. The discharge amount in the steady state is about I>^131506.doc -161 · 200948759 g/hr. After 40 hours of operation, the liquid phase component was discharged from the line 64 to the storage tank 510 at about 82 g/hr. The liquid system discharged from line 62 contains a solution of about 99.8% by weight of hexamethylene diisocyanate. The yield based on hexamethylenediamine was 70.9%. The continuous operation was carried out for 10 days, and no deposit was accumulated on the wall surface of the thin film distillation apparatus 501. [Example 14] Step (14-1): Preparation of hydrazine, Ν'-hexanediyl bis-carbamic acid dibutyl ester, except for supplying 3293 g (l8.9 m〇l) instead of carbonic acid double (2) In addition to the reaction of dibutyl carbonate, 523 g (4.5 m〇1) hexamethylenediamine, and 87 g of sodium methoxide (28% methanol solution) of Reference Example 2, the reaction and the examples were carried out. Step 1 (1) The same method. The solution after the reaction was analyzed by liquid chromatography, and as a result, ν, Ν·-hexanediyl-bis-aminocarbamic acid di(n-butyl) ester was obtained in a yield of 98.8%. The reaction liquid was supplied to an acid ion exchange resin (Amberlyst-15 (spherical): manufactured by ROHM &amp; HAAS), which was adjusted to remove moisture, and was kept at 80 〇c by an external sleeve. In the middle, sodium methoxide is neutralized. This solution is transported via line 25 to storage tank 206. • Step (14-2): Low-boiling ingredients are used to distill off the alcohol using the apparatus shown in Figure 3. The middle section of the continuous multi-stage distillation column 302 filled with Dixon packing (6 πιπιφ) having an inner diameter of 5 cm and a column length of 2 m was passed through the preheater 3〇1 from the line "about 290 g/ The hr is continuously fed in liquid form to the mixture of the storage tanks 2 to 6. The heat required for the distillation is supplied by circulating the liquid in the lower portion of the column via the line 33 and the reboiler 131506.doc-162-200948759 304. The liquid temperature at the bottom of the multi-stage distillation column 3〇2 is 150 ° C, and the pressure at the top of the column is about 70 kPa. The gas from the top of the continuous multi-stage distillation column 3〇2 is passed through the line 32 to the condenser. The condensation in 3〇3 was continuously discharged from the line 34 to the storage tank 305 at about 50 g/hr. From the bottom of the column, it was continuously discharged to the storage tank 306 at about 240 g/hr via the line 33. The apparatus shown in Fig. 4 was used. The middle portion of the continuous multi-stage distillation column 402 having an inner diameter of 5 cm and a column length of 2 m filled with a Dixon packing (6 ηπηφ) is passed through a preheater 4〇1, Line 41 回收 is continuously fed in liquid form at about 240 g/hr to the mixture in tank 306. The heat required for distillation is obtained by passing the liquid in the lower portion of the column through the tube. The road 43 and the reboiler 404 are circulated and supplied. The liquid temperature at the bottom of the continuous multi-stage distillation column 4〇2 is 15 〇 ° C, and the pressure at the top of the column is about K3 kPae to make the column from the continuous multi-stage distillation column 4〇2 The top distillate gas is condensed in condenser 4〇3 via line 42 and continuously discharged from line 44 to storage tank 4〇5 at about 132 g/hr. From the bottom of the column via line 43, it is continuous at about 108 g/hr. It is discharged to the storage tank 4〇6. • The mixture discharged to the storage tank 406 is subjected to liquid chromatography analysis, and as a result, the mixture contains about 98.5% by weight of iN,N,-dihexyl-bis-aminocarbamic acid di(n-butyl). Ester. Step (14-3): The isocyanate is produced by thermal decomposition of N,N,-hexanediyl-bis-aminocarbamic acid di(n-butyl), and the reaction is carried out using a device as shown in FIG. The thin film distillation apparatus 5〇1 having a heat transfer area of 0.1 m2 is heated to 27 〇 (&gt;c, the internal pressure is about 13 kPa. The mixture recovered in step 〇4_2) to the storage tank 4〇6 is heated to 17 ( The TC is supplied to the upper portion of the film evaporator 501 via a line 5 以 at about 26 〇. Further, it is fed from the line 51 at about 25 6 g/hr. Dibutyltin laurate. From the bottom of the thin film distillation apparatus 501, the liquid phase component is discharged from the line 53 and circulated to the upper portion of the thin film distillation apparatus 501 via the line 54. The gas phase component is discharged from the line 52. The middle portion of a continuous multi-stage steaming tower 5G2 having a Dixon packing (6 having an inner diameter of about 5 and a tower length of 2 ❹ ❹ m), and a gas phase component continuously discharged from the film suffocating device 501 via the g path 52 Distillation separation of the gas phase component is carried out. The heat required for the distillation separation is supplied by circulating the liquid in the lower portion of the column through the line 56 and the reboiler 504. The liquid temperature at the bottom of the continuous multi-stage distillation column 5〇2 is 16 (TC, the top pressure is about 5 〇kpa. The gas from the tower top of the continuous multi-stage steaming tower 502 is condensed via the line 55. In the 5〇3, the V condensation is continuously discharged from the t-way 57. The gas phase component is discharged from the line 59 of the continuous multi-stage steaming tower 5〇2 which is lower than the line 52. The filling is filled with the Dixon packing (6) The middle section of the continuous multi-stage steaming tower 5G5 having an inner diameter of about 5 (10) and a length of 2 ^, the continuous feeding of the gas discharged from the pipeline to form a steaming separation of the gas phase components. The heat is supplied by circulating the liquid in the lower portion of the column through the line 61 and the reboiler 507. The liquid temperature at the bottom of the continuous multi-stage steaming tower 5G5 is (10). c, the pressure at the top of the column is about U kPa. The gas from the tower top of the continuous multi-stage steaming tower 5〇5 is condensed in the condenser via the line 6G, and continuously discharged to the storage tank 509 via the line ^. The discharge amount in the steady state is about 75.1 g/hr. After 40 hours of operation, the liquid phase component is from about 1 to the storage tank 510 from the line 64. The liquid system discharged from the official road 62 contains about 99.8% by weight of diisocyanide. 131506.doc -164 - 200948759 The solution of the diester was 75.1% based on the yield of hexamethylenediamine. The continuous operation was carried out for 48 hours. The result was found to be accumulated on the wall of the upper part and the side part of the thin film distillation apparatus 5〇1. [Example 15]. Step (15-1): The production of N,N'-hexanediyl-bis-aminocarbamic acid bis(3-methylbutyl) ester was used as shown in FIG. The pipe D4 is closed, and a mixture of 639 g (5 5 © m〇l) hexamethylenediamine and 64 g of water is supplied from the storage tank 1001 through the pipe m to a SUS with a stack of 5 L. Reaction Valley | § 1004. The liquid temperature in the reactor 1〇〇4 was adjusted to about 80 ° C. The pressure in the reactor 1004 was reduced to 30 kPa, and the water was removed from the condenser. The water was condensed in the condenser 1007. The pipe D6 is discharged. 3333 g (16.5 mol) of bis(3-hydrylbutyl) carbonate of Reference Example 1 is supplied from the storage tank 1002 to the reactor 1004 via the line D2 to set the liquid temperature in the reactor 1004. Adjusted to about 8 (rC. 6 4 g of sodium methoxide (manufactured by Wako Pure Chemical Industries, Ltd., 28% methanol solution) was supplied from the storage tank 1〇〇3 to the SUS reaction via the line D3. In 1004, the reaction was carried out. The solution after the reaction was analyzed by liquid chromatography, and N,N,-hexanediylcarbamic acid bis(3-fluorenylbutyl) was produced in a yield of 99.7%. The tube D4 was closed, and the reaction solution was supplied to an acidic ion exchange resin (Amberlyst-15 (spherical): manufactured by ROHM &amp; HAAS) containing moisture removal and insulated by an external sleeve. In the column 1〇〇5, sodium methoxide was neutralized. The solution was transferred to a storage tank 1006 via line D5. 〇 131506.doc -165- 200948759 • Step (1 5-2): Low boiling component removal The alcohol was distilled off using the apparatus shown in FIG. The middle section of the continuous multi-stage distillation column 302 filled with Dixon packing (6 ηηπιφ) having an inner diameter of 5 cm and a column length of 2111 was passed through the preheater 3〇1 from the line 31 at about 280 g/hr. The mixture is recovered as a continuous feed to the tank 6 in liquid form. The heat required for the steaming station is supplied by circulating the liquid in the lower portion of the column through the line 3 3 and the reboiler 304. The liquid temperature at the bottom of the continuous multi-stage distillation column 3〇2 was 160 ° C, and the pressure at the top of the column was about 70 kPa. The gas distilled from the top of the continuous multi-stage distillation column 〇 3 02 was condensed in the condenser 3 〇 3 via line 32, and continuously discharged from the line 34 to the sump 3 〇 5 at about 67 g/hr. From the bottom of the column, through line 33, it was continuously discharged to the storage tank 3〇6 at about 213 g/hr. The carbonate was distilled off using a device as shown in FIG. The middle section of the continuous multi-stage steaming tower 402 filled with Dixon packing (6 ππηφ) having an inner diameter of 5 cm and a tower length of 2 m was passed through the preheater 1 from the line 41 at about 213 g/hr. The mixture was recovered as a mixture of tanks 3〇6 in a continuous liquid feed. The heat required for steaming is supplied by circulating the liquid in the lower portion of the column through the line 43 and the reboiler 404. The liquid temperature at the bottom of the continuous multi-stage distillation column 4〇2 was 160 ° C. The top pressure was about 2.6 kPa. The gas distilled from the top of the continuous multi-stage distillation column 4〇2 was condensed in the condenser 403 via the line 42 and continuously discharged from the line 44 to the storage tank 405 at about 78 g/hr. From the bottom of the column, it is continuously discharged to the storage tank 406 at a flow rate of about 135 g/hr. The mixture discharged to the storage tank 406 was subjected to liquid chromatography analysis, and as a result, the mixture contained about 98.2% by weight of bismuth, hexanediyl bis-aminocarbamic acid bis(3-methylbutyl) vinegar. 131506.doc -166- 200948759 .Step (15-3): The thermal decomposition of N,N'-hexanediyl-bis-aminocarbamic acid bis(3-methylbutyl) ester is used to produce isocyanate. The device shown is reacted. The thin film distillation apparatus 5〇1 (manufactured by K〇bek〇eco-solutions Co., Ltd., Japan) having a heat transfer area of 0.1 m2 was heated to 27 (rc, and the internal pressure was about kPa). The step (15-2) was recovered. The mixture to tank 406 was heated to 16 Torr. (:, supplied to the upper portion of thin film evaporator 5〇1 via line 50 at about 280 g/hr. Again, feed from line 51 at about 25.2 g/hr. Dibutyltin laurate (manufactured by Wako Pure Chemical Industries, Ltd.). From the bottom of the thin film distillation apparatus 5, the liquid phase component is discharged from the line 53 and circulated to the thin film evaporation device 501 via the line 54. The gas phase component is discharged from the line 52. The continuous feeding is carried out to the middle section of the continuous multi-stage distillation column 502 filled with a Dixon packing (6 ηηπιφ) having an inner diameter of about 5 cm and a column length of 2 m. The gas phase component discharged from the thin helium distillation apparatus 501 via the line 52 is subjected to distillation separation of the gas phase component. The heat required for the distillation separation is performed by circulating the liquid in the lower portion of the column through the line 56 and the resolver 504. Supply. The liquid temperature of the test bottom of the continuous multi-stage steaming tower 5 () 2 is 15〇1, and the pressure at the top of the tower is about 5〇kpa. The gas from the tower top of the continuous multi-stage steaming tower 502 is continuously discharged from the pipeline 57 via the pipeline condensing condenser 5〇3. Since the continuous multi-stage steaming tower 5〇2 The liquid phase component is discharged from the line 59 at the position of the line 52. The middle section of the continuous multi-stage steaming 5G5 having an inner diameter of about 5 and a length of 2 m filled with a Dixon packing (6 ππηφ) is continuously advanced. The liquid phase component discharged from the pipeline π is subjected to steam separation of the gas phase component. The heat required for the steaming chamber separation is obtained by passing the liquid in the lower portion of the tower through the line 61 and the reboiler 131506.doc-167· The supply of the liquid at the bottom of the continuous multi-stage distillation column 505 is 15 〇 C 'the top force is about 1.5 kPa. The gas distilled from the top of the continuous multi-stage steaming tower 505 is passed through the line 60. It is condensed in the condenser 506 and continuously discharged to the storage tank 509 via the line 62. The discharge amount in the steady state is about g/hr. After 40 hours of operation, the liquid phase component is discharged from the line 64 at about g/hr to Sump 510. The liquid system discharged from line 62 contains about 99.8% by weight of a solution of diisohexyl hexamethylene diester relative to hexamethylenediamine. The yield was 97.2%. The continuous operation was carried out for 10 days, and no deposit was found on the wall surface of the thin film distillation apparatus 5〇1. [Example 16] • Step (16-1): N,N'-hexanediyl -Production of bis-amino bis(3-methylbutyl) phthalate The bis(3-mercaptobutyl) carbonate of Reference Example 1 was placed in a 1 L-shaped flask. The eggplant type flask is equipped with a three-way cock, a fractionation tower with a reflux condenser connected to a distillation column filled with a spiral packing No. 3 and a distillate receiver, and a thermometer to perform vacuum/nitrogen replacement in the system. The bis(3-mercaptobutyl)carbonate was purified by distillation. When a distillate of about 2/3 of the amount added was obtained, the flask was cooled to complete distillation purification. The distillate was subjected to 1H-NMR measurement, and as a result, the distillate contained about 99% by weight of bis(3-methylbutyl) carbonate. Further, the metal atoms contained in the distillate are below the minimum detection limit (0.001 ppm) in terms of iron, cobalt, nickel, zinc, tin, copper, and titanium. In addition to being supplied as a distillate for recovery, 3535 g 〇 75 m〇i) carbonic acid bis 131506.doc -168- 200948759 (3-methylbutyl) ester, 407 g (3,5 mol) hexamethylenediamine, 6.8 g The reaction was carried out in the same manner as in Example 1 except that the sodium methoxide (28% methanol solution) was reacted. The solution after the reaction was analyzed by liquid chromatography, and the yield was 94.0%. N,N'-hexanediyl-bis-amino decanoic acid bis(3-methylbutyl) is formed. The line 24 is opened, and the reaction liquid is supplied to the acid ion exchange which is adjusted to contain moisture. Resin (Amberlyst-15 (spheroidal): &amp; manufactured by HAAS) and neutralized with sodium methoxide by an external casing held in a column of 8 〇t. The solution was transported to the storage via line 25. 206. Τ θ • Step (16-2): distillation of the low boiling component to the middle of the continuous multi-stage distillation column 302, via the preheater 3〇1, from the pipeline

31 was continuously fed in liquid form at about 280 g/hr to a mixture of tanks 2〇6. The liquid phase component is continuously discharged from the bottom of the column to the storage tank 306 via line 33 at about 239 g/hr, to the middle of the continuous multi-stage distillation column 402, via the preheater 401, from the line 4 to about 239 g/ The same procedure as in the step (1-2) of Example 实施 was carried out except that the mixture was continuously recovered in a liquid form and returned to the mixture of the storage tank 3〇6. The gas distilled from the top of the continuous multi-stage distillation column 402 is condensed in the condenser 403 via the line 42, and is continuously discharged from the line 44 at / 157 g/hr to the storage tank at about 157 g/hr. 405. From the bottom of the column, via line 43, _ M is continuously discharged to the sump 406 at about 82 g/hr. The mixture discharged to the storage tank 406 was subjected to liquid chromatography analysis, and as a result, the mixture contained about 98.4% by weight of bis(3-methylbutyl) N, hexamethylenediamine. 131506.doc -169· 200948759 .Step (16-3): Preparation of isocyanate by thermal decomposition of N,N'-hexanediyl-bis-amino bis(3-decylbutyl) phthalate The device shown in Figure 5 reacts. A thin film distillation apparatus 501 (manufactured by K〇bele〇 eco-solutions, Japan) having a heat transfer area of 0.1 m2 was heated to 270 ° C to have an internal pressure of about 13 kPa. The mixture recovered in the step (16-2) to the storage tank 406 is heated to 2 ° C. 'Approximately 280 g/hr is supplied via line 5 to the upper portion of the thin film evaporator 5〇1' from the line 51 to 25.3 The same procedure as in the step (1-3) of Example 1 was carried out, except that dibutyltin dilaurate was fed in g/hr. The liquid was continuously discharged to the storage tank 509 via line 62 at about 131 g/hr. After 40 hours of operation, the liquid phase components were discharged from line 64 to storage tank 510 at about 77 g/hr. The liquid system discharged from line 62 contained a solution of about 99.8% by weight of hexamethylene diisocyanate. The yield relative to hexamethylenediamine was 91.7%. The continuous operation was carried out for 10 days. The deposit was not found on the wall surface of the thin film distillation apparatus 501. [Example 17] • Step (17-1): Ν, Ν·-hexanediyl-bis-amino bis(3-methylbutyl) phthalate was produced to the carbonic acid double (3- Ethyl acetonate iron (ruthenium) was added to methyl butyl) ester to prepare bis(3- mercaptobutyl) carbonate containing 11% of iron as a metal atom. In addition to supplying 3434 g (17.0 mol) of the bis(3-methylbutyl) carbonate, 395 g (3.5 mol) of hexamethylenediamine, and 6.6 g of sodium decoxide (28% methanol solution), the reaction was carried out. The same procedure is used in the procedure of Example 1 (〗 〖). 131506.doc -170- 200948759 The solution after the reaction was analyzed by liquid chromatography, and the result was N'N,N-hexanediyl-bis-aminocarbamic acid bis(3 methylbutyl) in a yield of 92.0%. ester. The line 24 was opened, and the reaction liquid was supplied to an acidic ion exchange resin (Amberlyst-1 5 (spherical): r〇hm &amp; HAAS), which was adjusted to remove moisture, and was insulated by an external casing to 8 In the column of 〇t 2〇5, 'sodium methoxide is neutralized. The solution is transported via line 25 to storage tank 206. Step (17-2): distillation of the low boiling component to the middle of continuous multistage distillation column 302, via preheater 301, from line 31 at about 280 g/ The hr is continuously fed to the mixture of the storage tank 2〇6 in a liquid form, and the liquid phase component is continuously discharged from the bottom of the column through the line 33 to the storage tank 306' at a flow rate of about 240 g/hr to the continuous multi-stage distillation column 4〇2. The middle stage is the same as the step (1_2) of the embodiment except that the mixture of the tank 306 is continuously fed from the line 41 at about 240 g/hr in a liquid state via the preheater 4〇1. method. The gas distilled from the top of the continuous multi-stage distillation column 402 was condensed in the condenser 403 via the line 42 and continuously discharged from the line 44 to the storage tank 405 at about 160 g/hr. From the bottom of the column, via line 43, it is continuously discharged to the storage tank 406 at about 80 g/hr.

G

G The liquid chromatography analysis of the mixture discharged to the storage tank 406 revealed that the mixture contained about 98.1% by weight. /〇 bis-yl-bis-amino bis(3-methylbutyl) decanoate. Step (17-3): Production of isocyanate by thermal decomposition of N,N'-hexanediyl-bis-aminocarbamic acid bis(3- mercaptobutyl) ester The reaction was carried out using a apparatus as shown in Fig. 5. 131506.doc • 171 - 200948759 A thin film distillation unit 5〇1 (manufactured by Kobdco ec〇-s〇iuti〇ns, Japan) with a heat transfer area of 0.1 m2 is heated to 27〇r, so that the internal pressure is about 13 kPP. The mixture recovered in the step (17-2) to the storage tank 4〇6 is heated to C, supplied via line 50 to the upper portion of the thin film evaporator 5〇1 at about 280 g/hr, and from the line 51 at about 25.2 g/ The same procedure as in the step (1-3) of Example 1 was carried out except that hr was fed to dibutyltin dilaurate. The liquid was continuously discharged to the sump 5〇9 via line 62' at about 127 g/hr. After 40 hours of operation, the liquid phase component was discharged from line 64 to the storage tank 510 at about 85 years old. The liquid system discharged from line 62 contains a solution of about 99% by weight of dihexamethylene diisocyanate. The yield relative to hexamethylenediamine was 87 5 〇/〇. The continuous operation was carried out for 10 days, and no deposit was accumulated on the wall surface of the thin film distillation apparatus 5〇1. [Example 18] 'Step (18-1): Ν, Ν·-hexanediyl bis-amino bismuth citrate bis(3-methylbutyl) ester was produced in addition to 2969 g (l4.7 mol) Refer to Example 1 for bis(3-methylbutyl carbonate), 488 g (4.2 mol) hexamethylenediamine, 8.1 g sodium decanoate (280/sterol solution), and carry out the reaction. The steps (丨_丨) are the same. The solution after the reaction was analyzed by liquid chromatography to give N,N'-hexanediyl-bis-aminocarbamic acid bis(3-methylbutyl) ester in a yield of 99.1%. The line 24' was opened to supply the reaction liquid to an acidic ion exchange resin (Amberlyst-15 (spherical): ROHM &amp; HAAS), which was adjusted to remove moisture, and was insulated by an external sleeve to 8 (rc). Pipe column 2〇5 131506.doc -172- 200948759 'Sodium neutralization of sodium decoxide. The solution is transported via line 25 to storage tank 206 〇•Step (18-2): Distillation of low boiling components continuously The middle stage of the distillation column 302 is continuously fed from the line 31 at a flow rate of about 300 g/hr to the mixture of the storage tanks 2 to 6 via the preheater 301, and the liquid phase component is passed through the line 33 from the bottom of the column. It is continuously discharged to the storage tank 306 at about 221 g/hr, to the middle of the continuous multi-stage distillation column 402, and is continuously fed into the storage tank from the line 41 at about 221 g/hr through the preheater 401 to the storage tank. The mixture was subjected to the same procedure as in the step (1) of Example 1. The gas distilled from the overhead of the continuous multi-stage distillation column 402 was condensed in the condenser 403 via the line 42, and the tube was condensed. The passage 44 is continuously discharged to the storage tank 405 at about 104 g/hr. The row is continuously discharged from the bottom of the tower via the line 43 at about 117 g/hr. To the storage tank 406. The mixture discharged to the storage tank 406 was subjected to liquid chromatography analysis, and as a result, the mixture contained about 98-7 wt% of 2 Ν, Ν,-hexanediyl-bis-amino decanoic acid bis(3-mercaptobutyl group). g. Step (18-2): The isocyanate is produced by thermal decomposition of N,N,-hexanediyl-bis-amino phthalic acid diphenyl ester using a device as shown in Fig. 11. The SUS reactor 1104 having the same shape as the SUS reactor 204 of Fig. 2 was heated to 270 ° C to have an internal pressure of about 13 kPa, and supplied to the reactor 1104 at 280 g / hr in the step (18-2). N,N,-hexanediyl-bis-aminocarbamic acid bis(3-mercaptobutyl) ester discharged to the storage tank 4〇6, and simultaneously from the storage tank 11〇2 via the line E2, at 25.3 g/hr Dibutyltin laurate is supplied to the reaction 131506.doc -173- 200948759 1104. The gas phase component is discharged from the line E4, and is filled with a Dixon filler (the inner diameter of the 6 illusion is about 5 cm, and the length of the tower is 2). The middle section of the continuous multi-stage distillation column U05 of m continuously feeds the gas phase component to carry out the distillation separation of the gas phase component. The heat required for the distillation separation is made by making the liquid in the lower part of the column The body is circulated through the line E6 and the reboiler 1108. The temperature of the liquid at the bottom of the continuous multi-stage distillation column 11〇5 is 150. (:, the top pressure is about 15 kPa, so that the continuous multi-stage distillation column U02 The overhead gas is condensed in the condenser 1107 via line E5 and continuously discharged from the line. The liquid phase component is discharged from the line E9' of the continuous multi-stage distillation column 〇 1105 below the line E4. The liquid phase component discharged from the pipe E9 is continuously fed to a middle portion of a continuous multi-stage distillation column 1106 filled with a Dixon packing (6 mm phantom inner diameter of about 5 cm and a column length of 2 m), and the liquid is discharged. Distillation separation of the phase components. The heat required for the distillation separation is supplied by circulating the liquid in the lower portion of the column via the line E and the reboiler. The liquid temperature at the bottom of the continuous multi-stage distillation column 1106 The pressure at the top of the column is about 1.5 kPa at 150 ° C. The gas distilled from the top of the continuous multi-stage distillation column u 〇 6 冷凝 is condensed in the condenser 1110 via line E10, via line E12, to about 88 The g/hr was continuously discharged to the storage tank. The liquid system recovered from the storage tank 11 contained a solution of about 99.8% by weight of diisocyanatohexane diacetate, and the yield relative to hexamethylenediamine was 64.4%. In the case of continuous operation in hours, it was found that deposits were accumulated on the wall surface of the reactor 1104. [Example 19] Cleaning of the reactor The membrane distillation apparatus 7〇1 in which the deposits were found in Example 4 was subjected to a cleaning operation. The thin film distillation device 701 is heated to 18 〇〇c to make the film vaporize 131506.doc -1 74- 200948759 The inside of the device 701 is an atmospheric pressure nitrogen atmosphere. The gas is supplied from the line 7 to about η. The heart is supplied to the benzene, discharged from the line 83, and the liquid phase component is recovered to the storage tank 711 via the line 89. As a result, no deposit was found inside the film evaporation device. [Example 20] to [Example 27] The operation of Example 4 was continuously carried out, and various cleaning solvents were used every 3 days, in the same manner as in Example 19. The cleaning operation was carried out, and the results are shown in Table 1. [Comparative Example 1] Step (A 1) . The production of N,N-hexanediyl-bis-aminocarbamic acid bis(3-methylbutyl) ester was as shown in the figure. The apparatus shown in Figure 9 is reacted. In the state in which the lines C4 and C6 are closed, 2909 g (14.4 mol) of the reference example of bis(3-fluorenylbutyl) is fed from the storage tank 9〇1 via the piping. The ester was supplied to a reaction vessel 9〇4 made up of a baffle with an internal volume of 5 L, and 349 g (13.0 mol) of hexamethylenediamine was supplied from the storage tank 902 to the reaction vessel 904 via a line C2. The temperature of the liquid in the reactor 9〇4 is adjusted to be about ribs, and 8.7 g of sodium decoxide (28% methanol solution) is supplied from the storage tank 903 via the line C3. The reaction was carried out in the reactor 904 made of SUS. The solution after the reaction was analyzed by liquid chromatography, and N,N'-hexanediyl-bis-aminocarboxylic acid bis (3) was produced in a yield of 99.0%. -methyl butyl acrylate. The reaction liquid was supplied to the line C4 ', and the acidic ion exchange resin (Amberlyst-15 (spherical): R〇hm &amp; HAAS), which was adjusted to remove moisture, was supplied. Use an external casing to keep 8 保温. (In the column 9〇5, sodium methoxide is neutralized. The solution is transported via line C5 to the storage tank 131506.doc -175- 200948759 906 °. Step (A-2): Distillation of low boiling components The alcohol was distilled off using a device as shown in Fig. 3. The middle portion of a continuous multi-stage distillation column 312 filled with a Dixon packing (6 ιηιηφ) having an inner diameter of 5 cm and a column length of 2 m was passed through The preheater 3〇1 is continuously fed from the line 31 at a rate of about 280 g/hr to the mixture of the storage tanks 2〇6. The heat required for the reaction and distillation is obtained by passing the liquid in the lower part of the tower through the pipeline. 33 and the reboiler 304 are circulated and supplied. The liquid of the bottom of the continuous multi-stage distillation column 3〇2 is at a temperature of l60 ° C, and the pressure at the top of the column is about 70 kPa. The tower of the continuous multi-stage steaming tower 302 The top gas is condensed in condenser 303 via line 32 and continuously discharged from line 34 to storage tank 305 at about 44 g/hr. From the bottom of the column via line 33, it is continuously discharged to storage tank 3 at about 236 g/hr. 〇6. Distillation of carbonate was carried out using a device as shown in Fig. 4. The inner diameter of 5 cm and the length of the tower were 2 m filled with Dixon packing (6 mm). The middle section of the multi-stage distillation column 402 is recovered from the line 41 ^ at about 23 6 g / hr in a continuous liquid feed to the mixture of the storage tank 306 via the preheater 4 。 1. The heat required for the reaction and steaming The liquid is supplied by circulating the liquid in the lower portion of the column through the line 43 and the reboiler 404. The liquid temperature at the bottom of the column of the continuous multi-stage distillation column 4〇2 is 160 ° C, and the pressure at the top of the column is about 2.6 kPa. The gas prepared from the top of the continuous multistage 4 Pavilion tower 402 is condensed in the condenser 403 via line 42 and continuously discharged from the line 44 to the storage tank 4〇5 at about 146 g/hr. 43' was continuously discharged to the storage tank 4〇6 at about 90 g/hr. The mixture discharged to the storage tank 406 was subjected to liquid chromatography analysis, and as a result, the mixture contained about 97.6% by weight of N,N,-hexanediyl-double -Amino phthalic acid bis 131506.doc • 176- 200948759 (3-methylbutyl) vinegar. Step (A-3): using N,N'-hexanediyl-bis-aminocarboxylic acid bis (3- Thermal decomposition of mercaptobutyl ester to produce isocyanate is carried out using a device as shown in Figure 5. Closed line 54 'film vaporizing device 501 with a heat transfer area of 〇.1 m2 , manufactured by Kobelco eco-solutions) heated to 27 〇. 〇, the internal pressure is about 13 kPa. The mixture recovered in step (A_2) to storage tank 4〇6 is heated to 160 乞, via line 50, to about 28 〇g/hr was supplied to the upper portion of the thin film evaporator 5〇1. Further, dibutyltin dilaurate (manufactured by Wako Pure Chemical Industries, Ltd.) was fed from the line 51 at about 25.1 g/hr. From the bottom of the thin distillation apparatus 501, the liquid phase component is discharged from the line 53 and recovered to the storage tank 510 via the pipe 54. The gas phase components are discharged from line 52. The middle portion of the continuous multi-stage distillation column 502 filled with a Dixon packing (6 ηιηιφ) having an inner diameter of about 5 cm and a column length of 2 m is continuously fed into the gas phase discharged from the thin film distillation apparatus 501 via the line 52. The component is subjected to distillation φ separation of the gas phase component. The heat required for the distillation separation is supplied by circulating the liquid in the lower portion of the column through the line 56 and the reboiler 504. The liquid temperature at the bottom of the continuous multi-stage distillation column 5〇2 was 150. (: 'The top pressure is about 5 kPa. The gas distilled from the top of the continuous multi-stage distillation column 502 is condensed in the condenser 5〇3 via the line 55, and continuously discharged from the line 57. Since continuous The liquid phase component is discharged from the line 59 of the stage distillation column 5〇2 below the line 52. The inner diameter is about 5 cm and the length of the tower is 2 m, which is filled with the Dixon packing (6 ππηφ). The middle stage of the distillation column 505 continuously feeds the liquid phase component discharged from the line 59 to carry out the distillation separation of the liquid phase component. The 131506.doc • 177· 200948759 required for the distillation separation is performed by making the liquid in the lower part of the column It is supplied through the circulation of the line 61 and the reboiler 5〇7. The liquid temperature at the bottom of the continuous multi-stage distillation column 505 is 15 ° C, and the pressure at the top of the column is about 5 5 kPa. The gas distilled from the top of the column 5 is condensed in the condenser 506 via the line 60, and continuously discharged to the storage tank 509 via the line 62. • Step (A-4): repeated use of the urethane for manufacture As shown in Figure 9, the device 'repeated the production of amino phthalate. Close the line C4 and discharge about 220 g to the storage tank 51. The mixture was supplied to the reaction vessel 904 via a pipe, and 2,909 g (14.4 mol) of bis(3-methylbutyl)carbonate was supplied from the storage tank 901 via a line ci to a SUS with a baffle having an internal volume of 5 L. In the reaction vessel 904, 349 g (3.0 mol) of hexamethylenediamine was supplied from the storage tank 9〇2 to the reactor 9〇4 via a line. The temperature of the liquid in the reactor 904 was adjusted to about 8 Torr. 〇, 8.7 g of sodium decoxide (28% methanol solution) was supplied from the storage tank 9〇3 to the sus reactor 9〇4 via a line to carry out a reaction. The solution after the reaction was subjected to liquid chromatography. Analysis, the hydrazine yielded N,N,-hexanediyl-bis-aminocarbamic acid bis(3-methylbutyl) ester in a yield of 92% by weight relative to the supplied hexamethylene diamine. The reaction solution was supplied to an acid ion exchange resin (Amberiy St_i5 (spherical): manufactured by ROHM &amp; HAAS) containing moisture removal, and was insulated by an external sleeve to 8 〇&lt;t. In the middle, the sodium zymide is neutralized. The solution is transported to the storage tank 906 via line C5. Step (A-5): distillation of the low boiling component The apparatus shown in Fig. 3 is used to carry out the alcohol hall. 131506.doc -178· 200948759 Continuous multi-stage distillation tower with a diameter of 5 cm and a length of 2 m filled with Dixon packing (6 ηιπιφ) The middle section of 302, through the preheater 301, is continuously fed from the line 31 at a rate of about 280 g/hr to the mixture of the storage tank 206. The heat required for the distillation is performed by passing the liquid in the lower portion of the column through the line 33. And the Buddha apparatus 304 is cycled and supplied. The liquid temperature at the bottom of the tower of the continuous multi-stage steaming tower 302 is 160 ° C. The top pressure is about 70 kPa. The gas distilled from the top of the continuous multi-stage distillation column 3〇2 was condensed in the condenser 303 via the line 32, and continuously discharged from the line 34 to the storage tank 305 at about 39 g/hr. From the bottom of the column, it was continuously discharged to the storage tank 3〇6 via the line 33' at about 241 g/hr. The carbonate was distilled off using a device as shown in FIG. The middle section of the continuous multi-stage distillation column 402 filled with Dixon packing (6 ηηηιφ) having an inner diameter of 5 cm and a column length of 2 m was passed through the preheater 40 1, from the line 41 at about 241 g/hr. 'The mixture recovered to the storage tank 306 by continuous feed in liquid form. The heat required for the steaming is supplied by circulating the liquid in the lower portion of the column through the line 43 and the reboiler 404. The liquid temperature at the bottom of the continuous multi-stage distillation column 4〇2 was 160 ° C, and the pressure at the top of the column was about 2.6 kPa. The gas distilled from the top of the continuous multi-stage distillation column 402 was condensed in the condenser 403 via the line 42, and continuously discharged from the line 44 to the storage tank 4〇5 at about 144 g/hr. From the bottom of the column, it is continuously discharged to the storage tank 4〇6 via the line 43 at about 97 g/hr. The mixture discharged to the storage tank 406 was subjected to liquid chromatography analysis, and as a result, the mixture of 5 liters contained about 94.3 wt% of N,N'-hexanediyl-bis-amino bismuth citrate bis(3-methylbutyl) vinegar. . • Step (A-6): Preparation of isocyanate using thermal decomposition of N,N'-hexanediyl-bis-carbamic acid bis(3-mercaptobutyl) vinegar 131506.doc -179· 200948759 Use Figure 5 The device shown is reacted. The closing line 54' was heated to 270 ° C by a film evaporation apparatus 5 having a heat transfer area of 〇·ΐ m2 so that the internal pressure was about 13 kPa. The mixture recovered in the step (A_5) to the storage tank 406 is heated to 16 (TC, supplied via line 5〇 to the upper portion of the thin film evaporator 501 at about 28 〇g/hr. Again, from the line 51 at about 24 2 g/hr feed dibutyltin dilaurate. From the bottom of the thin film distillation apparatus 5〇1, the liquid phase component is discharged from the line 53 and recovered from the storage tank 51 via the line 64. The gas phase component is supplied from the line 5 2 discharge.

The middle section of a continuous multi-stage steaming tower 5 〇2 filled with a Dixon packing (6 ηιιηφ) having an inner diameter of about 5 cm and a tower length of 2 m is continuously fed from the thin film steaming device 5 (H via a tube) The vapor phase component discharged from the channel 52 performs the vapor phase separation of the gas phase component. The heat required for the distillation separation is supplied by circulating the liquid in the lower portion of the column via the line 56 and the m5G4. The continuous multi-stage steaming tower is as The liquid temperature at the bottom of the column is 15 (TC, the pressure at the top of the column is about 5 〇 kpa. The gas taken from the top of the continuous multi-stage steaming tower 502 is condensed in the condenser, for example, via line 55, from line 57. Continuously discharged. The liquid phase component is discharged from the line 59 of the continuous multi-stage steaming material 502 which is lower than the line 52. (4) The inner diameter of the Di Di Song bulking material (6 _φ) is about 5 (10), and the length of the tower is 2 m. The middle part of the continuous multi-stage steaming tower 5Q5 continuously feeds the liquid phase component discharged from the pipeline π to carry out the steaming separation of the gas phase component. The heat required for the steaming chamber separation is made by passing the liquid in the lower part of the tower through the tube. (4) and (4) (4) 7 cycles of two pressures = the temperature of the liquid at the bottom of the tower of the steam tower 505 is (10) the gas taken from the top / U 1 makes it self-connected At the top of the multi-stage steaming tower 505, the milk is condensed via a line 6 in a condenser write, and continuously discharged to a storage tank 509 via a line 131506.doc 200948759 62. It is recovered from the line 62 at about 38.7 g/hr. The liquid 'The liquid contains about 99.8% by weight of hexamethylene diisocyanate. The above steps (A-4) to (A-6) are repeated for 1 day continuous operation, and the results are found in the reactor 904 and the column. 905, the storage tank 906, the thin steaming chamber 501, the storage tank 510, and the deposits on the wall surface of the connected pipes. [Comparative Example 2] • Step (Bl): 3-((3-A) Preparation of (butoxy)carbonylamino-methyl-3,5,5-trimethyl®cyclohexylaminocarbamic acid (3-mercaptobutyl) ester except for the supply of 3394 g (1 6.8 mol) of Reference Example 1 Bis(3-methylbutyl) carbonate, 596 g (3,5 mol) in place of hexamethylenediamine 3-aminomethyl-3,5,5-trimethylcyclohexylamine, 6.8 g sodium methoxide ( The reaction was carried out in the same manner as in the step (1 -1) of Example 1 except that the reaction was carried out in a 28% methanol solution. The solution after the reaction was analyzed by liquid chromatography, and the result was a yield of 99.5%. ((3-methylbutoxy) Amino group - cyclohexyl-3,5,5-trimethyl-ylcarbamic acid (3_-methylbutyl) ester The reaction solution is supplied to the moisture removal is accommodated Adjusted

An acidic ion exchange resin (Amberlyst-15 (spherical): manufactured by ROHM &amp; HAAS) was neutralized by sodium methoxide in a column 205 which was kept at 80 °C by an external sleeve. This solution is transported via line 25 to storage tank 2〇6. • Step (B-2): Low-boiling ingredients are used to distill off the alcohol using the apparatus shown in Figure 3. The middle section of the continuous multi-stage distillation column 302 filled with Dixon packing (6 πιπιφ) having an inner diameter of 5 cm and a column length of 2 m was passed through the preheater 301 from the line 31 at about 280 g/hr. The liquid continuous feed is recovered to a mixture of tanks 2〇6. Steam 131506.doc -181 - 200948759 The heat required for the distillation is supplied by circulating the liquid in the lower portion of the column through the line 33 and the reboiler 304. The liquid temperature at the bottom of the column of the continuous multi-stage distillation column 302 is 160 ° C, and the pressure at the top of the column is about 7 〇 kpa. The gas distilled from the top of the continuous multi-stage distillation column 3〇2 was condensed in the condenser 3〇3 via line 32, and continuously discharged from the line 34 to the storage tank 3〇5 at about 43 g/hr. From the bottom of the column, it was continuously discharged to the storage tank 3〇6 via the line 33' at about 23 7 g/hr. The carbonate was distilled off using a device as shown in FIG. The middle section of the continuous multi-stage distillation column 402 having an inner diameter of 5 cm and a column length of 2〇1 © filled with a Dixon packing (6 rnmcj), via the preheater 4〇1, from the line 41 237 g/hr was continuously fed in liquid form to a mixture of tanks 3〇6. The heat required for the distillation is supplied by circulating the liquid in the lower portion of the column through the line 43 and the reboiler 404. The liquid temperature at the bottom of the continuous multi-stage distillation column 4〇2 was 160 C, and the pressure at the top of the column was about 2.0 kPa. The gas distilled from the top of the continuous multi-stage distillation column 4〇2 was condensed in the condenser 403 via the line 42, and discharged from the line 44 to the storage tank 405 at a rate of about 138 g/hr. From the bottom of the column, it is continuously discharged to the storage tank 406 via a line 43 at about 98 g/hr.液相 The mixture discharged to the storage tank 406 was subjected to liquid chromatography analysis, and as a result, the mixture contained about 99.0% by weight of 3-((3.methylbutoxy)carbonylamino group_methyl-3,5,5- Trimethylcyclohexylaminocarbamic acid (3-decylbutyl) ester. Step (B-3): using 3-((3-methylbutoxy)carbonylamino-methyl-3,5, 5. Thermal decomposition of dimercaptocyclohexylamino decanoic acid (3-ylidene butyl) vinegar to produce isogastric acid vinegar The reaction was carried out using the apparatus shown in Fig. 5. The film having a heat transfer area of 0.1 m2 was steamed. The apparatus 501 is heated to 27 CTC, 131506.doc • 182. 200948759 to have an internal pressure of about 0.13 kPa. The mixture recovered in the step (B-2) to the storage tank 4〇6 is heated to 170 ° C, via line 50, About 200 g/hr is supplied to the upper portion of the thin film evaporation apparatus 501. Further, the gas phase component is discharged from the line 52 from the line 51 at a rate of about 25 2 ^ 匕 of monobutyltin laurate. From the thin film distillation apparatus 501 The liquid phase component was hardly recovered at the bottom. The middle section of the continuous multi-stage distillation column 502 filled with a Dixon packing (6 ηιηιφ) having an inner diameter of about 5 cm and a column length of 2 m was continuously fed from a thin portion. The vapor phase component discharged from the steaming device 501 via the line 52 performs distillation/separation of the gas phase component. The heat required for the distillation separation is supplied by circulating the liquid in the lower portion of the column through the line 56 and the reboiler 504. The liquid temperature at the bottom of the continuous multi-stage distillation column 5〇2 is 15 (TC, the top pressure is about 5 〇kpa. The gas distilled from the top of the continuous multi-stage distillation column 502 is condensed via the line) Condensed in the vessel 5〇3, continuously discharged from the line 57. The gas phase component is discharged from the line 59 of the continuous multi-stage distillation column 5〇2 below the line 52. The filling is filled with a Dixon packing (6 The middle section of a continuous multi-stage steaming tower 505 with an inner diameter of about 5 and a tower length of 2 ❹ m, continuous feeding from the pipeline bay

The gas phase component is subjected to distillation separation of the gas phase component. The heat required for the distillation separation is supplied by circulating the liquid in the lower portion of the column through the line 61 and the reboiler 5?7. The liquid temperature at the bottom of the tower of the continuous multi-stage steaming tower 505 is 15 〇 ° C. The top magic is about Μ kPa. The gas from the tower of the continuous multi-stage steaming tower 5〇5 is condensed in the condenser 5〇6 via the line 6 and continuously discharged to the storage tank 5G9 via the line 62. The discharge amount in the steady state is about 1 (1 g/hP). The liquid system discharged from the line 62 contains a solution of about 99.8% by weight of isophorone diisocyanate. The yield based on hexamethylenediamine was 91.5%. \3\506Aoc -183 200948759 The continuous operation was carried out for 24 hours, and it was found that deposits were accumulated on the wall surface of the thin film distillation apparatus 501. [Comparative Example 3] - [Comparative Example 5] The operation of Example 4 was continued, and various washing solvents were used every 30 days, and the washing operation was carried out in the same manner as in Example 15. 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. . 2,6-Dimethylphenol 1000 g/Hr 2 hours 〇 Example 21 210 ° C 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 〇C 2,4-(cr,a-dimethylbenzyl)phenol 1200 g/Hr 1 hour 〇 Example 24 200 ° C 4-ethoxyphenol 1100 g / Hr 2 hours 〇 Example 25 270〇C 4-dodecylphenol 1300 g/Hr 1 hour 〇 Example 26 200 °C Salicylic acid 800 g/Hr 2 hours 〇 Example 27 220 〇C benzoic acid 800 g/Hr 4 hours 〇 Comparative Example 3 200 ° C n-dodecane 1000 g/Hr 4 hours X Comparative Example 4 200. . Naphthalene 1000 g/Hr 4 hours X Comparative Example 5 180 ° C 1-Phenylphenol 1000 g/Hr 4 hours X 〇: No attachment X was found after the cleaning operation: Attachment G was found after the cleaning operation [Industrial UTILITY] The method for producing an isocyanate of the present invention can efficiently produce isocyanate without using highly toxic phosgene. Therefore, the production method of the present invention is industrially useful and has 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 view showing the apparatus for producing a urethane of the embodiment of the present invention - 184 - I31506.doc 200948759. Fig. 3 is a conceptual view showing a low boiling component distillation apparatus according to an embodiment of the present invention. Fig. 4 is a conceptual view showing a low boiling component distillation apparatus according to an embodiment of the present invention. Fig. 5 is a conceptual view showing an apparatus for producing an isocyanate according to an embodiment of the present invention. Fig. 6 is a conceptual view showing an apparatus for producing an isocyanate according to an embodiment of the present invention. Fig. 7 is a conceptual view showing an apparatus for producing an amino phthalate ester of 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 schematic view showing a urethane producing apparatus according to an embodiment of the present invention. Fig. 10 is a conceptual view showing a urethane producing apparatus of an embodiment of the present invention. Fig. 11 is a conceptual view showing an apparatus for producing an isocyanate according to an embodiment of the present invention. [Explanation of main component symbols] (Fig. 1) Distillation column type reactor thin film distillation apparatus 101, 107 102 103 &gt; 106 13l506.doc • 185 200948759 104 105 111 , 112 , 117 121 , 123 , 126 , 127 1 , 2 , 3, 4, 5, 6, 7, high pressure dad removal carbon tank reboiler condenser lines 8, 9, 10, 11, 12, 13, 14, 15, 16, 17 (Figure 2) 〇201, 202 , 203 ' 206 204 205 21 , 22 , 23 , 24 , 25 ( Fig. 3 ) 302 305 ' 306 301 303 304 31 , 32 , 33 , 34 , 35 ( Fig. 4 ) 402 405 ' 406 401 403 sump stirrer column Pipeline continuous multi-stage distillation tower storage tank preheater condenser reboiler line continuous multi-stage distillation tower storage tank preheater condenser 131506.doc -186 200948759 404 41 , 42 , 43 , 44 , 45 ( Figure 5 ) 501 502 '505 508 , 509 , 510 503 , 506 504 ' 507

50, 51, 52, 53 , 54 , 55 , reboiler line thin film distillation unit continuous multi-stage distillation tower storage tank condenser reboiler line 56, 57, 58, 59, 60, 61,

70, 71, 72, 73, 74, 75, 62, 63, 64 (Fig. 6) 701 702 '705 '708 703, 706, 709 704, 707, 710 711 thin film evaporation unit continuous multi-stage distillation tower condenser Boiling tank line 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88 '89 (Fig. 7) 721, 722, 723 ' 725 724 tank agitation tank 131506.doc -187- 200948759 A1, A2, A3, A4 (Fig. 8) Pipeline 801, 804, 807 Continuous multi-stage distillation column 802, 805, 808 Condenser 803 ' 806 &gt; 809 Reboiler B1, B2, B3, B4 , B5, B6, B7, B8, B9, BIO, B11, B12, B13, B14, B15 © (Fig. 9) Pipes 901, 902 '903, 906 Storage tank 904 Stirring tank 905 Columns Cl, C2, C3, C4 , C5, C6 (Fig. 10) Pipeline 1001, 1002 '1003, 1006 Storage tank 1004 Stirring tank Q 1005 Column 1007 Condenser D1, D2, D3, D4, D5, D6 (Fig.) Pipes 1102, 1409, 1411 Storage tank 1104 Stirring tank 1105, 1106 Continuous multi-stage distillation column 1107, 1110 Condenser 131506.doc -188- 200948759 Reboiler piping 1108, 1112

El, E2, E3, E4, E5, E6, E7, E8, E9, E10,

El 1, E12, E13 〇

131506.doc -189·

Claims (1)

200948759 X. Patent application scope: 1 - A method for producing isocyanate, which is a method for producing isocyanate by thermal decomposition reaction of amino carboxylic acid vinegar, the method comprising the following steps: a thermal decomposition reactor from which the thermal decomposition reaction is carried out The low boiling component is recovered as a gas phase component; the liquid phase component containing the amino carboxylic acid vinegar is recovered from the bottom of the thermal decomposition reactor; and a part or all of the liquid phase component is supplied to the thermal decomposition reactor. Upper part. 2'. The production method of claim 1 wherein the urethane is supplied to the thermal decomposition reactor at a temperature ranging from 50 ° C to 180 ° C. 3. The production method according to claim 1, wherein the amino phthalate is supplied as a liquid to the thermal decomposition reactor. 4. The production method according to claim 1, wherein the amino phthalate is produced by reacting a carbonate with an amine compound. 5' The production method of claim 4, wherein the reaction reactor for producing the amino phthalate ester is the same as or different from the thermal decomposition reactor, and the reactor for the preparation of the amino decanoic acid and the thermal decomposition reaction The apparatus is selected from at least one selected from the group consisting of a column reactor and a tank reactor. 6. The production method of claim 1, 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. . 7. The production method according to claim 1, wherein the thermal decomposition reaction is carried out in a liquid phase. The method for producing a product is the same as the method for producing a carbonic acid ester and an amine compound. In the mixture containing the urethane, one or all of the hydroxy compounds and/or part or all of the carbonate are separated, and the resulting mixture is supplied to the thermal decomposition reaction apparatus. The manufacturing method of the monthly item 8 wherein the separation is carried out by steaming, and the distillation separation is carried out at 180 ° C or lower. The manufacturing method of claim 1, wherein a part or all of the liquid phase component recovered from the bottom of the thermal decomposition reactor is supplied to the thermal decomposition reactor in a temperature range of 5 (rc to 18 〇〇c) 11. The manufacturing method according to claim 4, wherein the amount of the carbonic acid is used in a stoichiometric ratio with respect to the amine group constituting the amine compound. 12. The manufacturing method of claim 1, wherein further And a method of producing the high-boiling by-products of the thermal decomposition reactor, wherein the acid-based aromatic hydroxy compound is produced by the method of claim 12, wherein the acid-based aromatic hydroxy compound is produced according to claim 12, wherein the method of claim 4, wherein The carbonate is a compound represented by the following formula: [Chemical Formula 1] The anthracene (1) (wherein the aromatic R1 of the formula 12 represents an aliphatic group having a carbon number of 1 to 12 or a carbon number of 6 15. The method of claim 14, wherein the carbonated vinegar contains 131506.doc 200948759 ppm~10% of a metal atom. 16. 17. 18. 〇©19, 20. 21. In the manufacturing method of claim 15, Gan | ^ ^ where 'the metal atom is selected from the group consisting of iron, recorded, tin, steel, and samarium One or more of them. For example, the π $ Item 14 &amp;method&apos; wherein the carbonic acid has a number of 5 to 7 aliphatic groups or a carbon number of 6 to 7 aromatic groups. The method of claim 4, wherein the amine compound is a compound represented by the following formula (7): [Chemical Formula 2] r24nh2) &quot; (2) (wherein R represents an atom selected from the group consisting of carbon and oxygen; The carbon number is a group of aliphatic groups and an aromatic group having a carbon number of 6 to 20, which has a valence equal to η; η is an integer of 2 to 1 )). The process according to claim 18, wherein the amine compound is a diamine compound wherein η is 2 in the compound represented by the formula (2). The method of claim 1, wherein the low-boiling component which is produced by the thermal decomposition reaction and recovered as a gas phase component is supplied as a gas component to the distillation column, and in the distillation column, from the low-boiling component The hydroxy compound from the carbamate is separated from the isophthalate from the amino phthalate. The method of manufacturing claim 1 wherein the low-boiling component formed by the thermal decomposition reaction of 131506.doc 200948759 and recovered as a gas component is recovered from the base compound of the amino carboxylic acid vinegar, respectively. And isocyanate from an amino phthalate. 22. The method of manufacture of claim 1, wherein the isocyanate is recovered by distillation from the liquid phase component. 23. The method of claim 14, wherein the carbonate is in the formula (1)*R is an aliphatic group having a carbon number of from 1 to 12, which comprises the following steps (1) and (2); The method comprises the steps of: (1): reacting an organotin compound having a tin-oxygen-carbon bond with carbon dioxide to obtain a reaction mixture containing a dialkyl carbonate; and (2): separating the reaction mixture to obtain a carbonic acid Dialkyl esters and residual liquids. 24. The method of claim 14, wherein the carbonate is in the formula (1) wherein R1 is an aromatic group having 6 to 12 carbon atoms, which is used in addition to the above steps (1) and (2), The method comprises the following step (3): Step (3): reacting the dialkyl carbonate separated in the step (2) with the aromatic hydroxy compound A to obtain a diaryl carbonate, which is a by-product The alcohol is recovered. 25. The method of claim 23 or 24, wherein the carbonate system comprises the following steps (4) and steps in addition to the step (1) and the step (2), or the steps (1) to (3). Step (4): Step (4): reacting the residual liquid obtained in the step (2) with an alcohol to form an organotin compound having a tin-oxygen-carbon bond and water, and removing the water from the reaction system; 131506.doc 200948759 Step (5): The tin-tin compound obtained in the step (4) is used as the tin-oxygen-carbon bond of the step (1):::, and reused. The composition of claim 25, wherein the alcohol of the step (4) in the step (3) is reused. The alcohol is 2': the production method of claim 25, wherein when the radical compound is an alcohol, it is used as the alcohol of the step (4), and when the radical compound is an aromatic fluorene compound, as the step (3) Aromatic transalkylation. The carbonate which is separated is used as a carbon. The thermal decomposition reaction of the urethane therein. The production method of the claim 8 is an acid ester reuse. 29. The production method according to claim 1 is carried out in the absence of a solvent. The manufacturing method according to claim 4, wherein the amine compound is supplied to the reactor for reacting the carbonate with the amine compound, is in a liquid state Go on. 3. The production method according to claim 4, wherein the amine compound is supplied to a reactor for reacting the carbonate with the amine compound, and is carried out as a mixture with an alcohol, water or carbonate. 131506.doc